109

5.1
Introduction
The innovative engineering development of optoelectronics has contributed to the
expansion of information technology over the past 25 years. This development has
been essential for modern information technologies through high-speed communi-
cation and information processing.
For example, there are lens technologies for optical fibers and discs; laser technol-
ogies for printers and copiers; light sensor technologies including digital processing
for charge coupled devices (CCDs) and complementary metal oxide semiconductors
(CMOSs); and flat panel display technologies for liquid crystal displays. These tech-
nologies are increasingly seen in digital cameras, cellular phones with cameras,
DVD recorders, and various sensor cameras for automotive applications.
Optical devices are extremely important, since they play a central role in optical
transmission, recording, replay, and display. For these optical parts, transparent
materials with optical properties have been used. Glass materials have been conven-
tionally used and are the most reliable, and are thus used in important parts for
which high stability is required. However, they are not suitable for mass production.
Plastic materials are suitable for mass production and, therefore, widely used for
many optical devices. In addition to the mass-productivity, low weight is another
attractive feature. As for transparent plastic materials, poly(methyl methacrylate)
(PMMA) and polycarbonate (PC) have excellent transparency and are used exten-
sively. In addition, alicyclic acrylates and cycloolefin polymers (COPs) with various
optical properties have been developed. Furthermore, optical polyester (O-PET) and
a certain series of polysulfones have recently been developed and used.
A notable example can be seen in the compact disc market where transparent
plastic materials were accepted to the market in large quantities. The use of plastic
pick-up lens for optical discs significantly lowered the total cost and thus greatly
expanded the compact disc market. As information technology advances, sophistica-
tion in the use of transparent plastic materials for optical devices becomes more
important. Therefore the development of the technology of these materials is essen-
tial.
5
Optical Plastics
Koji Minami (Zeon Corporation, Kawasaki, Japan)
5 Optical Plastics
This chapter compares the physical properties of some of the transparent plastic
materials currently in use.
5.2
Quality Requirements for Optical Plastics
5.2.1
Transparency
The most required property of optical plastics is high transparency at specific wave-
lengths. The transparency of a plastic is determined by (1) molecular structure, (2)
molecular conformation formed by molding or other causes, and (3) impurities.
5.2.1.1 Molecular Structure
The transparency of a polymer is intimately related to its molecular structure. Var-
ious interatomic/intermolecular interactions in a polymer being exposed to light
cause optical absorption in the ultraviolet to visible region due to electron transitions
or optical absorption in the infrared region due to vibrational transitions. The
absorption in the infrared region does not affect absorption in the visible region. For
absorption due to electron transitions a
e
mostly in the ultraviolet region, Urbach’s
rule is known [1, 2]:
a
e
¼ Aexp
B
k
(5.1)
where A and B are inherent to each molecule and k is the optical wavelength. At
500 nm, a
e
of PMMA is reported as <1 dB/km whereas that of polystyrene is
98 dB/km from this formula [3]. The value of a
e
is high when a polymer has a ben-
zene ring structure, as in the phenyl groups that are found in most polycarbonates
and polystyrenes. On the other hand, PMMA is a typical transparent material with
excellent transparency because its molecular structure has no group that absorbs
within the visible region. Thus, materials that are barely affected by electron transi-
tions are desirable in order to obtain high transparency. Light absorptions occur, for
instance, in pfip* transitions in double bonds as typified by azo or phenyl groups,
or nfip* transitions in C=O bonds.
The reflectance (R) depends on refractive index (n) as follows:
R ¼
ðnÀ1Þ
2
ðnþ1Þ
2
. (5.2)
This formula indicates that materials with low refractive index show low reflec-
tance and accordingly high light transmittance. Commonly, plastic lenses are coated
with inorganic materials for which the refractive indices are lower than those of
plastics. Figure 5.1 shows a comparison of light transmittance data for PMMA, PC,
and COP.
110
5.2 Quality Requirements for Optical Plastics
5.2.1.2 Molecular Conformation
Randomness of molecular chains is essential for polymer transparency. Crystal and
non-crystal regions of a crystalline polymer generally have different refractive
indices. This causes scattering of light at the boundary between two such regions. A
multicomponent polymer such as polymer alloy behaves similarly. There is also
light scattering loss caused by isotropic and anisotropic density fluctuations called
Rayleigh scattering [2, 4].
5.2.1.3 Impurities
Polymers may be colored due to various additives such as antioxidants, plasticizers,
ultraviolet absorbers (UVAs), coloring agents (pigments and dyes), or oxidized resin
damaged in thermoprocessing. Small amounts of residues such as catalysts that are
added at the time of polymer synthesis may unintentionally cause coloring of the
polymer.
5.2.2
Refractive Index
The refractive index varies depending on molecular polarizability and weight per
unit volume (density) as in the Lorentz–Lorenz equation [5]:
111
0
10
20
30
40
50
60
70
80
90
100
250 350 450 550 650 750
Wavelength / nm
T
r
a
n
s
m
i
t
t
a
n
c
e

/

%
PMMA
PC
COP
Figure 5.1 Comparison of light transmittance of PMMA, PC, and COP.
Sample thickness 3 mm. PC: Panlite AD5503, Teijin chem.; PMMA: Acrypet VH,
Mitsubishi rayon; COP: Zeonex 330R.
5 Optical Plastics
n
2
À1
n
2
þ2
¼
4
3
pNa (5.3)
where n is the refractive index, a the polarizability, and N the number of molecules
in 1 cm
3
.
As the result of Eq. (5.3), the refractive index values depend on molecular refrac-
tion and molecular volume of macromolecules as follows:
n ¼
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1þ2½RŠ=V
1À½RŠ=V
s
(5.4)
where [R] is the molecular refraction and V the molecular volume.
The Abbe number is expressed as
V
D
¼
n
D
À1
n
F
Àn
C
. (5.5)
This formula corresponds to Fraunhofer’s D-line (589.2 nm), F-line (486.1 nm),
and C-line (656.3 nm). The Abbe number is the wavelength dependence of refractive
index. The higher the refractive index, the smaller the Abbe number and thus the
larger the wavelength dispersibility, as shown in Figures 5.2 and 5.3 and Table
5.1 [6–13]. Usually an almost straight line can be observed for all polymers when
plotting refractive index against Abbe number.
112
1.40
1.45
1.50
1.55
1.60
1.65
1.70
20 30 40 50 60 70
Abbe number
R
e
f
r
a
c
t
i
v
e

i
n
d
e
x
PC
PMMA
Alicyclic Acrylate
COC(1)
COC(2)
COP(1)
COP(4)
PSU
O-PET
Figure 5.2 Relationship between refractive index and Abbe number for various polymers
at 25 C. PC: Panlite AD5503 at room temperature; PMMA: Parapet at 23 C; Alicyclic acrylate:
Optrez OZ1330; COC(1): Apel 5104DP; COC(2): Topas 5013; COP(1): Zeonex 480R;
COP(4): Arton FX4727; PSU: Udel P-1700; O-PET: OKP-4.
5.2 Quality Requirements for Optical Plastics
Table 5.1 Abbe numbers and refractive indices of optical polymers
material brand name temperature
(C)
refractive index,
D-line (587.6 nm)
Abbe number,
V
D
polycarbonate Panlite room temp. 1.5836 31.7
poly(methyl methacrylate) Parapet 23 1.4913 58.5
alicyclic acrylate Optrez OZ1330 25 1.5096 52
cycloolefin polymer Apel 5014DP 25 1.5434 56.2
Topas 5013 25 1.5333 56.1
Zeonex 480R 25 1.5251 56.0
Arton FX4727 25 1.523 52.0
polysulfone Udel P-1700 – 1.634 23.5
optical polyester OKP-4 30 1.6070 27.6
Plastics usually have a larger linear coefficient of expansion (5 ” 10
–5
–10 ” 10
–5
)
than glass (5 ” 10
–6
–10 ” 10
–6
). Additionally, the specific volume of plastics is
strongly affected by temperature and pressure, especially above the glass transition
113
1.460
1.480
1.500
1.520
1.540
1.560
1.580
1.600
1.620
1.640
1.660
300 500 700 900 1100
Wavelength nm
R
e
f
r
a
c
t
i
v
e

i
n
d
e
x
PSU
O-PET @30°C
PC @room temp.
COC(1)
COC(2)
COP(1)
COP(3)
Alicyclic acrylate
PMMA @23°C
Figure 5.3 Wavelength dependence of refractive index for various polymers at 25 C.
PC: Panlite at room temperature; PMMA: Parapet at 23 C; Alicyclic acrylate: Optrez OZ1330;
COC(1): Apel 5104DP; COC(2): Topas 5013; COP(1): Zeonex 480R; COP(3): Zeonex 330R;
PSU: Udel P-1700; O-PET: OKP-4.
5 Optical Plastics
temperature (Figure 5.4). Commonly optical elements made from thermoplastics
are fabricated by injection molding. In a certain molding process, melted plastic is
pressed and flowed into the mold cavity and then cooled rapidly. Because this
melted plastic is cooled from the skin layer to core in the injection molding process,
temperature and pressure distributions occur in the molding. By this means, certain
density distributions, i.e., refractive index distributions, are generated in the mold-
ing. These distributions are affected by sprue/runner shapes and injection and cool-
ing conditions.
As mentioned above, it is important to control optical properties by specifying
mold designs and molding conditions. Generally, one way to avoid nonuniformity of
cooling is to keep the mold temperature high and to fill the mold with melted plastic
in the shortest possible time. Recently, certain molding technologies have been
under consideration in order to control refractive index distribution using molding
techniques [14].
114
8.0E-04
8.5E-04
9.0E-04
9.5E-04
1.0E-03
1.1E-03
1.1E-03
1.2E-03
1.2E-03
20 120 220 320 420
Temperature °C
S
p
e
c
i
f
i
c

v
o
l
u
m
e

m
3
/
k
g
0MPa
50MPa
100MPa
150MPa
200MPa
Figure 5.4 Dependence of specific volume on temperature and pressure.
Polymer: Zeonex E48R.
5.2 Quality Requirements for Optical Plastics
5.2.3
Birefringence
Another important property of optical parts is the birefringence that appears in a
molding. When light passes through a material, velocities of light differ between
two orthogonally arranged vibrating surfaces. This is called birefringence. If this
phenomenon occurs in lenses, they become sensitive to orientation when used in
polarized light, or no image formation can be achieved around the focal area.
There are several explanations for the cause of birefringence of polymers. Gener-
ally birefringence is categorized into: (1) orientational birefringence given by
Dn ¼ f Dn
0
(5.6)
where f is the orientational coefficient, n the average refractive index, and Dn
0
the
intrinsic birefringence given by
Dn
0
¼
2p
9
ðn
2
þ2Þ
2
n
&
M
N
A
Da (5.7)
in which & is the density, M the molecular weight per unit, N
A
Avogadro’s number,
and Da the major difference of polarizability; and (2) stress birefringence given by
Dn
s
¼ Cr (5.8)
where C is the photoelastic coefficient and r the stress. In these cases, each polymer
has characteristic constants of intrinsic birefringence and photoelastic coefficient.
Tables 5.2 and 5.3 give the intrinsic birefringence and photoelastic coefficient,
respectively, of several polymers [15].
Table 5.2 Intrinsic birefringence of polymers.
polymer intrinsic birefringence, Dn
0
polystyrene –0.1
PPE
a
0.21
PC 0.106
PVC 0.027
PMMA –0.0043
PET 0.105
PE 0.044
a Poly(phenylene ether).
115
5 Optical Plastics
Table 5.3 Photoelastic coefficients of polymers.
polymer photoelastic coefficient, C (”10
–13
cm
2
/dyn)
PMMA –6
PC 72
COP (Zeonex 480R) 6.5
PS –55
As for a specific method to minimize the birefringence of polymers, the refractive
index or polarizability may be minimized using Eq. (5.6). To minimize polarizability,
various measures have been recently used such as the introduction of alicyclic struc-
tures into the main chain. In order to minimize the stress birefringence of Eq. (5.8),
the synthesis of structures with positive and negative constant birefringence within
the same macromolecule has been reported.
5.2.4
Stability
5.2.4.1 Heat Resistance
Heat resistance may be required depending on the intended service environment of
optical plastics. Normally stability to 85 C is required for laser beam printer (LBP),
CD/DVD, and cameras for cellular phones. For automotive applications in the pas-
senger area, the temperature specification is up to 100–110 C; for applications in
the engine area, it is up to 150 C.
Optical polymers are required to have higher deflection temperature under load
than 85 C. Figure 5.5 shows a comparison of the deflection temperature under load
for various optical polymers [6–13].
Some plastics cannot be used in situations involving large environmental
changes, because the temperature dependence of refractive index, dn/dT, of plastics
is about 10–100 times higher than that of glass. For instance, Table 5.4 gives a com-
parison of the focal shifts of plastic and glass lenses. Both lenses have a focal dis-
tance of approximately 20 mm and thickness of 2 mm with a temperature change
from 20 to 80 C calculated by
f ¼
R
1
R
2
n
ðnÀ1Þ½nðR
1
ÀR
2
ÞþðnÀ1ÞdŠ
(5.9)
where n is the refractive index, R
1
and R
2
the radii of curvature of the lens, and d the
thickness of the lens. In this case, the focal shift value of the plastic lens is approxi-
mately 19 times larger than that of the glass lens. It is necessary to consider this fact
when designing optic elements made of plastics.
116
5.2 Quality Requirements for Optical Plastics
Table 5.4 Comparison of focal shifts of plastic and glass lenses.
plastic: Zeonex 480R glass: Schott N-BK7
linear expansion coefficient 6.0 ” 10
–5
8.3 ” 10
–6
temperature (C) 25 80 25 80
r
1
(mm) 34 34.1122 32 32.0416
r
2
(mm) –15 –15.0495 –15 –15.0068
refractive index, n 1.5273 1.5214 1.51872 1.51856
thickness, d (mm) 2.000 2.0066 2.000 2.0009
focal distance, f (mm) 20.02 20.31 19.98 19.99
refractive index shift –0.006 –0.0002
focal shift 0.291 0.015
5.2.4.2 Moisture Absorption
The influence of volume change on optical properties in high-temperature and
high-humidity environments cannot be clearly expressed. Usually, the reliability of
an optical device is evaluated by accelerated tests in high-temperature and high-
humidity environments. For example, it is determined using the performance
change of an optical device under conditions of 60 C, 90% RH, and 500 h duration
117
0
20
40
60
80
100
120
140
160
180
200
PSU PC COP(1) COC(1) COC(2) COP(4) O-PET Alicyclic
acrylate
PMMA
D
e
f
l
e
c
t
i
o
n

t
e
m
p
e
r
a
t
u
r
e

u
n
d
e
r

l
o
a
d

1
.
8
0
M
P
a



/


°
C
Figure 5.5 Comparison of the deflection temperature under load for various optical polymers.
PC: Panlite AD5503; PMMA: Acrypet VH; Alicyclic acrylate: Optrez OZ1330;
COC(1): Apel 5104DP; COC(2): Topas 5013; COP(1): Zeonex 480R;
COP(4): Arton FX4727; PSU: Udel P-1700; O-PET: OKP-4.
5 Optical Plastics
as a reference. Figure 5.6 shows the water absorption of some major optical plastics
[6–13].
Even a relatively small water absorption affects size distortion and density. In
order to obtain optically stable materials various developments have been attempted
to reduce the water absorption. From recent actual examples, the introduction of ali-
cyclic structures and the use of a polyolefin with alicyclic structure (cycloolefin poly-
118
Condition 23°C, water, 24hr
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
PSU PC COP(2) COC(1) COC(2) COP(4) O-PET Alicyclic
acrylate
PMMA
W
a
t
e
r

a
b
s
o
r
p
t
i
o
n

r
a
t
e

%

Figure 5.6 Comparison of the water absorption of some optical polymers.
PC: Panlite AD5503; PMMA: Acrypet VH; Alicyclic acrylate: Optrez OZ1330;
COC(1): Apel 5104DP; COC(2): Topas 5013; COP(2): Zeonex E48R;
COP(4): Arton FX4727; PSU: Udel P-1700; O-PET: OKP-4.
-0.0004
0.0000
0.0004
0.0008
0.0012
0.0016
0 5 10 15
Time (day)
C
h
a
n
g
e

o
f

r
e
f
r
a
c
t
i
v
e

i
n
d
e
x
d
-
l
i
n
e
,

2
5
°
C
COP
PMMA
0.0
0.5
1.0
1.5
0 5 10 15
W
a
t
e
r

a
b
s
o
r
p
t
i
o
n


%
PMMA
COP
Figure 5.7 Change of refractive index due to water absorption for PMMA (Delpet
80NH) and COP (Zeonex E48R). Sample thickness 3 mm; condition: 50 C, 90% RH;
measurement by V-block method at 23 C, 50% RH; instrument: Kalnew precision
refractometer KPR-200.
5.2 Quality Requirements for Optical Plastics
mer) have produced good results. Figure 5.7 shows the change of refractive index
due to water absorption for PMMA and COP. From these data it can be seen that
the refractive index is much affected by water absorption. The details are discussed
later.
5.2.4.3 Residual Stress
It is also important to prevent size distortion and tilt due to the residual stress at the
time of plastic molding. Optimization of molding conditions will minimize the re-
sidual stress of a molded item and, as a result, minimize warp progression. Large
residual stress can also be removed by annealing below the glass transition tempera-
ture (see Figure 5.8).
119
-0.8
-0.4
0
0.4
0.8
20 30 40 50 60
Radius mm
R
a
d
i
a
l

d
e
v
i
a
t
i
o
n

d
e
g
Immediate after molding
1day
3day
6day
7day
Mold temperature
75°C
-0.8
-0.4
0
0.4
0.8
20 30 40 50 60
Radius mm
R
a
d
i
a
l

d
e
v
i
a
t
i
o
n

d
e
g
Immediate after molding
1day
3day
6day
7day
Mold temperature
80°C
Figure 5.8 Change of radial deviation of optical disc. Sample
thickness 0.6 mm, diameter 120 mm, optical disc substrates
made from COP (Zeonor 1060R), measurements at room
temperature.
5 Optical Plastics
5.3
Plastics
5.3.1
Acrylate Polymers
5.3.1.1 PMMA
This is one of the major materials used in optical plastics. It is made by polymeriz-
ing the monomer methyl methacrylate. It is used as a pellet-shaped material for pro-
cessing or offered as cast board manufactured by polymerizing the monomer by
pouring it into a mold sandwiched between glass boards. The chemical structure of
PMMA is shown in Figure 5.9.
The material characteristics are as follows:
.
high transparency;
.
low birefringence;
.
outstanding hardness;
.
high light deterioration resistance; and
.
high Abbe number.
Tables 5.5 and 5.6 give catalog values for PMMA polymers offered by Mitsubishi
Rayon Co. Ltd. and Kuraray Co. Ltd [7, 16]. With its high transparency and hardness,
PMMA is used in various transparent parts.
As for optical use, PMMA is used in large lenses such as condensers, Fresnel
lenses, projection TV lenses, and lenses for car lamps; it is also used for small- to
medium-sized high-precision lenses such as optical lenses for LBP, lenses for dis-
posable cameras, and optical pick-up lenses. With its high transparency it is also
used in light guide plates for LCD backlights and in light diffusing devices for illu-
mination in which elements are diffused. It is also used in cover materials for dis-
plays, instruments, and gauges, and for the covers of rear lights of automobiles.
120
C
C
CH
3
O
O
n
CH
3
CH
2
Figure 5.9 Chemical structure of PMMA.
5.3 Plastics 121
The problems of PMMA as an optical material include (1) water absorbing prop-
erty: change of refractive index and size due to water absorption; and (2) heat resis-
tance: glass transition temperature of 100 C is insufficient in some environments.
The development of various polymers is in progress to solve these problems.
Various companies have shown good results of their own efforts to minimize bire-
fringence, ideally to zero. One well-known example is the development of an acry-
late-containing alicyclic structure called Optrez

by Professor Koike of Keio Univer-
sity and Hitachi Chemical Co. Ltd [17].
5.3.1.2 Alicyclic Acrylate
By replacing some side-chain methyl groups with cyclic functionalities in PMMA,
the following properties have been obtained:
.
low birefringence;
.
low water absorption; and
.
high heat resistance.
Optrez

is now on the market from Hitachi Chemical Co. Ltd. The major physi-
cal properties are given in Table 5.7 and the chemical structure is shown in Figure
5.10 [18]. Water absorption is reduced, being approximately half of that of PMMA.
The light stability remains high, being similar to that of PMMA. It is used for simi-
lar purposes to PMMA. It has been already used in optical lenses, CD pick-up
lenses, LBP lenses, and others.
C
C
CH
3
O
O
m
CH
2
C
C
CH
3
O
O
n CH
3
CH
2
Figure 5.10 Chemical structure of an alicyclic acrylate.
5 Optical Plastics 122
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5.3 Plastics
5.3.2
Polycarbonate
5.3.2.1 Optical Polycarbonate
Polycarbonate (PC) is the most commonly used optical material. General PC is poly-
merized from bisphenol-A with carbonyl chloride or diphenylether. It is mostly used
for CD-DA. It is also used for optical discs including CD-ROM, CD-R/RW, MD,
DVD-ROM, DVD-Video, and DVD–R/RW. The chemical structure is shown in Fig-
ure 5.11.
The characteristics of PC are as follows:
.
low levels of impurities;
.
transparency;
.
high refractive index, high scattering;
.
heat resistance;
.
moldability (transferability); and
.
high intensity.
With these characteristics it is not only used for optical discs but also for optical
lenses and optical films for liquid crystals. It has one of the best impact strengths
among the various engineering plastics, and thus is used for multiple purposes. It is
also used for grading of building materials and for lenses for car lamps. The suppli-
ers are GE plastics, Bayer, Dow Chemical, Teijin Chemicals, Mitsubishi Engineering
Plastics, Idemitsu Petrochemical, Asahikasei, and others. It is the most widely used
material for optical disc storage. Table 5.8 gives the physical properties of Panlite

AD-5503 offered by Teijin Chemicals Co. Ltd [6].
A problem with PC is that it has large birefringence. The photoelastic coefficient
of PC is approximately 10 times greater than that of PMMA. Thus, for high-density
optical discs, such as magnetic optical discs, when the incident angle is large, the
birefringence becomes large. This may cause read errors. The following measures
can be taken to reduce the birefringence [19]:
.
improvement of fluidity;
.
introduction of monomer with structure different from bisphenol-A; and
.
mixing with other materials, such as polystyrene, that off-set the large photo-
elastic coefficient.
127
O C
CH
3
CH
3
O C
O
n
Figure 5.11 Chemical structure of PC.
5 Optical Plastics
Table 5.8 Typical properties of polycarbonate: Panlite (Teijin Chemicals Ltd).
property unit test method condition AD-5503 L-1225Y
density kg/m
3
ISO 1183 – 1200 1200
water absorption % ISO 62 in water; 23 C, 24 h 0.2 S0.2
light transmittance % ASTM D1003 3 mm thickness 89 88
refractive index – ASTM D542 – 1.585 1.585
Abbe number – ASTM D542 – 30 30
tensile modulus MPa ISO 527-1 and -2 1 mm/min 2450 2400
tensile yield stress MPa ISO 527-1 and -2 50 mm/min 63 62
tensile yield distortion % ISO 527-1 and -2 50 mm/min 6 6
tensile fracture designation
distortion
% ISO 527-1 and -2 50 mm/min >50 >50
flexural modulus MPa ISO 178 2 mm/min 2400 2350
flexural strength MPa ISO 178 2 mm/min 96 92
load-deflection
temperature
C ISO 75-1 and -2 1.80 MPa 124 128
0.45 MPa 138 141
coefficient of linear
expansion
”10
–4
/C ISO 11359-2 parallel 0.7 0.7
vertical 0.7 0.7
5.3.2.2 Low-Birefringence Polycarbonate: ST-3000
Teijin-Bayer Polytec Ltd, jointly operated by Teijin Chemicals and Bayer, undertook a
joint development and has now started marketing a new material called ST-3000, a
low-birefringence PC [20, 21]. This is a material that solves the problems of the large
birefringence of conventional PC. Compared to conventional PC it is characterized
by the following:
.
50% lower birefringence than normal PC;
.
25% lower water absorption than normal PC; and
.
high rigidity.
This material is used for some high-density optical discs and (optical) films that
require a low birefringence, which can be achieved using this new material.
5.3.3
Cycloolefin Polymer
Recently COP, which was originally developed around 1990, has been used as an
optical material for parts that require high quality. COP is a polymer with an alicyc-
lic structure synthesized using a cycloolefin as a monomer. Its main chain has a
bulky cyclic structure. This polymer is amorphous and has high transparency and
heat resistance. It has also outstanding environmental durability and no hygroscopic
property when it is composed only of hydrocarbons.
128
5.3 Plastics
It has already been commercialized as Zeonex

and Zeonor

by Zeon Corpora-
tion, Apel

by Mitsui Chemicals, Topas

by Ticona, and, although not a complete
carbon hydride, Arton

by JSR.
These materials have high heat resistance and no property transformation due to
moisture absorption. They are thus used in optical parts that would otherwise use
PMMA.
5.3.3.1 Zeonex

/Zeonor

[22, 23]
The Zeonex

materials are polymers obtained by ring-opening metathesis polymer-
ization of norbornene derivatives and then complete hydrogenation of double
bonds. The catalyst and other impurities used in the polymer synthesis have been
almost completely removed. Its transparency is outstanding even among COPs. It is
a transparent and colorless material with no light absorption in the visible region.
The chemical structure is shown in Figure 5.12.
The major characteristics are as follows:
.
Low specific gravity (approximately 1.0). This is less than that of PMMA/PC.
.
Transparent. No absorption in the whole visible region; almost the same
transmittance as PMMA.
.
Low water absorption. The lowest water absorption among optical plastics.
.
Low scattering. Refractive index is approximately 1.51–1.53. The wavelength
dependence is relatively weak.
.
Low birefringence. Outstanding birefringence performance especially to
diagonal incident light compared to PC. The optoelastic constant is the same
as that of PMMA.
.
Heat resistance. Glass transition temperature is 123–138 C. This is sufficient
for normal use.
.
High processability. High fluidity and excellent and accurate moldability.
The general physical properties are given in Table 5.9. COP has the lowest water
absorption among all transparent plastics. Thus distortion or change of optical prop-
erties due to water absorption is a minimum (Figure 5.13). This plastic is suitable
for optical devices such as lasers used for the visible region.
The photoelastic coefficient of Zeonex

or other COPs is less than that of PC and
the same as that of PMMA. The actual birefringence is higher than that PMMA and
lower than that of PC. The dependence on the incidence angle of birefringence is less
pronounced than for PC, and thus it has been used for optical discs (Figure 5.14).
129
CH
2
n
CH
2
R1
R2
Figure 5.12 Chemical structure of COP.
5 Optical Plastics 130
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5.3 Plastics 131
Astigmatism
Spherical aberration
Coma aberration
0.00
0.02
0.04
condition-A condition-B
0
5 10 15 20 25
0.00
0.02
0.04
condition-A condition-B
Time / day
λRMS
-0.04
-0.02
0.00
0.02
0.04
condition-A
condition-B
Figure 5.13 Change of the spherical aberration of optical lenses made from
PMMA (filled circles) and COP (Zeonex 480R, open circles) under the condition
of high temperature and humidity. Condition A: 60 C, 90% RH, 168 hours;
condition B: 25 C, 50% RH.
COP PC
0 0.375 5.875
10 1.5 10
20 4.75 41.25
30 10.625 91.875
0
20
40
60
80
100
0 5 10 15 20 25 30 35
Incident angle / °
R
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COP
PC
Incident angle
Optical disc storage
Figure 5.14 Comparison of incidence angle dependence of birefringence
(retardation) of COP (Zeonex 480R) and PC. Sample: optical disc storage with
diameter 86 mm and thickness 1.2 mm; measurement point: 30 mm distance
from the center of the optical disc.
5 Optical Plastics
The transparency of Zeonex

is at the same level or higher than that of PMMA,
which is known to have the best light transmittance among transparent plastics.
Thus, with this property and also because of its dimensional stability it is used for
the prisms of compact cameras.
Zeon Corporation also offers Zeonor

, which is a polymer characterized by trans-
parency, high fluidity, and high heat resistance like Zeonex

without refractive
index or birefringence properties. With these characteristics, it is used for the trans-
parent parts of optical discs and light guide plates for LCD backlights (Table 5.10).
132
Table 5.10 Typical properties of cycloolefin polymer: Zeonor (Zeon Corporation).
property unit method condition 750R 1020R 1060R
specific gravity – ASTM D792 – 1.01 1.01 1.01
water absorbance % ASTM D570 – <0.01 <0.01 <0.01
light transmittance % ASTM D1003 3 mm thickness 92 92 92
glass transition temperature C JIS K7121 – 70 105 100
deflection temperature under
load
C ASTM D648 1.80 MPa 68 101 99
coefficient of linear expansion 1/C ASTM E831 – 7 ” 10
–5
7 ” 10
–5
7 ” 10
–5
melt flow rate g/10 min JIS K6719 280 C, 21.18 N 27 20 –
260 C, 21.18 N – – 14
flexural modulus MPa ISO 178 – 1800 2100 2100
flexural strength MPa ISO 178 – 55 80 76
tensile strength MPa ISO 527 – 42 53 53
modulus of elasticity in tension MPa ISO 527 – 2000 2200 2100
tensile elongation % ISO 527 – 140 90 60
Izod impact strength J/m ASTM D256 with notch 80 60 18
Dupont impact strength J – – 35 36 26
Rockwell hardness – ASTM D785 M scale – 20 20
volume resistivity X m IEC 93 – >10
16
>10
16
>10
16
dielectric breakdown strength kV/mm ASTM D149 Short-time
method, 1 mm
70 70 70
dielectric constant – IEC 250 1 MHz 2.3 2.3 2.3
dielectric tangent – IEC 250 1 MHz 0.0002 0.0002 0.0002
flammability – UL-94 – (94HB) 94HB 94HB
characteristics
a
– – – good secondary
molding
processability
high moisture-
proofing, high
strength
high fluidity
Data represent experimental results and do not guarantee specific performance levels
in actual usage.
a Heat-resistant grades are also available.
5.3 Plastics
5.3.3.2 Cycloolefin Copolymer (COC): Apel

/Topas

As polymers synthesized by copolymerization of norbornenes and alpha-olefins,
Apel

and Topas

have been commercialized by Mitsui Chemical Co. Ltd and
Ticona, respectively.
The characteristics are very much similar to those of COP:
.
low specific gravity;
.
transparency;
.
low water absorption;
.
low scattering;
.
low birefringence;
.
heat resistance; and
.
high processability.
They are particularly known for their low birefringence and high fluidity.
Apel

is synthesized by copolymerization of tetracyclododecene (TCD) and alpha-
olefin. Table 5.11 [24] gives the general physical properties. In particular, with a bire-
fringence less than that of PMMA and transparency in the red laser region, it is
often used in DVD pick-up lenses. The chemical structure of Apel

is shown in Fig-
ure 5.15.
Topas

is a copolymer of norbornene and alpha-olefin. Table 5.12 [25] gives the
general physical properties and Figure 5.16 shows the chemical structure. The bire-
fringence is similar to that of PMMA; however, the transparency is outstandingly
high. Topas

is used in various optical lenses.
133
CH CH
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Figure 5.15 Chemical structure of Apel

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5 Optical Plastics
5.3.3.3 Norborne Functional Polymer: Arton

JSR offers Arton

which is a COP with ester groups. The ester groups cause some
amount of water absorption compared with other COPs, but lead to easy surface
coating, adhesion, and other surface treatments. Table 5.13 [10] gives the general
physical properties and Figure 5.17 shows the chemical structure.
The characteristics of this polymer are as follows:
.
low birefringence;
.
high fluidity;
.
high heat resistance; and
.
easy surface treatment and adhesion.
It is used in optical films, optical lenses, and light guide plates for LCD.
136
CH CH
2
R
m n
Figure 5.16 Chemical structure of Topas

.
CH
2
n
CH
2
C
O
O
CH
3
CH
3
Figure 5.17 Chemical structure of Arton

.
5.3 Plastics
5.3.4
Other Resin Materials
The challenges with optical plastics include the achievement of low birefringence,
high refractive index, and high durability (low moisture absorption and high heat
resistance).
137
Table 5.13 Typical properties of norbornene functional polymer: Arton (JSR).
property unit method condition F5023 FX4726 FX4727 D4531 D4532
optical
refractive index – ASTM D542 D-line, 25 C 1.512 1.522 1.523 1.515 1.514
transmittance % ASTM D1003 3.2 mm thickness 93 93 93 93 93
haze % ASTM D1003 3.2 mm thickness 0.6 0.6 0.6 0.6 0.6
Abbe number – ASTM D542 25 C 57 52 52 57 57
stress optic coefficient 10
–8
cm
2
/N JSR method 546 nm 3 1 1 4 4
birefringence nm ellipsometer 633 nm <20 <20 <20 <20 <20
thermal
glass transition
temperature
C DSC 20 C/min 167 125 120 135 145
heat deflection
temperature
C ASTM D648 18.2 ” 10
4
Pa 162 115 110 130 140
mold shrinkage % ASTM D955 MD direction 0.5–0.7 0.5–0.7 0.5–0.7 0.5–0.7 0.5–0.7
coefficient of linear
expansion
10
–5
/C ASTM D696 6 9 9 8 8
heat conductivity W/m/C JSR method 100 C 0.17 0.16 0.16 0.17 0.17
melt flow rate g/10 min JIS K7210 260 C, 98 N 8 60 120 45 40
mechanical
tensile stress MPa ASTM D638 75 75 70 75 75
elongation at break % ASTM D638 15 10 10 15 15
flexural stress MPa ASTM D790 125 120 120 120 120
flexural modulus MPa ASTM D790 3000 3000 3000 3000 3000
Izod impact strength J/m ASTM D256
1
4 in notched 20 20 20 20 20
Rockwell hardness – ASTM D785 R scale 125 125 125 125 125
pencil hardness – JIS K5401 H H H H H
electrical
dielectric breakdown
strength
kV/mm ASTM D149 1 mm 30 30 30 30 30
volume resistivity 10
16
Xcm ASTM D257 >1 >1 >1 >1 >1
dielectric constant – ASTM D150 1 MHz 3 3 3 3 3
dielectric loss – ASTM D150 1 MHz 0.02 0.01 0.01 0.02 0.02
arc resistance s ASTM D495 3 mm 190 180 180 190 190
chemical resistance
dilute sulfuric acid ASTM D543 soaking, 23 C, 1 week
1, tolerant
2, limited tolerance
3, not tolerant
1 1 1 1 1
NaOH (10%) 1 1 1 1 1
methyl alcohol 1 1 1 1 1
isopropyl alcohol 1 1 1 1 1
acetone 2 2 2 2 2
toluene 3 3 3 3 3
methyl ethyl ketone (MEK) 2 2 2 2 2
other
density – ASTM D792 – 1.08 1.06 1.06 1.08 1.08
water absorption % ASTM D570 23 C, water, 1 week 0.4 0.2 0.2 0.2 0.3
5 Optical Plastics
5.3.4.1 Optical Polyester (O-PET)
A new type of polyester has been suggested for optical use [26]. The chemical struc-
ture of an example of such an optical polyester is shown in Figure 5.18 [27]. This
polymer is synthesized from 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorine (BPFE), eth-
ylene glycol, and dimethylterephthalate (DMT).
Osaka Gas Co. Ltd and Kanebo Ltd have co-developed an amorphous polyester
material, OKP-4. It is now available commercially from Osaka Gas Chemical. The
characteristics of OKP-4 are as follows:
.
high refractive index (>1.6); and
.
low birefringence.
Table 5.14 gives the catalog values of some of its properties.
Table 5.14 Typical properties of optical polyester: OKP-4 (Osaka Gas Chemical).
property unit method condition OKP-4
density kg/m
3
ISO 1183 1220
water absorption % ISO 62 water, 23 C, 24 h 0.15
light transmittance % ASTM D1003 3 mm thickness 90
refractive index – ASTM D542 Abbe 1.607
Abbe number – ASTM D542 27
tensile modulus MPa JIS K7113 2000
tensile yield strength MPa JIS K7113 60
tensile yield distortion % JIS K7113 4
flexural modulus MPa JIS K7203 2300
flexural strength MPa JIS K7203 99
heat distortion temperature C ISO 75-1 and -2 1.80 MPa 105
coefficient of linear expansion 10
–4
/C ISO 11359-2 0.7
138
n
C
O
CH
2
CH
2
O C
O
O
m
C
O
CH
2
CH
2
O C
O
O CH
2
CH
2
O O
Figure 5.18 Chemical structure of an optical polyester.
5.3 Plastics
5.3.4.2 Olefin–Maleimide Copolymer
TOSOH Corporation proposes a newly developed material, an olefin–maleimide co-
polymer, named TI-160 [28]. This polymer is under development. The characteristics
are as follows:
.
low birefringence; and
.
outstanding rigidity and hardness.
The general physical properties are given in Table 5.15 [29].
Table 5.15 Typical properties of olefin–maleimide copolymer: TI-160 (TOSOH Corporation).
property unit TI-160 PC PMMA
light transmittance % 89 88 92
haze % 1 1 1
Abbe number – 50 29 55
stress optic coefficient 10
–12
/Pa 6 100 –4
heat deflection temperature C 130 136 95
flexural stress at yield MPa 125 92 113
flexural modulus GPa 4.6 2.2 3.1
Izod impact strength kg cm/cm 1.5 75 1
pencil hardness 3H B 3H
water absorption % 0.5 0.2 0.4
5.3.4.3 Polysulfone (PSU)
PSU is an excellent engineering plastic with high heat resistance. The characteris-
tics of this polymer are as follows:
.
Heat resistance. The heat deflection temperature is 343 F (174 C).
.
High refractive index (>1.6).
.
High intensity.
Typical applications of PSU are in food service components, plumbing fixtures,
membranes, and laboratory animal cages. PSU is stable as regards stress, chemicals,
and steam or gamma sterilization required for medical applications. PSU is not
commonly used for optical purposes because it is colored yellow, but it is used in
heat-stable lenses. The general physical properties of the PSU Udel

P-1700 are giv-
en in Table 5.16 [29] and its chemical structure is shown in Figure 5.19.
139
5 Optical Plastics
Table 5.16 Typical properties of polysulfone: Udel P-1700.
property method
a
value
b
value
c
general
specific gravity D792 1.24 1.24
water absorption, 24 h D570 0.30% 0.30%
melt flow at 343 C, 2.16 kg D1238 6.5 g/10 min 6.5 g/10 min
mold shrinkage D955 0.007 in/in 0.007 mm/mm
mechanical
tensile strength D638 10.2 kpsi 70.3 MPa
tensile modulus D638 360 kpsi 2.48 GPa
tensile elongation at break D638 50–100% 50–100%
flexural strength D790 15.4 kpsi 106.2 MPa
flexural modulus D790 390 kpsi 2.69 GPa
tensile impact strength D1822 200 ft-lb/in
2
420 kJ/m
2
Izod notched impact strength D256 1.3 ft-lb/in 69 J/m
thermal
deflection temperature at 264 psi (1.8 MPa) D648 345 F 174 C
coefficient of linear expansion D696 31 ppm/F 56 ppm/C
glass transition temperature 374 F 190 C
electrical
dielectric strength D149 425 V/mil 17 kV/mm
dielectric constant at 60 Hz D150 3.3 3.3
dielectric constant at 103 Hz 2.9 2.9
dielectric constant at 106 Hz 4.1 4.1
dissipation factor at 60 Hz D150 0.0007 0.0007
dissipation factor at 103 Hz 0.001 0.001
dissipation factor at 106 Hz 0.006 0.006
volume resistivity D257 3 ” 10
16
Xcm 3 ” 10
16
Xcm
color
NT 11 (natural) light amber
NT 06 (natural) very light amber
CL 2611 (clear) nearly water white
optical
refractive index 486.1 nm 1.650
587.6 nm 1.634
656.3 nm 1.623
Abbe number 23
light transmittance; 1.8/2.5/3.3 mm thickness D1003 86/85/84%
haze; 1.8/2.5/3.3 mm thickness D1003 1.5/2.0/2.5%
yellowness index; 1.8/2.5/3.3 mm thickness D1925 7.0/10/13%
a ASTM.
b US customary units.
c SI units.
140
5.4 Summary
5.4
Summary
Table 5.17 gives the physical properties of various plastics for optical use. Table 5.18
gives the refractive index data reported by plastics suppliers. Figure 5.20 shows the
retardation data for various plastics. Table 5.19 gives a comparison of some optical
plastics. We select the materials that have characteristics in accordance with quality
requirements.
141
O C
CH
3
CH
3
O S
O
n
O
Figure 5.19 Chemical structure of PSU.
0
10
20
30
40
PMMA Alicyclic acrylate COC(2) COP(2) COP(3)
R
e
t
a
r
d
a
t
i
o
n

n
m
Figure 5.20 Retardation data for various polymers.
PMMA: Acrypet VH; COC(2): Topas 5013; COP(2): Zeonex E48R; COP(3): Zeonex 330R.
Measurement by minute area automatic birefringence analyzer: KOBRA CCD, wavelength 590 nm.
Sample: injection molded plate, size 65 ” 65 ” 3t mm. Measurement point: diagonally 75 mm
distance from the gate which is located at one corner of the sample plate.
5 Optical Plastics 142
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5.4 Summary
Table 5.18a Refractive index of PMMA: Parapet HR1000S (Kuraray Co. Ltd).
temperature (C) wavelength (nm) Abbe number, V
D
435.8 486.1 546.1 587.6 656.3 827.3
23 1.5019 1.4972 1.4933 1.4193 1.4888 1.4848 58.5
Instrument: Kalnew KPR-20 precision refractometer.
Conditions: range= no. 1 (1.25–1.7); mode= auto stand.,
intermediate solvent; n
d
= 1.49.
Table 5.18b Refractive index of PC: Panlite (Teijin Chemicals Ltd).
temperature theoretical wavelength (nm) Abbe number, V
D
486
n
F
587
n
d
656
n
C
room temp. 1.5966 1.5836 1.5782 31.7
Measurement: Atago 2T Abbe refractometer.
Light source: Mitsubishi Rayon ELI-050 halogen lamp.
Homogeneous light from JOBIN YVON H.20 UV;
wavelength 400–700 nm.
Table 5.18c Refractive index of alicyclic acrylate: Optrez (Hitachi Chemical Co. Ltd).
grade temperature (C) wavelength (nm) Abbe number, V
D
F-line
486.1
D-line
587.6
C-line
656.3
LD
786.5
OZ-1000 25 (50% RH) 1.5053 1.4995 1.4966 1.4937 57.4
OZ-1100 25 (50% RH) 1.5087 1.5025 1.4998 1.4965 56.5
OZ-1310 25 (50% RH) 1.5121 1.5059 1.5027 1.4997 53.8
OZ-1330 25 (50% RH) 1.5162 1.5096 1.5064 1.5031 52.0
Measurement: transmission refractometer.
143
5 Optical Plastics 144
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5.4 Summary
Table 5.18g Refractive index of cycloolefin copolymer: Apel 5014DP (Mitsui Chemicals Inc.).
temperature (C) wavelength (nm) Abbe number, V
D
g-line
435.8
F-line
486.1
d-line
587.6
C-line
656.5
LD
786.5
5 1.5571 1.5518 1.5450 1.5421 1.5385 56.2
25 1.5556 1.5503 1.5434 1.5406 1.5371 56.0
50 1.5532 1.5478 1.5410 1.5382 1.5347 56.4
75 1.5505 1.5451 1.5383 1.5355 1.5320 56.1
dn/dT (”10
–5
/C) –9.5 –9.7 –9.6 –9.5 –9.4
Table 5.18h Refractive index of cycloolefin copolymer: Topas 5013 (Ticona).
temperature (C) wavelength (nm) Abbe number, V
D
435.8 486.1 546.1 587.6 656.3 706.5 768.2 1014
15 1.5465 1.5411 1.5367 1.5344 1.5315 1.5302 1.5285 1.5253 55.7
25 1.5455 1.54 1.5354 1.5333 1.5305 1.5289 1.5275 1.524 56.1
50 1.5428 1.5374 1.5331 1.5308 1.528 1.5263 1.525 1.5218 56.5
75 1.5403 1.535 1.5305 1.5283 1.5255 1.5238 1.5225 1.5191 55.6
dn/dT (”10
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/C) –10.4 –10.7 –10.1 –10.1 –10.0 –10.6 –10.0 –10.1
Table 5.18i Refractive index of optical polyester: OKP-4 (Osaka Gas Chemical).
temperature (C) wavelength (nm) Abbe number, V
D
436 486 546 589 656
30 1.6370 1.6230 1.6130 1.6070 1.6010 27.6
Table 5.18j Refractive index of polysulfone: Udel P-1700.
temperature (C) wavelength (nm) Abbe number, V
D
486.1 587.6 656.3
25 1.650 1.634 1.623 23.5
145
5 Optical Plastics 146
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References
As stated previously, improved polymers are now under consideration as a result of
various recent technology developments. These polymers are very good as regards
mass-productivity compared to glass; however, they do not necessarily reach the
same level of environmental stability and variety of refractive index as glass. Cur-
rently, appropriate materials are selected for each use. In the future, further develop-
ments of materials are expected, enabling more applications in various fields. The
main areas of research and development concern
.
high-refractive-index materials;
.
low-birefringence materials; and
.
materials with higher environmental stability, mainly heat resistance.
147
References
[1] F. Ubrbach, Phys. Rev. 92, 1324 (1953).
[2] F. Ide, Refractive index control of transparent
high polymers, Kikan Kagaku Sosetsu 39,
3 (1998).
[3] T. Kaino, M. Fujiki, and K. Jinguji, Rev. ECL
32, 478 (1984).
[4] T. Kakezawa, et al., J. Appl. Polym. 46,
1835 (1992).
[5] N. Tanio, Koubunshikakou 46, 210 (1997).
[6] Catalog of Panlite

AD5503 furnished by
Teijin Kasei.
[7] Technical data of Parapet

furnished by
Kuraray.
[8] Technical data of Apel

5013DP furnished by
Mitsui Chemicals.
[9] Technical data of Topas

furnished by
Ticona.
[10] Catalog of Arton

, JSR.
[11] Catalog of Optrez

, Hitachi Chemicals.
[12] Technical data of Udel

furnished by Solvay
Japan.
[13] Catalog of OKP-4, Osaka Gas Chemical.
[14] JP2002–283426, JP8–015503, JP7–325206,
JP7–281003.
[15] T. Inonu and H. Saito, Funct. Mater. 3,
25 (1987).
[16] Catalog of Acrypet

, Mitsubishi Rayon.
[17] H. Kawaki, Technology and Application of
Plastic Lens System (CMC Publishing, 2003),
pp. 80–86.
[18] H. Kawai, Refractive index control of trans-
parent high polymers, Kikan Kagaku Sosetsu
39, 191 (1998).
[19] H. Yoshioka, Refractive index control of trans-
parent high polymers, Kikan Kagaku Sosetsu
39, 118 (1998).
[20] E. Matsui and T. Makimoto, Recent Transpar-
ent Plastics and the Market (CMC Publishing,
2001), pp. 70–80.
[21] Optical Plastics; Kougaku-you-toumeijusi
(Gijutu-jouhou Kyoukai, 2001), pp. 63–67.
[22] T. Kohara, Refractive index control of trans-
parent high polymers, Kikan Kagaku Sosetsu
39, 133 (1998).
[23] K. Minami, Recent Transparent Plastics and the
Market (CMC Publishing, 2001), pp. 23–37.
[24] Catalog of Apel

, Mitsui Chemicals.
[25] E. Broc and F. Osan, Topas

: cyclo-olefin co-
polymers, MetCon ’98, Polymers in Transi-
tion, 1998.
[26] Y. Yoshida, et al., JSR Tech. Rev. 103,
34 (1996).
[27] M. Fuji, et al., Refractive index control of
transparent high polymers, Kikan Kagaku
Sosetsu, 39, 122 (1998).
[28] Optical Plastics; Kougaku-you-toumeijusi
(Gijutu-jouhou Kyoukai, 2001), pp. 99–103.
[29] Catalog of Udel

, Solvay.
Chapter 1
Introduction
important in many industrial applications. These range from photolithography to
light curable coatings and inks, to holography, and to numerous other
applications. In order to adequately describe the chemistry of these materials, it
is necessary to first explain the manner in which polymers interact with light.
This chapter is an attempt to present some of the background and aid in
understanding the discussions of light-associated reactions of polymeric
materials for readers not familiar with the subjects of photochemistry and
photophysics. The information presented in this introduction was obtained from
the fundamental sources listed in the references. What is presented here,
however, is not a thorough discussion of the subject. For a detailed discussion
the reader is encouraged to go to the original sources in the references.
1.1. The Nature of Light

All electromagnetic radiations travel in vacuum at the speed of C=
2.9979x10
10
cm /sec.
1,2
Light is a form of electromagnetic radiation and,
therefore, also travels at that speed. The fact that light travels at the same speed
as other electromagnetic radiations leads to the assumption that light is wavelike
in character. Our concept of light, however, is that it also consists of packets of
energy that have wave like properties. In each packet there is a range of
energies.
2
These cannot be represented by one wavelength, but rather by a whole
spectrum of wavelengths. The energy of each particular wavelength in the wave-
packet is a discrete unit, a quantum.
Electromagnetic radiation is described in terms of a transverse plane
wave involving associated electric and magnetic fields. It is supposed that the
electric vector E and magnetic vector H which describe the respective field
strengths are aligned in planes at right angles to one another, with both planes
perpendicular to the direction of propagation of the wave.
1
A convenient model
for the variation of the field strength as a function of time t and distance x along
the axis of propagation is given in Cartesian coordinates by the sinusoidal
functions in the following equations
1
:
E
y
= A sin 2t(x / ì - vt)
H
z
=(e/µ)
1/2
A sin 2t(x/ì - v t)
1
Photoresponsive and photocrosslinkable polymeric materials are
In these equations E
y
is the electric field strength vector lying in the xy-plane
and increasing along the y-axis, H
z
is the magnetic field strength vector lying in
the xz-plane and increasing along the z-axis, A is the amplitude of the electric
vector (the intensity of the wave is proportional to A
2
), e is the dielectric
constant, and µ is the magnetic permeability of the medium through which the
wave is transported. In a vacuum e=µ and they are approximately unity in air.
The length of the wave, that is, the distance between adjacent maxima in the
vectors measured at any instant along the direction of wave propagation (the x-
axis) is ì, while v is the frequency or number of complete cycles of vector
position change per second. The relationship between ì and v is
1,2
:
C / v = ì
where, C is the velocity of the radiation. The frequency v is independent of the
medium through which the radiation passes. Wavelength ì and velocity C, on
the other hand depend on e and µ of the medium.
Ordinary light is not polarized. It consists of many electromagnetic
vectors that are undulating in fixed, though randomly oriented with respect to
each other, planes. When the light is polarized in a plane, it is believed that all
the waves have their electric vectors oriented in the same direction. When the
light is polarized elliptically then it is believed that two plane waves of equal
wavelength and frequency and with identical directions of propagation have the
electric vectors perpendicular to one another and out of phase.
The above described model is incomplete and, even called naive by
some.
1
Mathematically, however, it can successfully account for many
observations concerning light, and this theory has been used successfully to
explain many practical phenomena associated with optics.
1.2. The Energy of Radiation
It is possible to calculate the energy associated with any particular
wave length of radiation from the following relationship:
E = hv = hC / ì
where h is a proportionality constant, called Plank's constant, equal to
6.625x10
-27
ergs second /quantum. The velocity of light, designated by C, in
vacuum is 2.9979 x 10
10
cm./ sec, and ì is the wavelength of light, expressed in
centimeters. In a medium containing any matter the light will propagate at a
different speed. In this case, the velocity of light, C' is expressed by an equation
C' = C / (cµ)
1/2
2
Light-Associated Reactions of Synthetic Polymers
where c is the dielectric constant of the matter and µ represents the magnetic
permeability.
The energy associated with one mole of quanta is known as an Einstein.
It is equal to the energy associated with a particular wavelength multiplied by
the Avogadro's number, 6.023 x 10
23
(the number of molecules contained in one
mole of matter). As an example we can take ultraviolet light with wavelength
equal to 300 nm. The energy or an Einstein of light of 300 nm will be
1,2
:
E
300
= h C / ì = 6.67x10
-27
x 3.0x10
10
x 6.023x10
23
x 10
10
/ 300 x 10
-7
x 4.20 =
= 95.7 Kcal / mole
The above calculation shows that at the wave length of 300 nm there is enough
energy in an Einstein to rupture carbon to carbon chemical bonds of organic
molecules.
1.3. Reaction of Light with Organic Molecules
If monochromatic light passes through a uniform thickness of an
absorbing homogeneous medium with the absorbing centers acting
independently of each other, then the energy of light that is absorbed follows the
Lambert-Bouguer law. According to this law of physics the light absorbed is
independent of the intensity of the incident light and the intensity of radiation is
reduced by the fraction that is proportional to thickness of the absorbing system.
In addition, Beer’s law states that absorption is proportional to the number
of absorption centers. The two laws are usually combined and expressed as
follows
1,3-6
:
dI/dl = kcI
where I is the intensity of the radiation, l is the length of the optical path,
through the absorbing medium, c is the concentration of the absorbing centers,
and k is proportionality constant. While there are no know exceptions to the
Lambert-Bouguer law, there are deviations from Beer’s law due to partial
ionization, molecular association and complexation and fluorescence.
Portions of organic molecules or whole molecules that have t bonds
can absorb light radiation, provided that it is of the right wave length. Particular
groupings or arrangements of atoms in molecules give rise to characteristic
absorption bands. Such groups of atoms, usually containing t bonds, are
referred to as chromophores. Examples of such molecules with t bonds are
compounds that contain carbonyl or nitro groups, and aromatic rings. A
molecule that serves as an example of carbonyl arrangement, one that is often
quoted, is a molecule of the formaldehyde. In this molecule, the carbon atom is
linked to two hydrogens and to one oxygen by o bonds. The hybrid sp
2
orbitals
1. Introduction 3
bond one electron of carbon with a second electron of oxygen in an sp orbital.
Also, in a second sp orbital of a pair of unbonded n electrons on oxygen point
away from the carbon atom. The orbitals of formaldehyde, the simplest of the
carbonyl compounds were illustrated by Orchin and Jaffe,
7
as shown in Figure
1.1.
Figure 1.1. The Orbitals of Formaldehyde ( from Orchin and Jaffe
18
)
As described above, the molecule has a o and t bonded skeleton, shown above.
The carbon atom is attached to two hydrogen atoms by single and to oxygen
atom by double bonds. This bonding of the carbon to the two hydrogens and one
oxygen atoms is by means of sp
2
hybrid orbitals. The orbitals are approximately
at 120
o
angles from each other. In the ground state of the molecules the pair of
electrons that form a bond are paired and have opposite or antiparallel spin. In
this state the formaldehyde molecule is planar. The Pauli exclusion principle
states that no two electrons can have all quantum numbers identical. That means
that if two electrons are in the same orbital and three of their quantum numbers
are the same, the fourth quantum number, the spin quantum number, must be
different. The total spin quantum number of a molecule is designated by a letter
J and the sum of the spins of the individual electrons by a letter S. The spin
quantum number of a molecule J is equal to |2S| + 1.
This arrangement of electrons in the p orbital can generate t bonding
and t* antibonding.orbitals. Absorption of light energy by a chromophore
molecule, results in formation of an excited state and an electronic transition
from the ground state to an excited state. Such light may be in the ultraviolet or
in the visible region of the electromagnetic spectrum, in the range of 200 mµ to
approximately 780 mµ. Promotion of electrons out of the o bonding orbitals to
the excited states requires a large amount of energy and rupture of bonds in the
process. On the other hand, the electronic transition to promote one of the n
electrons on the oxygen atom in formaldehyde to the antibonding or the non-
bonding orbital, t* level require the least amount of energy. The name, as one
might deduce, is a type of orbital where the electrons make no contribution to
4
Light-Associated Reactions of Synthetic Polymers
1. Introduction
the binding energy of the molecule. In formaldehyde this n ÷÷ t* transition to
the excited state gives rise to an absorption band (at about 270 mµ). This is a
relatively weak band and it suggests that the transition is a forbidden one
(forbidden does not mean that it never occurs, rather that it is highly
improbable). It is referred to as a symmetry forbidden transition. The reason for
it being forbidden is crudely justified by the fact that the ʌ* is in the xz plane
(see Fig. 1.1.) The n electrons in the p
y
.orbital are in the xz plane and
perpendicular to the ʌ* orbital. Because, the spaces of the two orbitals overlap
low. As stated above, in the ground (normal) state of the molecules two
electrons are paired. The pairing means that these electrons have opposite or
anti-parallel spins. After absorbing the light energy, in the singlet excited state
the two electrons maintain anti-parallel spins. The n ÷÷ t* excitation,
however, can lead to two excited state, a singlet (S
1
) and a triplet (T
1
) one with
an absorption band (at about 250 mµ). Intersystem crossing to a triplet state
from the singlet results in a reversal of the spin of one of the electrons and an
accompanying loss of some vibrational energy. This is illustrated in Figure 1.2.
energy
ground
state
singlet
excited
state
triplet
excited
state
Figure 1.2. Illustration of the Singlet and the Triplet States
The intersystem crossing from the singlet to triplet states can occur with high
efficiency in certain kinds of molecules, particularly in aromatic and carbonyl-
containing compounds. Electron-electron repulsion in the triplet state is
minimized because the electrons are farther apart in space and the energy is
lower in that state than that of the corresponding excited singlet one. Solvents
can exert a high influence on the n ÷÷ t* transitions. While the intersystem
crossing is a forbidden transition (see above) it can actually occur with high
frequency in certain molecules like aromatic or carbonyl compounds.
been fully described in various books on photochemistry
1,3-5
It will, therefore, be
discussed here only briefly. The transitions are illustrated here in a very
5
so poorly, the likelihood of an electronic transition from one to the other is quite
The chemical mechanism of photoexcitation of organic molecules has
simplified energy diagram that shows the excited singlet state and the various
paths for subsequent return to the ground state in Figure 1.3.
enrgy
ground state
S
2
S
1
T
2
T
1
b
a a' c h i d
(triplet)
(triplet)
(singlet)
(singlet)
f
e
Figure 1.3. Diagram depicting excitation and relaxation pathways of an
.
The energy diagram (Fig. 1.3.) represents energy states of a molecule that
possesses both n and t* electrons. S
1
and S
2
are the singlet excited states. T
1
and
T
2
are the excited triplet states. Solid lines represent electronic transitions. They
are accompanied by absorption or emissions of photons. Radiationless
transitions are represented by doted lines. The above diagram shows the lowest
singlet state S
1
, where the electrons are spin paired and the lowest triplet state
T
1
, where the electrons are spin unpaired. The electron is excited by light of a
particular wavelength into an upper singlet level, S
2
. Relaxation follows via an
internal conversion process to S
1
level. The excess energy is dissipated by
vibrational interactions giving rise to evolution of heat. At the S
1
level there are
three possible ways that the excited state becomes deactivated. The return to the
ground state from the triplet one requires again an inversion of the spin. In
Figure 1.3., a and a’ represent the energies of light absorbed , b, h, and i the
energies of internal conversion, c represents return to the ground state by way of
fluorescence and d return by way of phosphorescence.
The Franck-Condon principle helps the understanding of the electronic
transitions. In simple terms, what it states is that during an electronic transition
the various nuclei in the molecule do not change their position or their moment.
9
What it means is that electronic transitions are much more rapid (10
-15
sec.) than
nuclear motions (10
-12
sec.) so that immediately after the transitions the nuclei
have nearly the same relative positions and velocities that they had just before
6
electron
Light-Associated Reactions of Synthetic Polymers
1. Introduction
the transitions. The energy of various bonding and antibonding orbitals increases
for most molecules in the following order,
o < t < n < t- < o-
In molecules with heteroatoms, such as oxygen or nitrogen, however, the highest
filled orbitals in the ground state are generally nonbonding, essentially atomic,
n orbitals. This is a case with ketones and aldehydes. These molecules possess
electrons that are associated with oxygen that are not involved in the bonding of
the molecule, the n-electrons
C O
H
H
n-electrons
Whether n electrons will be promoted to either o* or t* antibonding orbitals
As explained above, in the triplet state the spin of the excited electron
becomes reversed. This results in both electrons having the same spin. From
purely theoretical approach, such an electronic configuration is not allowed. Due
to the fact that the excited electron cannot take up its original position in the
ground state until is assumes the original spin, the triplet state is relative long
lived. For instance, in benzophenone at 77
o
C the lifetime can be 4.7x10
-3
seconds. Orchin and Jaffe wrote
7
that the triplet state has a lifetime of 10
-3
seconds. By comparison, the lifetime of a singlet state is about 10
-8
to 10
-7
seconds. Also, in the triplet state the molecule behaves as a free-radical and is
very reactive. The carbon atom has a higher electron density in the excited state
than in the ground state. This results in a higher localized site for photochemical
excited state is electron deficient, it reacts similarly to an electrophilic alkoxy
radical. It can, for instance, react with another molecule by abstracting
hydrogen. This is discussed further in Chapter 2.
At higher frequencies (shorter wavelength) of light, if the light energy
is sufficiently high, t ÷÷ t* transitions can also take place. All aromatic
compounds and all conjugated diene structures possess delocalized t systems.
Because there are no n electrons, all transitions in these systems are t ÷÷ t*.
In general, the excited states of molecule are more polar than the ground states.
Polar solvents, therefore, tend to stabilize the excited state more than the ground
state. As shown in Figure 1.2, the triplet state is lower in energy that the
corresponding singlet state. This is due to the fact that the electron-electron
repulsion is minimized, because they do not share each other’s orbitals as stated
by the Pauli exclusion principle Thus less energy is required for the triplet state.
7
depending upon the structure of the carbonyl compound.
activity at the orbital of the oxygen. Because the carbonyl oxygen in the
The chemical reactivity of organic molecules is determined principally
by the electron distribution in that molecule. When the electron distribution
changes, due to absorbtion of light and subsequent transitions, photochemical
reactions take place while the molecule is in an electronically excited state. The
phenomenon of light absorption, formation of the excited states and subsequent
reactions obey four laws of organic photochemistry, as was outlined by Turo
3
:
1. Photochemical changes take place only as a result of light being absorbed
by the molecules.
2. Only one molecule is activated by one photon or by one quantum of light.
3. Each quantum or photon which is absorbed by a molecule has a given
probability of populating either the singlet state or the lowest triplet state.
4. In solution the lowest excited singlet and triplet states are the starting
points for the photochemical process.
The relationship between the amount of light or the number of photons
absorbed and the number of molecules, that, as a result, undergo a reaction, is
defined as the quantum yield, u. It is defined as the number of molecules
involved in a particular reaction divided by the number of quanta absorbed in
the process.
1,3
Another fundamental law of photochemistry was formulated by
Grotthus and Draaper.
12
It states that only the light that is absorbed by a
molecule can be effective in producing photochemical changes in that molecule.
There is also a fundamental law of photochemistry that states that the absorption
of light by a molecule is a one-quantum process, so that the sum of the primary
processes, the quantum yield must be unity.
12
Also, the law of conservation of
energy requires that the sum of the primary quantum yields of all processes be
equal to unity. Mathematically this can be expressed as :
u
total
= _
i
u
i
= 1
Where u is the quantum yield. The quantum yield of photochemical reactions is
important because it sheds light on the mechanisms of reactions. The number of
molecules involved in a particular photoreaction can be established by an
analytical kinetic process and the number of quanta absorbed can be measured
with the aid of an actinometer. The quantum yield can also be expressed in
general kinetic terms
1
:
u
i
= |
ES
|
R
P
i
or u
I
= _
j
|
i
ES
|
j
R
P
j
i
The above equations signify that a quantum yield of a particular photoprocess is
the product of two or three distinct probabilities. These are: |
ES
, is the
probability that the excited state will undergo the primary photoreaction
necessary for the process. The probability that any metastable ground state
intermediate will proceed to stable products is P
i
and the probability that the
8
Light-Associated Reactions of Synthetic Polymers
1. Introduction
excited state will undergo the primary photoreaction necessary of the process is
|
R
.
The concept that matter can only acquire energy in discrete units
(quanta) was introduced in 1900 by Max Planck.
2
The corollary of the
quantization of energy is that matter itself must be quantized i.e., constructed of
discrete levels having different potential energies. Occupying these particular
levels are electrons that obviously possess the energy of the level which they
occupy. In a molecule the intramolecular motions of the electrons and the
associated molecular electronic levels must be taken into account. There are, in
addition to electronic levels, modes of vibration and rotation that are also
quantized. In other words, the absorption of a photon of light by any molecule is
a reaction of light with an atom or a group of atoms that must promote
transitions between quantum states. This requires two conditions. These are: (1)
for a molecular state m with energy E
m
there must be a state n of higher energy
E
n
so that hv = E
n
- E
m
; (2) there must be specific interaction between the
radiation and the light absorbing portion of the molecule that results in a change
in the dipole moment of the molecule during the transition. If we designate the
wave functions of the states m and n as ¢
m
and ¢
n
respectfully then the
transition moment integral that may not equal to zero, is:
R
mn
= (¢
m
/ P¢
n
)
where P is the electric dipole operator. It has the form of P = e_r
i
, where e is the
electronic charge and r
i
is the vector that corresponds to the dipole moment
operator of an electron i.
The increase in the energy of a molecules as a result of absorbing a
quantum of radiation can be expressed in the relationship
3-5
:
AE = hC / ì
where ì is the wavelength of the interacting radiation. All reactions that are
photochemical in nature involve electronically excited states at one time or
other. Each one of these states has a definite energy, lifetime, and structure. The
property of each state may differ from one to another and the excited states are
different chemical entities from the ground state and behave differently. The
return to the ground state from the excited state, shown in Figure 1.3. can take
place by one of three processes
3-5
:
(1) The molecule returns directly to the ground state. This process is
accompanied by emission of light of a different wavelength in the form of
fluorescence.
(2) An intersystem conversion process takes place to the T
1
state, where the
electron reverses its spin. The slower decay of excitation from the triplet state to
the ground state is accompanied by emission of phosophorescence.
9
(3) The molecule uses the energy of excitation to undergo a chemical reaction.
This dissipation of the excitation energy can also be illustrated as follows:
A
0
+ light
A*
A
0
+ fluorescence
A
0
+ heat
chemical reaction
where, A
O
represents any organic molecule and A* represents the same
molecule in an excited state.
In the process of energy dissipation from the singlet and return to the
ground states, the light emission by fluorescence is at a different wave-length
than that of the light that was absorbed in the excitation. This is because some
energy is lost in this process of the electron returning from its lowest excited
state to the ground state. The energy, however, may also, depending upon the
structure of the molecule, be dissipated in the form of heat, as shown above.
And, also, a third form of energy dissipation can occur when the molecule
undergoes a chemical reaction. Depending, again on the molecular structure, the
chemical reactions can be rearrangement, isomerization, dimerization (or
coupling), fragmentation, or attack on another
9-11
molecule. Some examples of
such reactions are:
hv
hv
hv

10 Light-Associated Reactions of Synthetic Polymers
1. Introduction
UV light
2
hv
N
O
R
CHO
H
3
C
NO
2
light
dark
R
CH
3
H
3
C
O
NO
2
Many other examples can be found in the literature. Most familiar isomerization
reaction is that of cis-stilbene to trans-stilbene, shown above. It was observed
that the quantum yield of stilbene cis-trans isomerization decreased with an
increase in viscosity of the medium.
8
In addition, it was also found that in a
polymeric matrix the photoisomerization is not inhibited, provided that it occurs
above the glass transition temperature of the polymer. An example of a
fragmentation of a molecule is the decomposition of disulfides upon irradiated
with ultraviolet light of the appropriate wavelength:
S S
hv
S
2
The same reaction takes place in peroxides. Ketones and aldehydes cleave by
the mechanism of the Norrish reaction.
11
1.4. Energy Transfer Process
The energy of excitation can transfer from an excited molecule to
another molecule. Thus, the term energy transfer
12,13
refers specifically to one-
step radiationless transfer of electronic excitation from a donor molecule to
another, qualified, acceptor molecule, from one chromophore to another one.
This excludes what is referred to as, trivial energy transfers that result from the
donor emitting light that is subsequently absorbed by an acceptor. Based on the
energy and spin conservation laws, there are two a priori requirements for
efficient energy transfer: (1) the process must be thermoneutral or exothermic to
occur with highest efficiency, because the activation energies have to be low
due to short lifetimes of electronically excited state, and (2) no net spin
changes should occur. If a donor molecule was in the triplet state at the time of
the energy transfer process, the acceptor molecule is then also promoted to the
triplet state. Transfer of singlet to singlet energy should be possible, but it occurs
less frequently, because of the shorter life times of the singlet states.
12,13
Energy transfer, is thus the process by which excitation energy passes
from one photoexcited molecule, often referred to as a sensitizerand in this
case designated as S*, to another adjacent molecule in its ground state, often
referred to as a quencher, in this case designated as Q. The quencher must have
a thermodynamically accessible excited state, one whose energy is lower than
that of S*. A donor molecule must possess sufficiently long lifetime to be an
efficient sensitizer. The reaction of energy transfer can be illustrated as follows:
S*+ Q ÷÷ S + Q*
S* ÷÷ S
0
+ hv
where * designates an excited state. In the process of energy transfer, S* returns
(or relaxes) to the ground state S. Energy transfer is further categorized as
involving singlet (paired electron spins) or triplet (unpaired electron spins)
states. Symmetry rules, as explained above, require a singlet S* to produce a
singlet Q* and a triplet S
3+
to produce a triplet Q
3+
.
The quenching reaction of the excited state is expressed in a equation
by Stern-Volmer. The reaction shown below is based on a quenching reaction
that is accompanied by a release of heat:
S* + Q ÷÷ Q* + S
0
(k
2
)
S* ÷÷ S
0
+ heat (k
3
)
12 Light-Associated Reactions of Synthetic Polymers
1. Introduction
The equation is written as follows:
u
0
/ u
Q
= {k
1
+ k
2
[Q] + k
3
} / (k
1
+ k
3
)
In experimental studies of energy transfer it is convenient to express the
experimental results in an other form of the Stern-Volmer equation, as follows,
u
0
/ u
Q
= 1 + k
q
t [Q]
where u
0
is the quantum yield for a particular process in the absence of a
quenching molecule,
u
Q
is the quantum yield of the quenched process
k
q
is the bimolecular rate constant for the quenching process
t is the lifetime of the state in the absence of a quenching molecules. It is
equal to 1 / (k
1
+ k
3
), and [Q] is the concentration of the quenching molecules.
Two processes were proposed to explain the mechanism of energy
transfer. In the first one, energy transfers result from the interactions of the
dipole fields of the excited donors and ground state acceptor molecules (long-
range: Forster (dipole-dipole))
5, 9
. This is referred to as the resonance transfer
mechanism. Such transfer is rapid when the extinction coefficients for
absorption to the donor and acceptor excited states involved in the process are
large (10
4
to 10
5
at the maximum). When the dipolar interactions are large,
resonance transfers are possible over distances of 50-100 Å. Close proximities
of donors and acceptors, however, are required for weakly absorbing molecules.
In the second mechanism
9
(short-range: Dexter (exchange)), the excited donor
and acceptor are in very close proximity to each other, (up to ~ 15 Å) such that
their electronic clouds overlap slightly. In the region of the overlap, the location
of the excited electron is indistinguishable. It may be at any one instant on either
the donor or acceptor molecule. Should the pair separate when the excited
electron is on the acceptor molecule, energy transfer has been achieved by the
mechanism of electron transfer.
Both absorption and emission processes may be intramolecular,
localized in a single molecule. On the other hand, they can also involve whole
crystals that may act as absorbers and emitters. Such energy transfers can
manifest themselves in different ways that include sensitized fluorescence or
phosphorescence, concentration depolarization of fluorescence, photo-
conduction, and formation of triplet acceptor molecules.
Intermolecular energy transfer can be electronic and vibrational, and
can take place in solid, liquid and gaseous phases. In addition, the sensitized
excitation of Q by S* has to take place within the time that the molecule S
remains in the excited state. In summary, theoretical and empirical
considerations suggest two modes of transfer, described above:
1. Only when the two molecules are in very close proximity to each
13
other and their centers are separated by the sum of their molecular radii will
transfer take place.
2. When the two molecules are at distances that exceed their collision
diameters, resonance transfer, or long range electronic excitation takes place
though Coulombic interactions.
The transfers that take place by mechanism 1 are limited by diffusion
of molecules in solution and should be affected by the viscosity of the medium.
Transfers by mechanism 2, on the other hand, should be much less sensitive to
the viscosity of the medium It was shown by Foster
5
that the rate constant of
resonance-energy transfer (mechanism 1), as a function of distance, is:
Rate Constant (S* ÷ Q*) = 1(R
o
/R)
6
/t S
where t S is the actual mean lifetime of S*, R is the separation between the
centers of S* and Q, and R, is the critical separation of donor molecules and the
acceptor molecule. The efficiency of energy transfer is expressed by Turro,
Dalton, and Weiss
13
as follows:
u
et
= k
et
[S*][Q] / {k
et
[S*][Q] + k
d
[S*]}
The transfer by long range excitation or mechanism 2 can be in the
form a singlet-singlet transfer, a triplet-singlet transfer, and a triplet-triplet
transfer. Due to the fact that the lifetime of triplet state of molecule is longer
than the singlet one, it is more probable to be the one to participate in energy
transfer. Molecules that undergo intersystem crossing with high efficiency, like
benzophenone, are efficient triplet sensitizers. Such molecules must possess
high energy in the triplet state and a life time of at least 10
-4
seconds.
The two types of intermolecular energy transfers can be expressed as
follows:
Forster (dipole-dipole) long-range: k
SQ
(R) = k
S
0
(R
0
SQ
/R)
6
Dexter (exchange) short-range: k
SQ
(R) = k
SQ
0
exp(-oR)
The nomenclature that was developed in connection with energy and charge
transfer processes is as follows, an eximer is a transient dimer formed by the
combination of an excited (usually aromatic) molecule and a second similar
(usually unexcited) molecule. Such a dimer bonds only in the excited state and
promptly dissociates in losing its excitation energy. The term exiplex was
explained by Birks
11
to describe a complex between two molecules, one a donor
and the other one, an acceptor, which subsequently dissociate in a deactivation
process. One of the components of the exiplex, either the donor or the acceptor,
is in excited state while the counterpart, acceptor or donor are is in the ground
state. An eximer is then just a special case in which the two constituent
14 Light-Associated Reactions of Synthetic Polymers
1. Introduction
molecules are identical. While numerous charge-transfer complexes can form
between certain molecules in the ground state, a number of compounds can form
only charge-transfer complexes when either the donor or the acceptor is in an
excited state . Formation of eximers was observed in a number of aromatic
polymers, such as polystyrene, poly(vinyl naphthalenes), poly(vinyl toluene)
and others.
12
An exterplex is composed of three molecules and often takes an
important role in pbotophysical and photochemical processes. Polymers with
pendant aromatic chromophores and dimeric compounds often show efficient
exterplex formation due to high local chromophore concentration in their
structure. It was observed that exiplex emission spectra from a chromophore is
usually broad, structureless, and red shifted to the corresponding monomer
fluorescence. The extend of such a shift is a function of the distance between the
two components of the complex. It is also strongly affected by the polarity of the
media. Martic et al.,
14
obtained emission spectra of the exiplexes of anthracene
and N,N, dimethyl-p-toluidine in toluene and in polystyrene. While the
maximum band of the emission spectra in toluene at 30
o
C is at 616 nm, in
polystyrene it is shifted to 400 nm. The exiplex emission spectra in a copolymer
of styrene with 4-N,N-diaminostyrene is at 480 nm. The maxima of the
emission spectra are temperature dependent. The maxima shifts in toluene
to longer wave length with an increase in temperature. The maxima approaches
common value at the glass transition temperature of polystyrene. Similar results
were reported by Farid et al.,
15
who studied formation of exiplexes of 4-(1-
pyrenyl)butyrate in different solvents and in polymers.
Chemical and physical changes take place in molecules when they
absorb energy and reach and excited state. This is particularly true of carbonyl
compounds. There is a change in the dipole moments of the molecules. This is
due to the fact that dipole moments depend upon the distribution of the
electrons. In carbonyl compounds this change is particularly large. Also the
geometry of the molecule changes from the ground to the excited states. In
addition, the chemical properties of the molecules change. Thus phenol, for
instance, is a weak acid, but in the excited state it is a strong acid. This can be
attributed to the ʌ ÷÷ ʌ* transition where one of the pair of ʌ electrons is
promoted to an anti bonding orbital.
By the same reason, the acid strength of benzoic acid is less than in the
excited state because the charge in this case is transferred to carbonyl group. The
excited states of both phenol and benzoic acid can be illustrated follows
12
:
15
solution to shorter wave length and in polystyrene it is the opposite, it shifts
OH
+ light
OH
C
O
OH
+ light
C
O OH
1.5. Electron Transfer Process
Simple migration of energy is a thermodynamically neutral process. It
allows the excitation energy deposited at a site in a solid or in a concentrated
solution to move to another position by transferring the excitation energy in the
absence of an intermediate quencher. Electron transfer, however, is a process by
which an electron is passed from an electron-rich donor to an electron-deficient
acceptor.
12
This reaction is substantially accelerated when the donor or acceptor
is excited. Electron transfer from an excited-state donor molecule D* to a
ground-state acceptor A generates a radical cation D
+
- and a radical anion A
÷
-.
The resulting radical ion pair exists as a charge-separated pair of ions:
D* + A ÷÷ D
+
- + A
÷
-
The oxidized and reduced species are usually highly energetic, storing a
substantial fraction of the energy absorbed from the photon. The charge
separation that occurs in such a photoinduced electron transfer provides a way to
convert the excitation energy of the excited molecule to a chemical potential in
the form of a radical ion pair.
Electron migration can also be a movement of an electron either to a
neutral electron donor from an oxidized one (D + D- ÷÷ D- + D) or from a
reduced acceptor to a neutral one (A- + A ÷÷ A + A-).
12
These thermoneutral
processes, that are called hole and electron migrations, respectively, permit
further spatial charge separation between an excited donor, D* and a reduced
acceptor, A- . This separation is beyond one that is initially produced in an ion
sensitizer, the energy migrations or the energy transfer moves the excited state
16
pair by photoinduced electron transfer. After the absorption of light by A to A
-

Light-Associated Reactions of Synthetic Polymers
1. Introduction
site where the excitation energy is converted to a radical ion pair by photo
induced electron transfer. A kinetic competition then takes place between the
rates of several possible next steps. These steps can be chemical reaction of the
radical ions, or they can be further charge migrations by sequential electron or
hole transfers, or actually nonproductive charge recombination, called back-
electron transfer. The back-electron transfer regenerates the ground states of
both the donor and the acceptor.
1.6. The Charge Transfer Processes in Polymeric Materials
Charge transfer in polymers is either electronic (transfer of electrons or
of positive charges alone) or it is ionic (transfer of protons or larger charged
species). Electronic conduction can be also of two types. One type is conduction
due to diffusion of electrons that are not localized on any particular molecule
(this is usually found in liquids or in gases). The other type can be by conduction
due to positive or negative charges that are localized on any particular part of the
molecules. Such charges can be exchanges between like polymeric molecules
(or between segments of single polymeric molecules). This can occur without
any net energy loss (resonant charge transfer). It was shown experimentally that
the electrical conductivity in many polymeric materials, subjected to short
irradiation pulses, consists initially of a “prompt” component. That means that
very rapid transfer of a considerable amount of charge takes place over a
comparatively short distance (~ 100 Å ). The movement of the charge is then
terminated as a result of trapping in “shallow” traps.
9,12,16
This is followed by a
“delayed” component that is very temperature dependent and probably indicates
a thermally activated charge-hopping process between the shallow traps. This
continues until terminated (after ~ 1 µ) by trapping in deep traps or by
recombination.
9,12,16
There is a major difference between eximers of polymers and those of
small molecules. The difference is that at least in some polymers a large part of
the excitation of the excimer site appears to be a result of singlet energy
migration.
12
Also, in polymeric materials with a number of identical
chromophores, either in the backbone or as pendant groups, when photons are
absorbed, the excited states cannot be considered as localized. In simple cases of
rigid lattices the excitations are distributed over the entire volume of the material
as a wave-like linear combination of local excitations.
7, 9,10,13
They are referred
to as tight-binding excitations.
9.10,13
As one might expect, excimer formations in
polymers depend upon the properties of the chromophores and upon their
location on the polymeric chain.
9
In addition, polymer tacticity, conformation,
and distance between chromophores can greatly affect the formation of eximers.
Also, it is possible to distinguish between two different types of energy transfers
in polymeric materials In the first one the transfer of excitation can take place
either from or to large molecules from small ones. Thus, for instance, a polymer
transfer of the excitation energy can be localized from a chromophore on one
17
polymeric chain to another. An example of a transfer to a small molecule is an
energy transfer from a polymer, like polystyrene to a scintillator molecule, like
1,4-bis[2-(5-phenyloxazolyl)]benzene shown below
14
:
O O
More than that, transfer can also take place from one group of atoms, or from a
chromophore, located on a polymeric chain in one section of the molecule,
intramolecularly, to another one located at another section of the same polymer.
Thus, in copolymers from monomers with two different chromophores groups,
the energy absorbed by one group of chromophores can be transferred to the
chromophores from the other group. This can take place by either Foster or
exchange mechanism. The possibility of energy transfer from one chromophore
to an adjacent different chromophore in polymeric chains depends to a large
extent upon the lifetime of the excitation and its alternative modes of
deactivation. For this reason the most readily observed form of energy migration
is one that occurs through the mechanism of the triplet.
7,9,12,16
Intermolecular energy transfer from one polymeric material to another
while the molecules are in solution or in the melt can also take place.
17
This was
demonstrated on an intramolecular excimer and exiplex formation in solutions of
polyesters containing naphthalene or carbazole moieties in their chemical
structures
17
:
O C
O
C
O
O CH
2
C
CH
3
(CH
2
)
CH
2
O
x
N
n
In general, the migrations of energy in polymers is somewhat more
complex, because chain folding and conformations are additional factors that
enter into the picture. The separation between interacting units can be affected
by the composition of the polymer, the geometry of the polymeric chains, and
the flexibility of the backbones.
18
18 Light-Associated Reactions of Synthetic Polymers
1. Introduction
There are two limiting cases for the effects of polymer folding on
energy-transfer efficiency. Folding of a polymer before excitation into a
conformation in which the sensitizers are held within a hydrophobic pocket
improves the efficiency of energy migration when a large number of
intramolecular hops or through bond interactions intervene between the
sensitizer and the ultimate trap.
12
If the polymers are flexible, however, they can
also bend after photoexcitation to bring otherwise distant chromophores close
enough so that energy can hop from one to the other, skipping intervening units
and thereby considerably shortening the effective migration distance along an
individual polymer chain.
12
For flexible polymers in solvents that promote
folding, this motion can take place even faster than excited-state decay.
18
Intramolecular singlet energy migration can also proceed via electronic
coupling through the bonds that form the polymer backbone. In a random walk,
the excitation energy migrates without directional control, moving back and
forth along a chain or across space. Through-space interactions between pendant
chromophores are also common in polymers with large numbers of absorbing
units.
18
One should also include movement of excitation across folds or loops
that can form in polymeric chains. Such folds can be the result of packing into
crystalline domains or simply from temporary collisions.
In principle, the excitation can be localized for some finite time
(however small) on a particular chromophore before it is transferred to another
one in the chain. Guillet defines intramolecular energy migration as any process
that involves more than one exchange of excitation energy between
spetroscopically identical chromophores attached by covalent bonds to a
polymeric chain.
12
He further terms “energy transfer” as a single step migration
between two chromophores, while one that involves several or more
chromophores as “energy migration”.
12
The, polymers with multiple sensitizers offer several routes for energy
migration This can be illustrated as follows
18
:
Route A Route B
A very common arrangement is for the photosensitive groups to be aligned
to each other for energy transfer. Also, as mentioned earlier, folding of a
polymer before excitation into such a conformation that the sensitizers are held
19
outside of a spiral arrangement of the polymeric chain in close enough proximity
within a hydrophobic pocket improves the efficiency of energy migration with
a large number of intramolecular hops. Efficiency of energy migration is also
helped through-bond interactions that intervene between the sensitizer and the
ultimate trap.
18
Also, as mentioned before, flexible polymer frameworks can
bend the polymeric chains in such a manner as to bring otherwise distant
chromophores close enough together so that after excitation the energy can hop
from one to another. In such a case the energy migration can skip intervening
units and thereby considerably shorten the effective migration distance along a
single polymer chain. As stated above, for flexible polymers in solvents that
promote folding, this motion can be even faster than excited-state decay.
18
Intermolecular energy migration can also occur between two different
polymeric molecules. Thus, for instance, Turro and coworkers investigated
inter- and intramolecular energy transfer in poly(styrene sulfonate). They found
that excimer formation between adjacent phenyl groups is a dominant reaction
both along a single chain and between two different chains.
13
At low densities
of excited states, singlet energy transfer between a sensitizer and its nearest
quencher (perhaps on another chain) dominates, whereas at high excited state
densities, energy migration takes place through the series of donors.
18
Webber reports that he uses the following equation (that he calls crude
but useful) to obtain rough estimates of the energy migration diffusion rate along
the polymer backbone
18
:
k
q
= 4t N
0
(D
Q
+ ^
g
)PR / 1000
where D
Q
is the normal diffusion constant of the quencher and k
g
is the energy
migration diffusion rate along the polymer.
In some aromatic vinyl polymers excimer emission can occur after an
initial excitation of an aromatic chromophore. This is followed by
intramolecular singlet energy migration, either along the polymer chain, or
intermolecularly along the chromophores. Here too, it can be to different chains
in a polymer that is in bulk and the chains are in close proximity to each other.
The process generally continues until the excitation is trapped at some chain
conformation that is suitable for excimer formation. Such a chain conformation
is referred to as eximer-forming site. If the polymer is in solution and viscosity is
low, interconversion of chain conformations proceeds fairly rapidly. In such
cases the lifetimes of any particular conformation is limited by the collision
processes as well as by the magnitude of the rotational barriers with respect to
thermal energy.
12
In the solid state, however, the rotational freedom of the
polymeric chain is considerably reduced. Large scale conformational changes
are unlikely. There still is the possibility, however, that adjacent chromophores
will be in a marginal eximer forming site.
13
The carbazole molecule is a good example of a chromophore that
readily forms excimers. This makes polymers that bear carbazole moieties
useful as photoconducting materials . It is described in Chapter 5.
20
Light-Associated Reactions of Synthetic Polymers
1. Introduction
It was originally observed by Schneider and Springer
19
that efficient
fluorescence occurs from small amounts of acenaphthalene that is
copolymerized with styrene. Fox and coworkers
18
observed the same effect in
a copolymer of styrene with small amount of vinyl naphthalene. The emission of
naphthalene fluorescence is much higher than from solution of a mixture of the
two homopolymers. It was suggested by both groups that this phenomenon is
due to energy migration between styrene sequences to the naphthalene moieties.
Guillet and coworkers carried out quantitative studies of this phenomenon with
various polymers that contained naphthalene or phenanthrene as the donors and
anthracene as the trap.
12
This effect is similar to one observed in ordered
chlorophyll regions of green plant chloroplasts (antenna chlorophyll pigments).
It was, therefore, named the antenna effect.
Work by Guillet demonstrated that the effect is not entirely due to
energy migration among the chromophores that form the antenna, but rather a
combination of migration and direct Forster energy transfer to the trap.
12
Guillet
concluded that energy migration and transfer in such systems are primarily due
to long-range Forster transfer by dipole-dipole mechanism (discussed earlier). In
the absence of any trap in the polymer the energy will migrate along the
backbone of the polymer chain until it is deactivated by some other processes. In
the presence of a singlet energy trap, the lifetime of the excitation will be
reduced and the length of energy migration will be reduced. The difference
between this form of energy transfer and one observed in solid aromatic
polymers is that the photon energy is collected within a single polymer molecule
and all energy transfer is intramolecular. The antenna effect permits collection
of the photon energy from the entire region of space (the hydrodynamic volume
of the polymer) and transmitting it to the traps located on the polymer chain.
The efficiency is relatively independent of concentration and can be very
efficient even in dilute solutions.
12
References
1. J.G. Calvert and J.N. Pitts, Photochemistry, Wiley, New York, 1967
2. F.K. Richtmeyer and E.H. Kennard, Introduction to Modern Physics,
McGraw-Hill, New York, 1947
3. N.J. Turo, Molecular Photochemistry, W.J. Benjamin/Cummings, New York
5. Cowan and Drisko, Elements of Organic Photochemistry, Plenum,
NewYork, 1978
4. Rohatgi-Mukherjee, Fundamentals of Photochemistry, Wiley, New York,
1978
21
1.7. The Antenna Effect in Polymers
5. T. Foster, Disc. Faraday Sec., 1959, 27, 1; Radiation Research,
Supplement, 1960, 2, 326 (1960); S.E. Webber, Chem. Rev., 1990, 90,
1460-1482
6. W.J. le Noble, Highlights of Organic Chemistry, Dekker, New York, 1974
7.
Miffin Co., Boston, 1967
8. D. Gegiou, K.A. Muszkat, and E. Fischer, J. Am. Chem. Soc., 1968, 90, 12
9. R. Srinivasan, J. Am. Chem. Soc., 1964, 86, 3318 ; K.E. Wilzbach and L.
Kaplan, J. Am Chem. Soc., 1964, 86, 3157; D. Schulte-Frohlinde, Ann.,
1958, 615, 114
10. A.S. Davydov, Theory of Molecular Excitations, McGraw Hill, New York,
1962; R.S.H. Liu and G.S. Hammond, J. Am. Chem. Sec., 1964, 86, 1892
11. J.B. Birks, Photophysics of Aromatic Molecules, Wiley-Interscience,
London, 1970
12. J. Guillet, Polymer Photophysics and Photochemistry, Cambridge
University Press, Cambridge , 1985
13. N.J. Turro, J.C. Dalton, and D.S. Weiss in Oranic Photochemistry, O.L.
Chapman, ed., Dekker, New York, 1969
14. P.A. Martic, R.C. Daly, J.L.R. Williams, and S.Y. Farid, J. Polymer Sci.,
Polym. Lett. Ed., 1977, 15, 295
15. S. Farid, P.A. Martec, D.R.Thompson, D.P. Specht, S.E. Hartman, and
J.L.R. Williams, Pure. Appl. Chem., 1979, 51, 241
16. T.J. Meyer, "Photoinduced Electron and Energy Transfer in Soluble
Polymers," Coord. Chem. Rev., 1991, 111, 47; W.G. Herkstroeter, Chapter
1, Creation and Detection of the Excited State, A.A. Lamola, ed., Dekker,
New York, 1971
17. S. Tazuke and Y. Matsuyama, Macromolecules, 1975, 8, 20; ibid., 1977, 10,
215
18. M.A. Fox, W.E. Jones Jr., D.M. Watkins, Chem. and Eng. News, 1993,
(March 15), 18
19. F. Schneider and J. Springer, Makromol. Chem. 1971, 146, 181
22
M. Orchin and H.H. Jaffe, The Importance of Antibonding Orbitals, Houton
Light-Associated Reactions of Synthetic Polymers
Chapter 5
light irradiation by undergoing reversible changes in their chemical structures
and/ or their physical properties. Also, photochromism refers to the
photoinduced reversible transformations in chemical compounds between two
electronic states characterized by different absorption spectra.
1
There are many
ways in which the photoresponsiveness of polymers can manifest itself. One
might observe changes in viscosity of polymeric solutions, in contraction of
polymeric chains, in sol-gel transitions, in electrical conductivity, or even in
color changes as a result of irradiation with light of an appropriate wavelength.
Another interesting manifestation of photoresponsiveness in some special
polymers is a change in the permeability to gases in films. These changes can
and are utilized in many ways. Thus, for instance, structural changes due to
isomerization are employed to align liquid crystals and photoconductivity is
utilized in xerography. Over the last two decades, the photoresponsive materials
have grown in practical and scientific importance, because such materials are
useful in many applications.
5.1. Polymers for Harvesting Sun’s Energy
5.1.1. Polymers with Norbornadiene Moieties
A different approach to harvesting light energy, however, is to utilize
pendant groups that reversibly absorb light energy, rearrange, and then release
this absorbed energy in a rearrangement back to the original structure. To that
end, research is going on in various laboratories to develop systematically
derivatized polymer arrays than can collect and convert light energy. Among
these, photorearrangements from norbornadiene to quadricyclane are back are
246
Photoresponsive Polymers
Photoresponsive polymers are materials that are able to respond to
The goal of harvesting light energy has led to research in polymeric
materials that could potentially mimic photosythesis. In such materials, the
choice of chromophores is the most critical variable. The location of the
chromophores on the polymeric chains and the tacticity of the polymers are also
very important. Weber points out, for instance, that among a number of
chromophores attached to polymeric chains naphthalene and carbazole form
very stable eximers, while phenanthrene and diphenyl anthracene do not.
2
At
present, many polymeric materials are known and utilized in the vast areas of
sive materials for displays and others. Fox and coworkers concluded, however,
mers
for photosynthesis.
3
nonsilver based imaging, information storage, remote sensing, electrorespon-
that noncompare in efficiency to naturally occurring photon harvesting poly
247
(about 96 kJ/mol) in a quadricyclane molecule and later recovered
4
ultraviolet light
> 310 nm
250 nm
This photoisomerization reaction is referred to as a valence
isomerization. It is a reaction in which electron reshuffling occurs and the nuclei
move to make or break new t and o bonds. A number of polymers were,
therefore, prepared with the norbornandiene moieties either in the backbone or
as pendant groups. Among them are polyesters that were synthesized with
donor-acceptor norbornadiene residues in the main chain
53
by polyaddition of
5-(4-methoxyphenyl)-l,4,6,7,7-pentamethyl-2,5-norbornadiene-2,3-dicarboxylic
acid or 5,6-bis(4-methoxyphenyl)-7,7-dimethyl-2,5-norbornadiene-2,3-
dicarboxylic acid, with bis(epoxide)s. This preparation of such polymers and the
accompanying photorearrangements can be illustrated as follows:
R'"
COOH
COOH
R'
R"
R'"
+
O
O
R""
O
O
O
O
R'"
O
O
O
R""
O
R' R"
R'"
OH OH
n
n
R' R"
R'"
R'"
O
O O
O
O
R""
O
OH OH
5. Photoresponsive Polymers
of considerable interest, because photoenergy can be stored as strain energy
248
The photorearrangements of the norbornadiene residues in the resulting
polyesters were observed to proceed smoothly to the quadricyclane groups.
Also, it was found that the norbornadiene residues in these polyesters show
resistance to fatigue in repeated cycles of the interconversions.
4
The goal to utilize photochemical valence isomerization between
norbornadiene and quadricyclane for solar energy collection and storage was
reported by others.
5
Nagai and coworkers synthesized five different polymers
with trifluoromethyl-substituted norbornadiene moieties in the side chains and in
the main chain
5
:
n
S
O
O
CF
3
CF
3
CF
3
n
O
O
OH
O
O
S
CF
3
CF
3
CF
3
n
S
O
O
O
CF
3
CF
3
CF
3
S
O
S
N
O
N
H
n
H
S
O
S
O
O
(CH
2
)
6
n
Light-Associated Reactions of Synthetic Polymers
249
All or the above polymers exhibit large absorption bands in the visible region of
the spectra and the norbornadiene moieties in these polymers isomerize very
rapidly. In addition, the norbornadiene moieties also exhibit efficient fatigue
resistance.
5
Kawatsuki
6
synthesized styrene polymers with pendant
norbornadiene groups attached via amide linkages:
CH
2
CH
NH C
O
C
R
O
n
where R is a methoxy or a ring substituted aniline group attached through the
nitrogen or through another position. These pendant groups also undergo
reversible conversions into quadricycline units in polymer films when irradiated
by ultraviolet light of two different wavelengths. The materials exhibit high
photosensitivity as well as a large red shift in the absorption spectrum upon
irradiation.
Sampei et al.,
7
reported that polyaddition of 2,5-norbornadiene-2,3-
dicarboxylic acid diglycidyl ester to adipoyl chloride gave a polyester containing
norbornadiene residues in the polymer backbone and in the pendant groups.
When a photochemical rearrangement of norbornadiene residues took place in
polymer films, the rate of the photochemical reactions in the polymer
backbones was higher than that in the side chains.
7
5.1.2. Polymers with Pendant Spiropyran Groups
An entirely different approach was taken by Rodriguez-Cabello and
et al.
5. Photoresponsive Polymers
Kawashima, et al.,
8
reported preparation of donor-acceptor type
norbornadiene carboxylic acids compounds with carbamoyl groups, such as
dipropylcarbamoyl, methylphenylcarbamoyl, propylcarbamoyl, and phenyl-
carbamoyl. Benzyl esters were also prepared. Addition of these groups to
polystyrenes formed polymers with pendant donor-acceptor type norbornadiene.
Some were formed with 100% substitution. It was found that the polymers
containing phenylcarbamoyl groups exhibits especially high photoreactivity. In
addition, the rate of the photochemical reaction in films of these norbornadiene
polymers increases efficiently by an addition of 4,4'—bis(diethyl-amino)
benzophenone photosensitizer. As a result, all the norbornadiene groups of the
polymers isomerize to the quadricycline groups in as little as 20 seconds. The
stored thermal energy of the irradiated polymers was found to be 32-52 kJ/mol.
250
coworkers
5
They prepared a molecular-scale machine that converts light into
mechanical work. The system uses a polypeptide modified by spiropyran and
undergoes transitions from reversible coil to o-helix when exposed to light.
Irradiating this polymer with UV light causes ring-opening reactions of the
spiropyran group and formation of charged species. The reactions are reversible
in sunlight to reform the spiropyran ring structure. Attaching as few as 2.3
spiropyran groups per 100 amino acid residues allows clear photomodulation of
the material. The reactions can be illustrated as follows:
N
O NO
2
O
O
Gly
NH
NH
Gly
O
Pro
Val
Dark or UV
sunlight
N
NO
2
OH
O
O
Val
Pro
Gly
NH
NH
Gly
O
5.1.3. Novel Approaches to Light Energy Harvesting Polymers
Groups, like 6-oxo-1,6-dihydropyrimidin-3-ium-4-oleates, are light
irradiated with UV light between 320 and 490 nm.
9
.
N N
R'
R'" R"
O
R""
O
hv
N N
R'"
R'
O
O
R"
R'"
This was utilized to form copolymers of methacrylates with colesteric
monomers.
10
An example of such copolymers and the rearrangement is shown
below
10
:
sensitive and undergo intramolecular photocyclization to bis-|-lactams when
Light-Associated Reactions of Synthetic Polymers
251
C O O
O O
n m
(CH
2
)
4 (CH
2
)
4
C O
O
S
N
N
O
O
C
2
H
5
CH
3
C
CH
3
(CH
2
)
3
H
C O O
O O
n m
(CH
2
)
4 (CH
2
)
4
C O
O
S
C
2
H
5
CH
3
C
CH
3
(CH
2
)
3
H
(CH
2
)
3
N
N
O
O
(CH
2
)
3
UV light
alkyl side group in the 5 position of the pyrimidinium oleate and by the
embedding of a mesoionic chromophore, as shown above.
10
In photosynthesis, antenna pigments harvest energy and transfer it into
a reaction center for redox reactions.
11
Different antenna chromophores that
surround the reaction center are arranged morphologically in an order of energy
gradient.
12-14
Such an arrangement allows the energy to be sequentially
transferred and efficiently funneled into reaction centers over small distances in
the direction of decreasing band gaps. Considerable research has been carried
was done not just to mimic the natural light-harvesting process,
12-14
but also for
possible applications and use in optoelectronic and biological systems.
15
It is
speculated that a conjugated polymeric backbone, with well-designed
interruptions of conjugation by insulating spacers, might allow tuning the
emission properties and by providing an alternate model.
16
Based on this concept, Krebs and coworkers
17
reported a synthesis of a
light harvesting material that consists of three structural domains. Two of them
5. Photoresponsive Polymers
It was found that the rate of photorearrangement is affected by the length of the
out on means to develop the sequential multistep energy transfer systems. This
252
are conjugated homopolymers that are linked with a zinc porphyrin:
Sections A and B of the above block copolymer are illustrated above. The
polymer has a constant ratio of the zinc porphyrin to the incorporated monomer
units, regardless of the molecular weight. The ratio of zinc porphyrin to the
Studies of energy transfer from the polymer to the zinc porphyrin showed that
there is actually very little energy transfer when the material is in solution. On
the other hand, there is quantitative energy transfer in the solid state. Also, it
was observed that the light-harvesting properties of the three-domain structures
depend on the chain lengths of the conjugated polymers.
Cheng and Luh reported that they are also trying to develop polymers
that would mimic natural photosynthesis with synthetic polymers.
18
They point
out that silylene moieties have been used extensively as insulating spacers.
18
In
general, when the silylene spacer contains only one silicon atom, no conjugative
interactions between the t systems and the silicon moiety is observed.
19
They
believe, therefore, that introduction of an energy gradient with three well-
designed chromophores into a silylene-spaced polymeric chain may lead to
sequential energy transfer. To achieve this goal, they carried out preparations of
regioregular silylene-spaced copolymers composed of energy gradients with
three different chromophores. One of the polymers prepared in this way can be
illustrated as follows:
polymer blocks can be varied in the material by varying the size of blocks A.
Light-Associated Reactions of Synthetic Polymers
A
B A
n
m
=
n
B
=
N
Zn
N
N N
A
253
Si
D
2
Si
D
2
Si Si
A
n
Their synthesis utilized rhodium-catalyzed hydrosilylation of bis-
vinylsilanes and bis-alkynes. The ratio of the three chromophores in the above
polymer is 1:2:1, corresponding to D1, D2, and A chromophores, respectively.
Cheng and Luh found that upon excitation of the donor chromophore D1 only
emission from the acceptor A was observed. This is quite encouraging.
19
The
chromophores and the acceptor were illustrated as follows:
D
1
=
or
D
2
=
or
N
O
N
A =
or
OC
4
H
9
OC
4
H
9
It has not been disclosed yet, at this time, how successful this whole approach is
to actually mimicking photosynthesis, but it appears to be a very interesting
concept.
A common
rearrangement
that takes place in the nitro groups in poly(|-nitrostyrene) and its dimeric model
compound upon irradiation with UV light
20
:
5. Photoresponsive Polymers
5.2. Photoisomerization Reactions in Polymeric Materials
photoisomerization reaction intramolecular is
254
CH
CH
NO
2
n
base
hv
CH
N
OH
O
n
This reaction, however, is accompanied by molecular weight loss and the
molecular weight of the photoproduct is considerable lower than that of the
starting polymer prior to irradiation. This may, perhaps, be due to hydrolysis of
the product with a trace amount of water in methyl alcohol/ammonia medium
that is used during the irradiation.
20
Whether this photoisomerization reaction
has practical utility, however, is not certain.
Among all the photorearrangements, a cis-trans isomerization reaction
is the most useful one. A well known example one is that of cis-stilbene to the
trans isomer. This reaction has been described in many books.
21
The
isomerization reaction takes place because many olefins in the excited singlet
and triplet states have a perpendicular instead of a planar geometry. This means
that in the excited state the cis-trans isomerism disappears. Upon return to the
ground state, S
0
, it is possible for either isomer to form. The return, however,
usually takes place to the more stable form. Generally, photoisomerization of
chromophores in dilute solutions is a first order reaction.
An example of olefinic groups rearrangement is work by Onciu et al.,
22
with trimellitic anhydride. This was followed by preparation of two series of
photoreactive copoly(amide-imide)s by direct polycondensation of the
bis(trimellitimide)s and 1,4-phenylenediacrilic acid with either 4,4'-diphenyl-
methanediisocyanate in one case or with 1,6-diisocyanatohexane in another
case, respectfully. All of the copoly(amide-imide)s were found to be soluble in
polar aprotic solvents and to yield transparent, flexible and tough films.
22
When
22
The fully
aliphatic amide moiety.
22
The same processes are also observed in the polymer
films.
22
Polymers prepared by condensation of 4,4'-diacetylstiblene as the
bis(ketomethylene)monomer with 4,4'-diamino-3,3'-dibenzoylstilbene, a
bi(amino ketone), exhibit photoviscosity effects in dilute solutions due to cis-
5.2.1. Photoisomerization of the Olefinic Group
who formed three bis(trimellitimide)s by condensing three aromatic diamines
trans-cis photoisomerization and (2 + 2) photocycloadditions.
the polymers are irradiated in solution the p-phenylenediacryloyl units undergo
aromatic polyamides, also undergo a photofries rearrangement. The photo-
fries reaction, however, is completely suppressed in polymers that contain an
Light-Associated Reactions of Synthetic Polymers
255
trans isomerization.
23
The preparation of the polymers and the photo-
rearrangements can be illustrated as follows:
H
2
N
CH CH
NH
2
O O
+
CH
CH
CH
3
O
CH
3
O
N
CH CH
N
CH CH
n
N
CH
CH
N
CH
CH
n
The changes in viscosity can vary from 2 to 23% as a result of irradiation.
5. Photoresponsive Polymers
5.2.2. Photoisomerization of the Azo Group
Azobenzene is a well-known photoresponsive chromophore, and its
photoinduced and thermal geometric isomerizations have been extensively
UV light
256
explored.
21
Azobenzene and its derivatives assume both trans and cis
conformations with respect to the azo linkage. Azo t ÷ t- excitation and azo n
÷ t- excitation trigger trans-to-cis and cis-to-trans isomerizations.
24-26
The azo
linkage normally exists in the more stable trans form. Also, the trans isomer of
azobenzene exhibits an intense absorption around 320 nm due to the t÷t*
transition, while the cis isomer shows a weak absorption of the n÷t* transition,
around 430 nm.
27
Reversible isomerizations between cis and trans structures
quantitatively.
28
By comparison, the thermal isomerizations from cis to trans
configurations take place due to low activation energy of the cis-to-trans
process. Isomerizations of the azo chromophore in compounds are often
accompanied by drastic changes in a number of properties such, as for instance,
changes in the dipole moments.
29
The isomerization back to the trans
configuration can be readily carried out either thermally, or by visible light
irradiation. Because, the isomerizations have a strong effect on physical
properties, the azobenzene units are potentially useful components for photo-
control of polymer structures and properties. As a result, the azobenzene
functionality has been incorporated in wide variety of polymers. Changes in the
molecular structure, such as cis-trans isomerization in polymers can induce
contraction and expansion of the polymeric chains on both microscopic and
macroscopic scale. This was demonstrated on a polymer with azo linkages.
Exposure from dark to light can result in a contraction of as much as 0.5 %
30
:
N N
N N
light
dark
Some interesting reports on photoisomerization of azo-polymers are presented
below, while the subsequent sections describe specific physical changes and
possible utilizations.
Thus, photochemical conformation changes were demonstrated in a
copolymer of styrene, where azobenzene structures are attached in the co-
monomer to the benzene portion through amide linkages
31
:
are due to these transitions. Photoisomerization can proceed almost
Light-Associated Reactions of Synthetic Polymers
257
NH
O
N
N
n
N
n
NH
O
N
ì = <380 nm
heat or visible light
After 10 minutes of irradiation with ultraviolet light the photostationary state is
reached, consisting of 79% of the cis isomer. Back isomerization to trans of the
sample is slow in the dark(less than 10% in 60 min), but is much faster when
exposed to visible light.
31
32
describes preparation of isophthalic type
polyesters that include monomers with pendant azo groups:
CO
X
CO
X
O
(Y)m
(CH
2
)n
O N N Me
where Y is a hydrogen or a lower alkyl group; m = 1-3; n = 2-18. Polyesters
based on this monomers are claimed to be useful for optical recording media
such as hologram recording media with low light absorption or loss and wide
range of working wave lengths. The preparation of the polyester consisted of
first heating diethyl-5-hydroxyisophthalate with 4-(6-bromohexyloxy)-4'-
methyl-azobenzene in acetone at reflux to give diethyl-5-{6-[4'-(4"-
methylphenyl-azo)phenoxyhexyloxy}isophthalate. This compound is
subsequently reacted with 4,4'-- bis(6-chlorohexyloxy)diphenyl ether in the
presence of Zn acetate in a vacuum at 160
o
to form a polyester. The patent
claims that coating the polyester on a glass plate and recording with either 532
A Japanese patent
5. Photoresponsive Polymers
258
nm or 515 nm incident light gave a hologram.
32
Izumi et al.,
33
prepared poly(p-phenyleneethynylene) and hetero-
aromatic-containing poly(phenylene)-based conjugated polymers with photo-
isomerizable azobenzene units in the main chain . These were formed by using
palladium-catalyzed cross-coupling reaction of 4,4'-diiodoazobenzenes with 1,4-
diethynylbenzenes and bis(trimethylstannyl)heteroaromatics, respectively. The
product, a polymer with a low degree of main-chain conjugation shows
reversible photoisomerization of azobenzene units. This is reported to be
accompanied by changes in electrochemical properties.
In addition, Izumi and coworkers, in a earlier study, also carried out
similar preparations of conjugated polymers with azobenzenes in the main
chain.
34-36
Application of various palladium-catalyzed coupling methods such as
the Suzuki coupling and the Heck reactions allowed formation of poly(p-
phenylene)- and poly(phenyl vinylene)-based polymers:
R"
R"
N
N
R"
R"
n
R"
R"
N
N
R"
R"
R'
R'
n
R'
R'
R"
R"
N
N
R"
R"
n
where R’,R” = H or n-C
6
H
13
Light-Associated Reactions of Synthetic Polymers
259
The preparation of the poly(p-phenylene)-based conjugated polymers
azobenzene units in the main chain can be illustrated
as follows
37
:
O
B
O
B
O
O
R'
R'
+
I
R"
R"
N
N
R"
R"
I
Pd
Base
R"
R"
N
N
R"
R"
R'
R'
n
where R' and/or R" can be hydrogens or n-C
6
H
13
. Despite their stiff structures,
these polymers are soluble in common organic solvents, such as chloroform,
toluene, and tetrahydrofuran, when either or both of the monomers possess n-
hexyl side chains on the aromatic rings. The resulting polymers were found to
possess high molecular weights (M
n
> 7 x 10
3
) and to be thermally stabile (to >
isomerizations in the solid state were found to take place at 20 °C. These
isomerization processes are also accompanied by changes in the three-
dimensional hydrodynamic volumes of the polymers.
37
Synthesis of a series of azobenzene-cored polyphenylene dendrimers
was reported.
38
The photoresponsive properties of these dendrimers were
investigated by optical spectroscopy and gel permeation chromatography The
polyphenylene dendrimers exhibit a photoresponsive behavior upon UV and
visible light irradiation, resulting in a reversible and appreciable changes of the
dendrimer structures.
38
Actually, formation of polyphenylene dendrimers with azobenzene
structures in the core was reported earlier.
39
The materials were also
demonstrated to exhibit a photoresponsive behavior upon UV and visible light
irradiation, resulting in reversible and appreciable changes in the dendrimer
structures.
Junge and McGrath
40
reported studying photoresponse of dendrimers
containing three interior azobenzene moieties that are radially configured about
the core. With each azobenzene capable of cis-trans isomerization, the
5. Photoresponsive Polymers
with photoisomerizable
350°C), Also, they exhibit fluorescence. Yet, photochemical trans-to-cis
260
dendrimers can exist in four discrete states, cis-cis-cis, cis-cis-trans, cis-trans-
trans, and trans-trans-trans. All states are detectable in solution and exhibit
different physical properties.
1
H NMR spectral data indicates independent, rather
than simultaneous isomerization of azobenzene units. Dark incubation in CH
2
Cl
2
solutions of the dendrimers maximized the n÷t* transition at 352-nm, and
irradiation with 350-nm light resulted in photoisomerization, as evidenced by a
decrease in the absorbance at 352-nm and an increase in the n ÷t* transition at
442-nm. The presence of sharp isobesic points in the absorption spectra during
isomerization can be expected on the basis of the independence of the
chromophores.
40
azobenzene side chains:
(CH
2
)
4
O
O N
N
n
(CH
2
)
4
O
n
O N
N
UV
Vis
and a ketone/spiroketal one:
O
O
(CH
2
)
4
(CH
2
)
4
x
y
O N
N
O N
N
O
O
(CH
2
)
4
(CH
2
)
4
x
y
UV
Vis
O N
N
O N
N
They found that the conformations of the polymers that contain the ketone units
only are not affected by the cis-trans isomerization. On the other hand, the
keto/spiroketal polymers drastically change in the main-chain conformations.
42
Nozaki et al.,
42
synthesized photoresponsive ¸-polyketones with
Light-Associated Reactions of Synthetic Polymers
261
Condensation of acryloyl chloride with 4-(phenylazo)aniline was used
to form a monomer p-(phenylazo)acrylamilide. The monomer was polymerized
to yield poly[p-(phenylazo)acrylanilide] that undergoes photochemical
interconversions between trans and cis isomers under UV or visible light
irradiation. This reaction is reversible and reproducible for the homopolymer
43
:
C O
NH
N
n
CH
2
CH
N
C O
NH
n
CH
2
CH
N
N
5.2.2.1 Changes in Viscosity and Solubility of Polymeric Solutions
Changes of viscosity in polymeric solutions that are associated with
photoinduced conformational changes of the macromolecules were observed by
Lovrien in 1967.
43
He reported that solutions of a copolymer of methacrylic
acid and N-(2,2'-dimethoxyazobenzene)acrylamide exhibit an increase in
specific viscosity when irradiated with UV light. He also observed a decrease in
the viscosity of a poly(methacrylic acid ) and chrysophenine solution in water
under the influence of UV light.
43
This was followed by various reports of
photoviscosity effects in solutions of azobenzene based polymers. Matejka and
Dusek
44
studied a copolymer of styrene and maleic anhydride with azobenzene
in the side chains. U.V. light irradiation of a solution of this polymer in 1,4-
dioxane causes a decrease in specific viscosity between 24 to 30 % and in
tetrahydrofuran between 1 and 8%. They also observed that this decrease in
viscosity is reversible. The magnitude of the effect was found to be related to the
quantity of azobenzene linkages present in the polymer.
Hallensleben and Menzel
45
found that irradiation of poly(5-(4-
phenylazobenzyl)-L-glutamate in 1,4-dioxane solution with UV light (ì > 470
nm) decreases the viscosity by 9% . Here too this change in viscosity is
accompanied by a trans to cis isomerization that was estimated to be 23%. With
5. Photoresponsive Polymers
and for a copolymer with methacrylic acid
262
additional irradiation by 360 nm UV light, the viscosity decreases an additional
9% and the isomerization to cis reaches 89 %.
Irie et al.,
46
synthesized a number of polyamides with azobenzene
groups in the backbone. All the polymers exhibit photoviscosity effects. In
solutions in N.N'-dimethylacetamide, a 60% reduction in specific viscosity can
be achieved by UV light irradiation (410 > ì > 350 nm). The initial viscosity is
regained by storage in the dark at room temperature for 30 hours.
Changes in viscosity of solutions in dimethylsulfoxide of a range of polyureas
with azobenzene groups in the polymer backbone were reported.
47
The
irradiations were carried out at 35
o
C with UV light between 410 and 350 nm.
It was observed that the intrinsic viscosity is about 40% lower during UV
irradiation than in the dark. Also, toluene solutions of polydimethylsiloxane with
azobenzene residues were shown to exhibit 20 % lower viscosity under UV light
irradiation than in the dark.
48
Recently, Fernando and coworkers
49
prepared a
series of copolymers of trans-4-methacryloyloxyazobenzene with methyl
methacrylate.
O
N
N
O
CH
2
CH
2
C
CH
3
C
CH
3
C
O O
CH
3
n m
All the polymers exhibit a photoviscosity effect when exposed to UV
irradiation at ì = 365 nm. This effect was attributed by them to conformational
contraction of the polymer chains due to dipole-dipole interaction between
neighboring chromophores.
40
illustrated as follows:
This conformational change might possibly be
Light-Associated Reactions of Synthetic Polymers
263
N
N
N
N
n
UV light
N
N
N
N
Also, when copolymers of polystyrene and 4-(methacryloyl-
amino)azobenzene containing 2.2 to 6.5% of the latter are irradiated in a
cyclohexane solution with 15 flashes of 347 nm. of light. the polymeric chains
contract.
50
This occurs at a high rate per second as a consequence of
isomerization. At a later stage, several hundred seconds after the flash there is
evidence of polymer aggregation and precipitation.
50
In addition, when azobenzene residues are introduced into the main
chain of poly(dimethylsiloxane), reversible solution viscosity changes can be
obtained by irradiation with ultraviolet light.
51
The conformational changes of
the polymer can be illustrated as follows:
5. Photoresponsive Polymers
264
CH
2
Si
O
Si
CH
2
N
C
CH
3
CH
3
CH
3
CH
3
O
N N
C
N
O
x
n
C
N
O
x
CH
2
Si
O
Si
CH
2
N
C
CH
3
CH
3
CH
3
CH
3
O
N
N
n
A shown above, the conformational changes are confined to the isomerization of
the azo group.
Isomerization from cis to trans and back of azo groups, however, is not
the only mechanism that can affect photoviscosity change in polymeric
solutions. Thus, reversible solution viscosity changes were also observed
48
in
solutions of poly(dimethylacrylamide) with pendant triphenylmethane
leucohydroxide in methanol. This can be illustrated as follows:
O
NH
2
O
NH
C OH
N
2
x
y
O
NH
2
O
NH
C N
2
x
y
light
heat
OH
Light-Associated Reactions of Synthetic Polymers
265
So, as shown, the viscosity changes are due to positive charges that form on the
pendant groups.
Also, when a terpolymer that consists of vinyl pyrrolidone, styrene that
is p-substituted with 9,10-diphenyl anthracene, and a flluorescein derivative of
acrylamide, is irradiated with light, there is a viscosity increase
52
:
CH
2
CH
N
O
CH
2
CH CH
2
CH
C O
NH C
O
NH
COOH
O O OH
x
y z
The absorption of light by the diphenylanthracene was found to result
in efficient intracoil sensitization by fluorescene. The quantum efficiency of this
process was determined to be 0.4 in methanol and 0.8 in water.
52
This increase
corresponds to a decrease in polymer coil size in water. Analysis of the
fluorescence decay also demonstrates that the intracoil energy transfer is
essentially a static process and that aggregation can result in nonexponential
fluorescence decay that is interpreted as a dynamic equilibrium that takes place
52
:
The solubility of a copolymer of styrene in cyclohexane was found to
change reversibly upon ultraviolet light irradiation when the copolymer contains
small amounts (~2 mol %) of spirobenzopyran among the pendant groups.
53
spirobenzopyran groups to the polar merocyanine form with the resultant
decrease in polymer-solvent interaction and subsequent precipitation of the
higher molecular weight fractions of the polymer. A copolymer with a high
content of spirobenzopyran groups (12.3 mol %) performs as a negative photo-
resist with high contrast.
53
5.2.2.2. Sol-Gel Reversible Conversions
Gel systems that respond to external light stimuli are of considerable
interest in many fields, from potential use in paints and coatings, to personal
5. Photoresponsive Polymers
This is believed to be due to photoisomerization of the pendant
between diphenylanthracene and a nonfluorescent dimer state
266
care items and drug delivery systems. Applications might also include
photonics, optical storage, and photoswitchable materials.
Ire and Iga demonstrated that photostimulated sol-gel transitions are
possible with gels of a polystyrene copolymer in carbon disulfide solution that
carry some azobenzene groups.
54
The transitions are reversible and take place
upon ultraviolet light irradiation. The polymer undergoes cis to trans
isomerization of the pendant azobenzene groups with a 62% conversion for
polymers containing as much as 10.5% of azo groups:
C O
NH
n
N N
m
O
NH
N N
n
m
Irradiation with light of wave length between 310 and 400 nm converts the
solution to a gel and visible light (>450 nm) reverts the gel back to the solution
The process is a result the trans isomerizing to the cis form upon irradiation with
UV light.
55
It suggests that cis azobenzene moieties in the pendant groups make
interpolymer crosslinking junctions that are more stable than the interactions of
the trans forms.
Lee, Smith, and Hatton observed
56
that the viscosity and gelation of
mixtures of hydrophobically modified poly(acrylic acid) and a cationic
photosensitive surfactant can be controlled reversibly by switching irradiation of
the sample between UV and visible.
1-x
(CH
2
)
11
CH
3
O
ONa+
O
NH
x
hydrophobically modified poly(acrylic acid)
Light-Associated Reactions of Synthetic Polymers
267
CH
3
CH
2
N N O(CH
2
)
4
N(CH
3
)
3 Br
surfactant
The planar trans form of the surfactant, that is attained by visible light
irradiation, is more hydrophobic than the nonplanar cis conformation of the
material that is attained by ultraviolet light irradiation. At the critical
aggregation concentration of the surfactant, micellar aggregates form on the
polymer and solubilize the alkyl side chains grafted on the hydrophobically
modified poly(acrylic acid), leading to physical crosslinking and gelation. The
hydrophobic trans (visible light) form, with a planar azobenzene group in the
surfactant tail, has a lower critical aggregation concentration than the more polar
cis (UV light) form, resulting in gelation at lower surfactant concentrations
under visible light. Reversible viscosity changes of up to 2 orders of magnitude
are observed upon exposure to UV or visible light. Observed viscosity maxima
of 5.6 x 10
4
cPa for the trans form and 2.2 x 10
3
cPa for the cis form of the
surfactant suggest that the trans form surfactant micelles are more effective at
solubilizing the alkyl side chains than are the more hydrophilic cis-form
micelles.
56

Harada and coworkers
57
reported forming a photoresponsive hydrogel
system by combination of o-cyclodextrin, dodecyl-modified poly(acrylic acid),
and a photoresponsive competitive guest, 4,4’-azodibenzoic acid. An aqueous
solution of dodecyl-modified poly(acrylic acid) exhibits a gel-like behavior,
because polymer chains form a network structure via hydrophobic associations
of C
12
side chains. When o-cyclodextrin is added to the gel-like aqueous
solution, the gel is converted to a sol mixture because hydrophobic interactions
of C
12
side chains are dissociated by the formation of inclusion complexes of o-
cyclodextrin with the C
12
side chains. Upon addition of 4,4’-azodibenzoic acid
to the binary sol mixture of the modified poly(acrylic acid) and o-cyclodextrin,
the cyclodextrin interacts predominantly with 4,4’-azodibenzoic acid:
HO
O
OH
O
+
5. Photoresponsive Polymers
N
N
268
HO O
O
NH
C
12
H
25
95 5
n
+
O
OH
HO
CH
2
OH
Hydrophobic associations of the C
12
side chains are restored, resulting in a sol-
to-gel transition. When this ternary gel mixture is irradiated with UV light, the
azobenzene compound isomerizes from trans to cis. As a result, the mixture
undergoes a gel-to-sol transition, because o-cyclodextrin formed inclusion
complexes more favorably with C
12
side chains than with cis-azobenzoic acid.
On the other hand, when the ternary sol mixture is irradiated with visible light,
the azo group isomerizes back from cis to trans and the mixture undergoes a sol-
to gel transition. Harada and coworkers
57
reported that these gel-to-sol and sol-
to-gel transitions occur repeatedly by repetitive irradiations of UV and visible
light.
5.2.2.3. Changes in Birefringence and Dichroism
Over the last twenty years there were reports that exposure to linearly
polarized light of some photoreactive films can generate optical anisotropy in
these films through an anisotropic polarization axis. This phenomenon received
more attention recently
58-60
If the axis-selective reaction is accompanied by
molecular reorientation, a large anisotropy can form. Thus, Kawatsuki et al.,
131
reported that in axis-selective triplet phtotosensitized reactions of photo-
crosslinkable liquid crystalline polymeric films achieve molecular reorientation.
Irradiation is done with linearly polarized light at 405 nm. Also, the molecular
reorientation is thermally enhanced. Four photosensitizers were used in this
work. These are as follows:
C
2
H
5
N
C
2
H
5
N
C
2
H
5
C
2
H
5
O
4,4’-(N.N’-bisdiethylamino)benzophenone
Light-Associated Reactions of Synthetic Polymers
269
NO
2
H
2
N
p-nitroaniline
NO
2
N
C
2
H
5
C
2
H
5
O
4-nitroacenaphthene 4-(N-dimethylamino)benzophenone
Also, several types of polymeric films were used in this work that are liquid
crystalline polymethacrylates with photocrosslinkable mesogenic side groups:
n
O
O
OCH
3
O
(CH
2
)
6
CH
2
O
O
In all cases the photoreactivity of the films was generated with less that 9%
doping. The axis-selective photoexcitation of the triplet sensitizers and the
polarization-preserved energy to the photoreactive mesogenic groups
determined the photoinduced optical anisotropy as well as the thermal
enhancement of the molecular orientation.
Amorphous polymers with pendant azobenzene groups were
demonstrated to be good candidates for optical data storage and other
electrooptic applications.
61
One such material can be illustrated as follows:
O
(CH
2
)
2
O
OCH
3
N
C
2
H
5
N
N NO
2
n
m
This is due in part to a mechanism that allows anisotropy to be optically
induced at room temperature in these materials.
62
The induced anisotropy
manifests itself in birefringence and in dichroism of long-term stability. The
anisotropy can, however, be eliminated by either optical or thermal means. The
5. Photoresponsive Polymers
270
followed by a spatial reorientation of the azo-aromatic side chain dipoles via
trans-cis-trans isomerization. By selectively exciting only the dipoles
possessing a sufficient dipolar component, or by absorption probability in a
single direction, a perfectly stable dipolar orientation is created that is
perpendicular to this direction.
62
When the external electric dc field poling is
done (see Chapter 6) at temperatures above the glass transition temperature, the
orientation of dipoles takes place (by the typical theoretical description of the
process) in one of the independent dipole responses.
63
The literature indicates,
however, that the resultant orientation order is not linearly dependent on the
chromophore content, especially at high chromophore concentration.
64, 65
The
conclusion is that there is some form of dipolar interaction between the azo
groups on the side chains that are next to each other on the polymer backbone.
Absorption maxima shifts to higher energy with increasing azo concentration.
indicate that the dipoles are associated in an anti-parallel fashion. This
interaction reduces the mobility of the side chain but enhances the orientation
stability.
It was demonstrated by Natansohn and coworkers
64, 65
how the trans-
cis-trans isomerization cycles of azobenzene bound in high glass transition
temperature polymers could be used to induce birefringence in the polymer
films. Linearly polarized light orients an excess of the azobenzene group
perpendicularly to the polarization direction, while circularly polarized light
restores the original disorder of orientations, thus "erasing" the induced
birefringence. This means that irradiation with an argon laser at 514 or 488 nm
process. The cis isomers are relatively short lived even in the absence of
irradiation. Thus, after the laser is switched off, only the trans isomers remain
present in the film.
65
In addition, it was also reported that circular dichroism and circular
birefringence can be induced in thin films of achiral polymer liquid crystals
containing 7 to 15 mol % azobenzene chromophores by irradiation with
circularly polarized light.
66
The polymer can be illustrated as follows:
CH
3
O
(CH
2
)
11
O
O
CN
O
(CH
2
)
6
N
O
NO
2
n
x
N
N
mechanism by which anistoropy is induced involves selective photoexcitation
will photochemically activate both the trans-cis and cis-trans isomerization
Light-Associated Reactions of Synthetic Polymers
271
Circular dichroism was observed not only for the azobenzene moieties
produces enantiomeric structures, and a chiroptical switch can be achieved by
alternating irradiation with left and right circularly polarized light. The level of
chemically bound) of the azobenzene chromophores, the amount of azobenzene
erased by heating the films above the clearing temperatures or by annealing the
films in the liquid-crystalline phase.
Two newly synthesized polyelectrolytes functionalized polymers with
branched side chains bearing electron donor-acceptor type azobenzene
chromophores were used as polyanions to build up multi-layer films through an
electrostatic sequential adsorption process
67
:
COOH COOCH
2
OCH
2
CH
2
N
OCH
2
CH
2
N
N
N Y
N
N
CH
2
CH
3
CH
2
CH
3
Y
m n
where ,Y is NO
2
in one polymer and COOH in the other. Poly(diallyldimethyl-
ammonium chloride) was used as the polycation. When dissolved in an
anhydrous dimethylformamide and also in a series of dimethylformamide-water
mixed solvents of different ratios, both azo polyelectrolytes formed uniform
multilayer films. This was done through the layer-by-layer adsorption process.
Altering the water content of the dipping solutions of both azo polyelectrolytes
was found to dramatically change the thickness of the sequentially adsorbed bi-
layers, chromophore orientation, and surface roughness of the multi-layer films.
On the other hand, the solvent effect on the hydrogen-aggregation in the multi-
layer films was determined by the structural details of the azo polyelectrolytes.
After the irradiation with a linearly polarized Ar+ laser beam at 488 nm,
significant dichroism was induced in the multi-layer films that were prepared
from the dimethylformamide dipping solution. Upon exposure to an interference
pattern of the Ar+ laser beam at modest intensities, optically induced surface
modulation on the multilayer surfaces were observed.
67
Enzymatic synthesis, employing horseradish peroxidase, was used to
prepare a photoactive azo polymer, poly-[4-(phenylazo)phenol], from 4-
(phenylazo)phenol.
68
Spectroscopic data show that the coupling reaction occurs
5. Photoresponsive Polymers
but also for the nonphotoactive mesogens, cyanobiphenyl groups, due to a
photoinduced chirality depends upon incorporation methods (doped or
cooperative motion. Circularly polarized light of the opposite handedness
units, and the sample temperature. The photoinduced circular dichroism can be
272
primarily at the ortho positions, with some coupling at the meta positions of the
phenol ring as well. This results in the formation of a branched polyphenylene
backbone with pendant azo functionalities on every repeat unit of the
macromolecules.
N
OH
N
n
This enzymatically synthesized azophenol polymer has an extremely high dye
content (nearly 100%) and is soluble in most polar organic solvents. It forms
good optical quality thin films. Polymer solutions show reversible trans to cis
poly(azophenol) films also exhibit photoinduced absorption dichroism and large
photoinduced birefringence with unusual relaxation behavior.
68
A photoresponsive azo-polymer was grafted onto polyethylene film.
69
The monomer used in the grafting reaction is 4-[N-(acryloxyethy)-N-
ethylamino]-4'-nitroazobenzene. It was found that the azo groups through rapid
cis-trans isomerization orient themselves perpendicularly to the polarization
488 nm this resulted in formation of anisotropic films.
69
There is considerable interest in using polymeric photorefractive
materials for holographic recording. The photorefractive effect must be
completely reversible so that the recorded holograms can be erased at will. Such
reversibility would make these polymeric materials suitable for real time optical
applications. This requirement, however, creates a real problem, because
recording and reconstruction of the stored information is done by illuminating
the material with a spatially homogenous light beam of the same wavelength.
The light gets diffracted by the reversible index modulation that, at the same
time, simultaneously erases the hologram. Earlier, it was demonstrated that
polymeric composites with high diffraction efficiency, two-beam coupling gain
coefficients, and ms response times can be prepated.
70,
Also, Blanche and
coworkers
71
demonstrated that recording of volume holograms on such
polymers with femtosecond pulses using two photon absorption coupled with a
nondestructive readout using cw lasers of the same wavelength is possible. The
polymer is a composite of poly(N-vinylcarbazole), N-ethylcarbazole, and benzyl
photoisomerizations of the azobenzene groups with long relaxation time. The
direction of the light. When the films are irradiated with polarized light of
Light-Associated Reactions of Synthetic Polymers
273
butyl phthalate. A photosensitizer, an electrooptic chromophore was sandwiched
between two coated transparent electrodes. It can be illustrated as follows
15
:
O
O
F
CN
F
The composite was fabricated into photorefractive samples by injection
molding.
5.2.2.4. Application to Optical Data Storage
Due to possible utilization of photoinduced orientation in polymeric
films in optical data storage, this phenomenon and the quadratic nonlinear
optical effects were extensively investigated in the last few years.
71
It was
reported, for instance, that to study photoisomerization in a polymeric
environment, a series of polymers containing azo dyes with large differences in
the second order transition temperature were compared.
71
Particular emphasis
g
and their molecular structure. As a result, it was shown that light-induced non-
polar orientation in very high Tg polyimides (Tg up to 350
o
C) can take place
even at room temperature. The polymers used in one of these studies can be
illustrated as follows
71
:
N
O
O
R
N
O
O
N
N
N
O
2
N
n
5. Photoresponsive Polymers
was placed on the relationship between photoisomerization, T of the polymers,
274
N
N
N
NO
2
N
O
O
R
N
O
O
n
where R = (CF
3
)
2
-C < in one polymer and -COO-(CH
2
)
2
-COO- in another.
From the behavior of the mean absorbance it was concluded that all the azo
chromophores revert to the trans form on completion of a thermal back reaction.
The observed increase in the dichroic ratio over the first 25 hours is believed to
be due to the thermal back isomerization and not due to the relaxation of the
induced orientation.
71
Heating polymers at 170
0
C for one hour fails to erase the
green light-induced dichroism in the samples. This dichroism is, however,
completely erased on heating the samples above their T
g
for 10 minutes.
Irradiation of the films with incident light gives holograms.
72
Also, polyesters were formed by melt transesterification
73
of
cyanophenyl)azo]phenoxy]alkyl]-l,3-propanediols, where the alkyl spacer is
hexa, octa, or decamethylene. The molecular weights of these polyesters ranges
between 5000 and 8900:
O
O
(CH
2
)
m
O
O
(X)
(X)
(X)
(X)
N
N CN
O
(CH
2
)
12
n
diphenyltetradecanedioate with a series of mesogenic 2-[-4-[(-4-
Light-Associated Reactions of Synthetic Polymers
275
Optical storage properties of these polyesters were studied through
measurements of polarization. anisotropy and holography. A resolution of 5000
lines/mm and diffraction efficiencies of about 40 % were achieved. Lifetimes
greater than 30 months for information storage was obtained, even though the
glass transition temperatures are about 20 °C. Complete erasure of the
information can be obtained by heating the films to about 80
o
C. It was also
claimed that the films can be reused many times without failure.
73
Belfield and coworkers
74
describe simultaneous two-photon absorption
as a process in which the probability of a ground to excited state transition scales
quadratically with incident intensity of the irradiation source. This nonlinear or
quadratic dependence makes two-photon excitation attractive for use in several
emerging technologies, such as two-photon fluorescence imaging, three-
dimensional microfabrication, and optical power limiting. Of greatest interest is
the possible development of organic three-dimensional optical data storage
media and processes.
Previously, Belford et al.,
75
reported the synthesis and characterization
of organic fluorescent dyes with high two-photon absorptivity. Based on their
findings, they reported that they have prepared a photosensitive polymer with a
high two-photon absorptivity group:
O
N
O
O
O
O
S C
14
H
21
C
14
H
21
x
y
z
Photophysical properties indicate, the this polymer undergoes two-
photon unconverted fluorescence.
74
Fluorescence properties of the polymer
were modulated in the presence and absence of a photoacid generator, providing
image contrast. A multi-layered assembly and bulk two-photon fluorescence
lithographic imaging provided both negative” and “positive” contrast images,
demonstrating the possibility of’ three-dimensional optical data read-out.
Furthermore, the photosensitive polymer was also responsive to two-photon
induced “writing” followed by “reading”, indicating the possibility of high
optical data density storage in the organic material.
74
5. Photoresponsive Polymers
276
5.2.2.5. Changes in Contact Angle of Water
Wu et al.,
76
reported syntheses of a series of novel azo
polyelectrolytes, starting with a reactive precursor, poly(acryloyl chloride). The
precursor polymer was functionalized by the Schotten-Baumann reaction with
several aromatic azo compounds containing hydroxyl end groups. The degrees
of functionalization were controlled by selecting suitable feed ratios between the
azo reactants and poly(acryloyl chloride) The unreacted acyl chloride groups
were hydrolyzed to obtain ionizable carboxylic acid structures.
O Cl
n
+
HOCH
2
CH
2
O
N
N
X
n
N
N
X OCH
2
CH
2
O
O
When irradiated by 365 nm UV light, azo polyelectrolytes showed a significant
photochromic effect. The contact angles of water on the surfaces of spin-coated
films of two of the polymers decreased upon UV irradiation. The extent of the
photoinduced contact angle changes depends on the type of the azo
chromophores and the degree of functionalization. Self-assembled multilayers of
the azo polyelectrolytes were formed by a layer-by-layer adsorption method. A
significant photochromic effect from cis-trans isomerization of the azo
changes of water on the self-assembled multilayers were also observed.
76
A reversible photocontrol of wettability of polymeric materials is
possible by a technique developed by Irie and Iga
54
When a copolymer of butyl
methacrylate and (2-hydroxyphenyl)-o-(4-vinylphenyl)benzyl alcohol is
irradiated with ultraviolet light, there is a large increase in the contact angle and
wettability of the material. This reverses back to the original structure in the
dark
54
:
chromophores was observed for the multilayers. Photoinduced contact angle
Light-Associated Reactions of Synthetic Polymers
277
H
9
C
4
O
O
C
OH
OH
n m
H
9
C
4
O
O
C
n
m
O
UV light
dark
.
low contact angle high contact
Polyacrylamide gels that contain triphenylmethane leucocyanide groups (1-4
mol %) exhibit reversible photostimulated dilation
72
upon irradiation with
ultraviolet light of 270 nm. The weight of the gels increases as much as 13 times
and the size expands approximately 2.2 times in each dimension as it swells with
water. The dilated gel de-swells in the dark. The cycles of dilation and
expansion, however, is suppressed by addition of salts, such as NaCI or KBr.
The salt effect and semiquantitative theoretical considerations of the behavior
of ions suggests an osmotic pressure differential between the gel inside and the
outer solution. This is produced by photodissociation of triphenylmethane
leucocyanide groups contained in the gel network and is the main driving force
of the photostimulated gel dilation angle.
C
OH
Z
NC CN
C
Z
NC CN
UV light
+
OH
5.2.2.6. Changes in Optical Activity
Conformationally restricted copolyaramides containing a combination
of 4,4'- azobenzene, 1,4-phenylene, and chiral 2,2'-binaphthylene main-chain
segments were demonstrated to exhibit photoresponsive chiroptical behavior.
77
This is due to multiple trans-cis-isomerization reactions triggered within the
polymer backbones. In contrast to the more randomly constructed counterparts,
5. Photoresponsive Polymers
contraction of the gel by photoirradiation can be repeated several times. The gel
278
copolymers that possess periodic backbone structures undergo reversible,
wavelength-dependent inversions in their optical rotations in response to
multiple UV- light/visible- light illumination cycles. Similar behavior is also
observed for smaller oligomers fitted with periodic arrangements of the
monomer units.
77
Also a new chiral menthone-based acrylic monomer, capable of trans-
cis isomerization, was synthesized and used to obtain a homopolymer and a
series of comb-shaped copolymers with a nematogenic monomer.
78
This
O
H
CH
3
The copolymers are capable of forming chiral nematic phases.. UV
irradiation significantly changes the step of the helix in copolymer samples with
planar orientation.
5.2.3. Liquid Crystalline Alignment
In the past ten or more years glass transitions and mobility in confined
polymer systems aroused much interest. It was influenced by need for alignment
in liquid crystalline flat panel displays, because in these displays films of
polyimides are widely used . The surfaces are usually treated to produce uniform
alignment of the liquid crystals into suitable "pretilt" angles. The treatments
consisted of rubbing process with velvet fabrics. Search for new methods,
however, led to development of molecular structures that undergo alignment
upon irradiation with linearly polarized UV light.
79-81
Polymer-stabilized liquid
crystals are low-molar-mass liquid crystal. Their bulk alignment or their texture
is stabilized by a polymer network. Such polymer network is usually in low
concentration.
82, 83
Several types of polarized-light-induced liquid crystalline
aligning of molecules were reported in the literature.
89
One photoalignment material is poly(vinyl cinnamate). The polymer
and its copolymers were reported to have the ability to align in thin films in the
direction perpendicular to the axis of the linearly polarized ultraviolet light. This
photoalignment mechanism has not been fully elucidated at present. A draw
back to using poly(vinyl cinnamate) and its copolymers is a low glass transition
temperature. As a result, they remain mobile after treatment and chain
orientation. Other materials with higher T
g
are, therefore, needed. Among the
monomer was illustrated as follows:
Light-Associated Reactions of Synthetic Polymers
279
most promising ones are polyimides. They form liquid crystal alignment layers
in flat-panel displays and possess good optical transparencies, adhesion, heat
resistance, dimensional stability, and are good insulators.
There are various reports in the literature about preparations of soluble
was reported by Lee et al.,
84
that they prepared a photoreactive polyimide with
cinnamate chromophores side groups :
N
F
3
C
N
O
O
O
O
CF
3
O O
O O
n
This polyimide is claimed to be thermally stable up to 340
o
C and has a
glass transition temperature of 181
o
C. Also, it was demonstrated that the
cinnamate chromophores, upon irradiation with linearly polarized ultraviolet
light, undergo both photoisomerization and dimerization. In addition, the light
exposure induces anisotropic orientation of the polymer main chains and of the
cinnamate side groups in the film. The irradiated films align homogeneously the
nematic liquid crystal molecules along one direction at an angle of 107
o
with
respect to the polarization. The liquid crystalline alignment was found to be
o
It was also reported
84
that photoreactivity of side-chain liquid-
crystalline polymers can align liquid crystals both in a parallel mode or
perpendicularly, depending on the degree of the photoreaction of the polymers.
Presumably this particular polymer can multi-photoalign the liquid crystal
pattern without a change of the direction of the linearly polarized UV light. The
chemical structure of such an aligning polymer is depicted as follows:
CH
2
CH
3
C
C
O(CH
2
)
6
O
O
O(CH
2
)
n
C
CH
CH
O
p
where n = 2 or 6
thermally stable up to 200 C.
5. Photoresponsive Polymers
photoreactive polyimides with cinnamate chromophore side groups. Thus, it
280
It was concluded,
84
therefore, that the liquid crystals align both parallel and
perpendicular to the incident E direction on the photocrosslinked polymer film
by changing the degree of the reacted cinnamoyl group. That can be controlled
by irradiation time. A bias-tilt angle between the liquid crystals director and the
substrate is also realized by controlling the irradiation angle of the light.
84
Another approach to liquid crystalline alignment is based on photo-
isomerization of azo compounds in polymeric materials or as part of the polymer
structure.
85-87
In recent years, investigation of the use of azobenzene-containing
polymers for liquid crystalline alignment became quite thorough because of the
potential application in holographic storage as well as optical and photonic use.
88-90
The photoalignment of liquid crystalline polymers containing azobenzene
groups has an advantage of local variation of the orientation order due to pixel
wise irradiation. This is a process that is reported to takes place via angular
dependent excitation, a series of cis-trans photoisomerization cycles, and
rotational diffusion within the steady state of the photoreaction. This results in
the photochromic side group becoming oriented perpendicularly to the electric
field vector of the incident light and establishing an oblate order in the films.
92
In this
procedure, films of liquid crystalline copoly(methacrylate)s with photochromic
or, alternatively, UV light is used. The light-induced ordering of the azobenzene
group is connected with cooperative alignment of the nonphotochromic co-
mesogenic and dye side groups even below the glass transition temperature.
They noted that the light-induced orientational order generated in the glassy
state is significantly amplified by the subsequent annealing of the irradiated
films at temperatures within the mesophases of co- and terpolymers.
Amplification factors up to 30 were found in this series of materials. By this
technique, the required dose or the irradiation time is significantly reduced by
the optimization of light-induced and thermal processing, respectively. This
procedure results in anisotropic monodomain films of nematic and smectic
polymers.
Another investigation also reported photo and thermal isomerizations
of azobenzene based groups that are covalently bound to copolymers of
methacrylates
101
:
Light-Associated Reactions of Synthetic Polymers
azobenzene and benzanilide side groups and related terpolymers (containing
In addition, an approach to photo aligning liquid crystals by a two step
procedure was reported by Stumpe, Gimenez, and coworkers.
additional dye side groups) are oriented by irradiation . Linearly polarized visible
281
OCH
3
(CH
2
) O N
N
CH
2
C
CH
2
C
X
C O
X
C O
O
y z
m
n
Here, kinetic data indicates that when these liquid crystalline polymers
are exposed to visible light, the azo groups orient themselves from a more or
less random arrangement to a perpendicular one. This is a photoselection
process.
101
It was also reported that photoinduced alignment in cast thin films of
liquid crystalline polymers, of 6-[4-(4-ethylphenyl)diazenylphenyloxy]hexyl
methacrylate,
O
N
N
C
2
H
5
C
C
O
(CH
2
)
6
CH
2
CH
3
O
n
and poly[4'-[6-(methacryloyloxy)hexyloxy]-4-cyanobiphenyl] were studied.
93
When the polymer films with cis-azobenzenes were subjected to irradiation with
linearly polarized light at 436 nm, biaxiality of the azobenzene moieties was
induced during the in-plane alignment process. On the other hand, when they
were exposed to unpolarized light at 436 nm, three-dimensional manipulation of
the polymer liquid crystals was achieved. Examination of the three-dimensional
alignment behavior by UV and FTIR spectroscopies, and by polarizing optical
microscopy techniques found that the azobenzene moieties become aligned
along the propagation direction of the irradiation light through repetition of
trans-cis-trans isomerizations. The induced anisotropy is large (an approximate
order parameter as 0.36), reversible, and stable (more than 5 months at room
three-dimensional reorientation efficiently together with the azobenzene
moieties due to the cooperative motion.
93
:
Han et al.,
91
also studied exposure of films of liquid crystalline
polymers with azobenzene side chains to linearly polarized light of 436 nm
that results in successive occurrences of uniaxial in-plane orientations, followed by
out-of-plane orientations of azobenzenes.
91
Two kinds of orientation modes
were observed. These are possibly extreme cases, when linearly polarized light
with the electric vector parallel to the xz-plane comes along the z-direction. One
is the uniaxial in-plane orientation of the azobenzene with a dipole moment
parallel to the x-axis from the x- to y-direction and the other is out-of-plane
5. Photoresponsive Polymers
temperature). A nonphotoactive mesogen, cyanobiphenyl, also underwent
282
(homeotropic) one toward the z-direction. Marked dependence of photo-
orientation processes on film temperatures was observed. In-plane orientation
slightly below the transition temperature between smectic and nematic phases,
gives rise to distinct transformations from in-plane orientation at the early state
to successive out-of-plane reorientations.
91
These orientations can be illustrated
as follows:
N N
N N
N N
N
N
in plane
out of plane
Zebger et al.,
94
reported that they prepared a liquid crystalline
polyester with azobenzene side groups:
O
O
O
CH
2
CH
CH
2
O
C
(CH
2
)
11
C
n
(CH
2
)
8
N
N
O
CN
They studied the effects of irradiation of the films of this polymer with linearly
polarized red light after photochemical pretreatment. Conventional photo-
orientation processes are usually done with linearly polarized green, blue, or UV
was generated in the glassy state. Photoorientation at higher temperatures,
Light-Associated Reactions of Synthetic Polymers
283
light of an argon laser (514, 488, or 351 nm). The found that orientation of 4-
cyano-4'-alkoxyazobenzene side groups can take place parallel to the electric
field vector upon irradiating of the films with linearly polarized red light. The
polyester is characterized by smectic and nematic phases and a strong tendency
light or an exposure to visible light of high power density to produce a certain
concentration of the trans-isomer, which destroys any initial orientation order
and J-aggregates. The orientation process is cooperative, whereas the light-
alkylene spacers and even of the main-chain segments into the same direction.
Zebger et al.,
94
concluded that the most probable mechanism of this two-step
process is the angular-selective transformation of the bulky trans-isomers to the
rod like cis-isomeric formed by the red light. The aligned cis-azobenzene side
groups become strongly J-aggregated. Very high values of dichroism of about
0.8 and birefringence of about 0.3 were generated as a result of this combination
of the photoinduced orientation process and the thermotropic self-organization,
which takes place simultaneously under the irradiation conditions. The process
results in a uniaxial prolate order of the film, whereas conventional photo-
orientation leads to a biaxial oblate order.
93
Thus, the direction of photo-
induced orientation and the type of the three-dimensional orientation order can
be controlled by the wavelength of the irradiating linearly polarized light. This
can also be done in the same film of a smetic polyester with 4-cyano-4'-
alkoxyazobenzene side group.
93
Also, it is interesting to note that in a diblock copolymer that contains
azobenzene groups
94
:
OCH
2
(CH
2
)
4
CH
2
O
Br
O
O
O
O
N N OCH
3
m
n
mesogenic groups.
94
It is important, therefore, to take into consideration any
possible steric hindrance that might occur in the preparation of the polymeric
material.
Zhao and coworkers
95, 96
reported that an azobenzene polymer network
can also optically align ferroelctric liquid crystals. This was done by dissolving
two chiral dimethacrylate and one chiral diacrylate monomers containing
5. Photoresponsive Polymers
to form J-aggregates. It requires a pretreatment by irradiation with ultraviolet
photoinduced birefringence shows microdomain structures, characteristic of
diblock copolymers. These structures hinder photoalignment of the azobenzene
induced orientation of the photochromic moiety causes an ordering of the
284
azobenzene groups in a commercial ferroelectric liquid crystal host. The
monomers were illustrated as follows:
O
N
O
O O
N
N
O
O
O
N
O
O O
N
N
O
O
methacrylate acrylate
O
O
O
N
N
O
O
O
O
The monomers were then thermally polymerized and simultaneously irradiated
with linearly polarized light. Two of the monomers were able to induce bulk
alignment of the liquid crystals in direction perpendicular to the polarized light.
Monomer #1 was effective in concentrations as low as 1%. It was also
concluded from the experimental evidence that the photoinduced bulk
alignment of the ferroelectric liquid crystals may take place by a mechanism that
is different from one that takes place in achiral azopolymers.
In addition, Zhao and coworkers
97
of ferroelectric liquid crystals using azobenzene polymer networks of polyethers
and polyepoxides. Bulk alignment was achieved by polymerizing several divinyl
ethers and diepoxide monomers bearing an azobenzene moiety. Here too,
thermal polymerizations were conducted in solution within the ferroelectric
liquid crystals, while exposing the reaction mixture to linearly polarized
irradiation. The monomers can be shown as follows:
reported photoinduced alignment
Light-Associated Reactions of Synthetic Polymers
285
O
O
N
N
O
O
O
N
N CN
O
O
O
O
O
O
O
O
N
N
O O
O
O
O O
O
CN
N
N
Polymerization of these monomers was achieved by cationic mechanism. The
monomers were also found capable of inducing and stabilizing bulk alignment
of the liquid crystals. Zhao and coworkers
97
concluded, however, that the
mechanism of action might be different from the one obtained with chiral
azobenzene polymethacrylates. Instead, the results suggest to them that the
mechanism might be based on formation of an anisotropic azobenzene polyether
or polyepoxide network.
In still another, subsequent work, Zhao and coworkers
98
used block
copolymers composed of polystyrene and liquid crystalline azobenzene-
5. Photoresponsive Polymers
containing polymethacrylate copolymers as a model system:
286
O(CH
2
)
6
O
O
O
O
N
N
OCH
3
m n
to investigate the confinement effects on the photoalignment, photochemical
phase transition, and thermo-chromic behavior of the azobenzene polymer. The
study showed
98
that when confined in the microphase-separated domains in the
diblock copolymers, the azobenzene polymer behaves differently than it does as
a homopolymer free from confinement. The confinement effects are manifested
by (1) decreased photoinduced and thermally enhanced orientation of
azobenzene mesogenic groups in different aggregation states, (2) slower
transformation from a liquid crystalline phase to the isotropic state triggered by
the trans-cis photoisomerization and slower recovery of the liquid crystalline
phase after the thermally induced cis-trans back-isomerization, and (3) severely
reduced and even suppressed changes in the aggregation states of azobenzene
groups on heating, which is at the origin of the thermo-chromic property. The
common cause of these confinement effects is the restriction imposed by the
confining geometry on either an order-disorder or a disorder-order
process involving the motion and rearrangement of azobenzene
groups.
98
Synthesis of liquid crystalline photoactive triblock poly(butyl acrylate)
thermoplastic elastomer copolymers with methacrylate-based azobenzene-
containing side-chain was reported.
99
Br O
O
O
O
(CH
2
)
3
CH
3
O
O
N N CH
3
O
(CH
2
)
6
O
2
n/2 m/2
It was found that when the solution-cast films are stretched at temperature
greater than T
g
, liquid crystalline microdomains can support part of the elastic
extension and, at the same time, deform to result in a long-range orientation of
azobenzene mesogens. The liquid crystal orientation is retained in the relaxed
film at T < Tg, which creates a thermoplastic elastomer whose glassy micro-
reorgani-
zation
Light-Associated Reactions of Synthetic Polymers
287
domains contain oriented azobenzene mesogens. The reversible trans-cis
photoisomerization of the azobenzene chromophore can be used to modulate the
mechanically induced orientation. Also, Zhao and coworkers
100
reported
recently preparation of liquid crystalline ionomers with azobenzene mesogens
and three metal ions, copper ++, zinc ++, and manganese++. They found that the
azobenzene mesogens. Ionomers with zinc and manganese ions showed
increased photoinduced birefringence and higher diffraction efficiency of
birefringence gratings obtained by excitation with spatially modulated light
polarization. On the other hand, ionomers with copper showed the opposite
effect. The copolymers can be illustrated as follows
100
:
N
N
CH
3
Cu
2
Zn
2
COO
C
(CH
2
)
6
O
O
Mn
2
Kawatsuki et al.,
101
described two different techniques for thermally
enhanced photoinduced reorientations of liquid crystalline polymethacrylate
films that contain 4-methoxyazobenzene side groups with various alkylene
spacer lengths:
C H
3
C
CH
2
C O
O
(CH
2
)
O N
N CH
3
p
n
One is the classical method based on photoselection and rotational diffusion in
the steady state of the cis-trans photoisomerization, which includes irradiating
with linearly polarized 365 nm light and subsequent annealing in the liquid
crystalline temperature range of the film. The spacer length and exposure dose
significantly influence the reorientation direction. In-plane reorientation
5. Photoresponsive Polymers
metal ions exert a significant effect on the photoinduced orientation of
288
perpendicular to the electric vector of the linearly polarized 365 nm light
generates polymer liquid crystals with short spacers, but out-of-plane
reorientation with a small degree of in-plane reorientation is predominant for
polymer liquid crystals with long spacers. The other is an alternative technique
based on an axis-selective trans to cis photoisomerization using linearly
polarized 633 nm light and thermally enhanced molecular reorientation.
Regardless of the spacer length, a high order of in-plane reorientation parallel to
cis of linearly polarized 633 nm light can be accomplished.
101
Zettsu and Seki reported
102
preparation of a group of azobenzene
containing polymers that can be used in photoinduced surface relief formations.
These are soft liquid crystalline azobenzene containing copolymers of acrylate
with methacrylate monomers bearing oligo(ethylene oxide) chains. The
copolymers display a smectic liquid crystal phase at room temperature. After
preexposure to ultraviolet light, thin films of the liquid crystalline polymers
show highly sensitive photoinduced material transfer to generate the surface
relief structures. The typical exposure dose required for full polymer migration
-2
10 5
O
O
R
CH
3
O O
O
N
N
O
x
1-x
n
The inscribed surface relief structures can be rapidly and fully erased either by
irradiation with incoherent nonpolarized ultraviolet light or by heating close to
the clear point of the soft liquid crystalline polymers. It is also possible to
chemically crosslink the polymers with mixed vapors of hydrogen chloride and
formaldehyde after surface relief inscription. This results in a drastic
improvement of the shape stability, maintaining the structure at high
temperatures up to 250 °C. After cross-linking, the trans-to-cis photo-
isomerization readily proceeds without any modification of the surface
morphology and can, therefore, be applied to the photoswitchable alignment of
nematic liquid crystals.
103
is as low as 50 mJ cm
Light-Associated Reactions of Synthetic Polymers
289
5.3. Photonic Crystals
There is interest in photonic band gap crystals, due to their potential ability to
increase light wave guiding efficiency, to increase the efficiency of stimulated
emission processes, and to localize light. Original chemical approach to
fabricating large face-centered-cubic photonic band gap crystals was based on
self-assembly of highly charged, monodisperse colloidal particles into
crystalline colloidal arrays. The arrays subsequently self-assemble due to long-
range electrostatic repulsions between particles.
103,104
These crystalline colloidal arrays are complex fluids that consist of
colloidal particles give Bragg diffraction pattern in ultraviolet, visible, or near-
infrared light, depending on the spacings of the colloidal particle array. More
recently, robust semisolid photonic crystal materials were formed by
polymerizing a hydrogel network around the self-assembled crystalline colloidal
arrays.
105
S
N
O
O
N
N N
O
O
S
This new photonic crystal material can be made environmentally responsive so
thermal or chemical environmental alterations as a result of a material volume
changes, thereby altering the arrays of the photonic crystal plane spacings and
diffraction wavelengths.
105
It is claimed
106
that these photonic crystals can be useful in novel
recordable and erasable memories and/or display devices. Information is
recorded and erased by exciting the photonic crystal with ~ 360 nm UV light
photonic crystal diffraction wavelength. Ultraviolet light excitation forms cis-
azobenzene cross-links while visible excitation forms trans-azobenzene cross-
links. The less favorable free energy of mixing of cis-azobenzene cross-linked
species causes the hydrogel to shrink and blue-shift the photonic crystal
diffraction.
106
Unless polymers contain long sequences of double bonds, they are
fairly good insulators, particularly in the dark. Nevertheless, a number of
common polymers show measurable increase in conductivity, when irradiated
with light. When polymeric materials, like poly(vinyl fluoride), poly(vinyl
or ~ 480 nm visible light. The information recorded is read out by measuring the
5. Photoresponsive Polymers
5.4. Photoconducting Polymers
290
acetate), poly(vinyl alcohol), or poly(N-vinyl carbazole) are exposed to light
they develop charged species. The species can migrate under an electric field
and thus conduct electricity. When poly(N-vinyl carbazole) is doped with
photosensitizers or compounds that form charge-transfer complexes, the
photosensitivity can be increased and even extended into the visible region of
the spectrum. Since discovery in 1957 that poly(N-vinyl carbazole) has
photoconductive properties, there has been increasing interest in the synthesis
and study of this and other polymeric materials with similar properties that allow
various photonic applications. Related polymers are presently utilized in

Photoconductive polymers can be p-type (hole-transporting), n-type
(electron-transporting) or bipolar (capable of transporting both holes and
electrons). To date, all practical photoconductive charge-transporting polymers
used commercially are p-type.
Poly(vinyl carbazole) and other vinyl derivatives of polynuclear
aromatic polymers , such as poly(2-vinyl carbazole) or poly(vinyl pyrene) have
high photoconductive efficiencies. These materials may take up a helical
conformation with successive aromatic side chains arranged parallel to each
other in a stack. In such an arrangement the transfer of electrons is facilitated.
Also, it is believed that the primary mechanism for poly(vinylcarbazole) charge
carrier generation is due to excitation of the carbazole rings to the first excited
singlet state. This polymer absorbs ultraviolet light in the 360-nm region and
forms an exciton that ionizes in the electric field. The excited state, by itself is
not a conductive species. The addition of an equivalent amount of an electron
acceptor, like 2,4,7-trinitrofluorenone shifts the absorption of this polymer into
the visible region by virtue of formation of charge transfer states. The material
becomes conductive at 550-nm. This associated electron-positive hole pair can
migrate through the solid polymeric material. Upon dissociation of this pair into
charged species, an electron and a positively charged hole, the electron becomes
a conductive state. To achieve this additional energy is required and can be a
result of singlet-senglet interaction,
107
singlet-triplet interaction,
108
singlet-
photon interaction,
107
triplet-photon interaction,
109
and two-photon interaction.
109
Kepler carried out fluorescence quenching studies and concluded that the
migration of the exiton is the most probable energy transfer mechanism of
poly(vinyl carbazole).
109
He, furthermore, suggested that the exiton can visit
one thousand monomer units during its lifetime.
109
This is a distance of about
200 Å .
Kang and coworkers
111
also explored steady-state and pulsed photo-
also trans-polyphenylacetylene films doped with inorganic and organic electron
acceptors, particularly iodine and 2,3-dichloro-5,6-dicyano-p-benzoquinone.
They concluded that charge transport occurs by a band like mechanism that is
photocopiers, laser printers, and electrophotographic printing plates.
Light-Associated Reactions of Synthetic Polymers
291
modulated by shallow electron traps in the undoped polymer and by trapping the
charge-transfer complex in the doped polymer.
111
Guillet
112
states that photoconductivity o is equal to the current density
J divided by the applied field strength c, where J is amperture/unit electrode
area. This is related to the number of negative-charge carriers (usually electrons)
per unit volume, and p, is the number or positive charge carriers (or positive
holes) per unit.
112
o = J/c = n eµ
n
+ p eµ
p
where e is the charge on the electron, and µ
n
and µ
p
are the mobilities of the
the charge carrying species can be determined from a relationship
112
:
µ = d
2
/Vt
where d is the thickness of the film, V is the applied voltage and t is the carrier
represents the number of generated carriers reaching the external circuit per unit
time, compared with the number of photons absorbed at the same time
112
:
G = J
p
/ eI
0
(1 - T)A
where J
p
is the photocurrent, e is the electric charge, I
0
is the number of
incident photons per cm
2
s
÷1
, T is the optical trasmittance of the film, and A is
As stated above, the primary mechanism for charge-carrier generation
in poly(vinyl carbazole) appears to be due to the excitation of the carbazole
rings to their excited singlet states.
112
While the singlet excited state is not a
conductive species, the conductivity is believed to be the result of an associated
electron-positive hole pair migrating through the solid polymeric material.
Dissociation of the electron pair produces a separate electron and a positive hole
in such a way that the electron ends up in the conducting state.
112
This requires
acquisition of more energy. One way that can be accomplished is by excitron-
surface interaction.
113
Regensburger published an absorption spectrum,
fluorescence spectrum and photocurrent spectrum for a 7.6 µ films of poly(N-
vinyl carbazole).
114
The shape of the response of the photoconductor to the
wavelength of the light flash is very close to the shape of the absorption spectra.
Bauser and Klopffer explain this as a result of interaction of singlet excitons
with trapped holes.
115
the area of the sample that is being illuminated.
5. Photoresponsive Polymers
negative and positive carriers, respectively. Photoconductivity and mobility of
5.4.1. Photoconductive Polymers Based on Carbazole
drift time. The photoeffect is evaluated in terms of the effective gain, G. It
292
N
CH CH
2
n
The optical transparency of poly(vinyl carbazole) films produced by this room
temperature process appears to be quite high, although transparency decreases at
high conversions. In film form, this material is useful for photoconductors,
charge-transfer complexes, and electroluminescent devices. The higher polymer
molecular weight typically enhances film mechanical properties.
116
Harhold and Rathe
127
reported that they have prepared poly(9-
n
formed by dehalogenating polycondensation of 3,6-bis(o,o-dichlorobenzyl)-
10,9-methylcarbazole with chromiun (II) acetate. This polymer was found to be
also highly photoconductive. It's dark conductivity increases by doping it with
arsenic pentafluoride.
117
Photoconductive polymers and copolymers were also synthesized by
Haque and coworkers
118
from 2-(9-carbazolyl)-1-propenyl vinyl ether:
N
CH
2
(CH
2
)
2
O CH CH
2
The polymers and copolymers form by a cationic polymerization mechanism,
using boron trifluoride or ethylalumionum dichloride as the catalysts.
118
Charge transfer complexes also form from poly(vinyl carbazole), that
acts as the donor, and poly[2-(methacroyloxy)ethyl-4,5,7-trinitro-9-oxo-2-
fluorene-carboxylate], that acts as the acceptor
145
:
Lyoo used a low-temperature initiator, 2,2'-azobis(2,4-dimethyl-
valeronitrile) to polymerize N-vinyl carbazole in a heterogeneous solution in a
mixture of methyl and t-butyl alcohols.
116
The polymer that formed has the M
n
molecular weights >3 x 10
6
. The author emphasized that this method provides
ultrahigh-molecular-weight polymer and conversions greater than 80%.
dipenylvinylene). The polymer (M = 10,000) was methylcarbazole-3,6-diyl-1,2--
Light-Associated Reactions of Synthetic Polymers
293
NO
2
NO
2
O
NO
2
C
O
CH
2
CH
2
O
C O
C
CH
3
CH
2
n
The required mole ratio of components in the complex is 1:1.
145
Charge transfer complexation occurs in a similar manner in poly(2-
carbazolylethyl acrylate) molecularly doped with 2,4,7-trinitrofluorene.
Quantum efficiency of the hole propagation of the copolymer with the 0.05 to
1.0 molar ratio of trinitrofluorene to carbazole chromophores is higher than in
the corresponding trinitrofluorene and ethyltrinitrofluorene doped homopolymer
of poly(2-carbazolylethyl acrylate).
119
Kim and Webber studied delayed emission spectra of poly(vinyl
carbazole) that was doped with dimethylterephthalate and pyrene.
120
On the
basis of their results they concluded that at room temperature
dimethylterephthalate does not completely quench the triplet excitation state of
poly (vinyl carbazole). They also concluded that phosphorescent states of
poly(vinyl carbazole)-dimethylterephthalate are similar, implying a significant
charge-transfer character in the former.
In 1985 Mitra
55
prepared polymeric triphenylmethane dyes based on
condensation polymers such as polyesters and polyurethanes:
O
CH
2
CH
2
N
O
C
C
O
m
O
CH
2
CH
2
N
CH
2
CH
2
O
C
C
C
O
O
N
CH
3
CH
3
N
CH
3
CH
3
n
Cl
O
5. Photoresponsive Polymers
O
294
These dyes were then shown to sensitize photoconductivity of poly(N-vinyl
carbazole).
Polyacetylene derivatives exhibit unique characteristics such as semi
conductivity, high gas permeability, helix inversion, and nonlinear optical
properties.
121
Attempts were made, therefore, to incorporate carbazole into
polyacetylene in hope of attaining enhance properties.
122
CH
N
C C
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
C
N
C C
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
C CH
n
It was found
122
that the current conducted by this polymer during irradiation is
40 to 50 time higher than it is in the dark On the other hand, the electron
mobility of the di-t-butylcarbazolepolyacetylene (shown above) is lower than in
poly(vinyl carbazole). This was attributed to the bulkiness of the butyl groups.
122
Siloxanes with pendant carbazole groups were synthesized by
Strohriegl
73
by the following technique:
N
(CH
2
)
x
CH CH
2
Si
O
CH
3
H
Si
O
CH
3
N
(CH
2
)
x
+2
The material, however, did not turn out to be photoconductive. The photo-
conductivity of copolymers was also investigated. Copolyacrylates with pendant
donor and acceptor chromophores, such as 2-N-carozolylethyl acrylate
Light-Associated Reactions of Synthetic Polymers
295
73
These copolymers:
CH
2
CH
C O
(CH
2
)
x
CH
2
CH
C O
2
n m
x
N
C
O
NO
2
NO
2
NO
2
can be prepared by free-radical copolymerization of the appropriate monomers.
Similar work was done earlier by Natansohn,
119
who copolymerized N-
methyl, 1,3-hydroxymethyl carbazolyl acrylate with acryloyl-3'-hyroxypropyl-
3,5-dinitrobenzoate:
O
O
N
CH
3
O
O
O
O
NO
2
NO
2
n m
Illumination of the copolymer samples induces a certain degree of ionization
accompanied by proton transfer. There is a permanent increase in the quantity of
radicals generated by light. Another number of radicals apparently forms during
illumination but disappears in the dark.
119
It was reported
123
that a polymer formed by condensation of N-(3-
isopentyl)-3,6-diformyl-carbazole and 4-14-bis(-aminoethyl)aminophenyl-
azo]nitrobenzene yields a new polyazomethine, carbazole-azo polymer. The
product is soluble in organic solvents. The polymer possesses carbazole
5. Photoresponsive Polymers
4,5,7-trinitrofluorenone-2-ethyl acrylate do exhibit photogeneration properties.
Photoconductivity in the visible is obtained by charge transfer complexation.
(CH )
296
moieties and azo type nonlinear optical chromophores in the backbone. It shows
high photoconductivity and nonlinear optical properties.
When spiropyran is incorporated into plasticized poly(vinyl chloride)
membranes and placed between two identical NaCl solutions and irradiated with
ultraviolet light for long periods the potential decreases.
125
This was shown by
Ryba and Petranek to be a result of the spiran ring opening up
125
:
N
NO
2
CH
3
CH
3
R
UV light
visible light
N
CH
3
CH
3
R
NO
2
O
When the irradiation is interrupted and the membrane is irradiated with visible
light, the potential returns to its original value, because the ring closes back to
the spiran structure.
125
The addition of electron donors, like dialkyl aniline, to Kapton
polyimide film,
N N
O
O
O
O
O
n
results in an enhancement of photocurrent by as much as five orders of
magnitude, compared with the virgin material.
126
Freulich explains the
mechanism of enhancement as a result of radiation absorption by the charge-
transfer complex formed between the added electron donor and the imide
portion of the polymer backbone.. Excitations are followed by rapid and
complete electron transfer from the donor to pyromelitimide to yield the radical
126
These species
undergo rapid back electron transfer. In other words, the dialkyl aniline donates
mechanism of the ion radical returning to the ground state.
Hoofman et al.,
127
studied the thermochromic, solvatochromic, and
photoconductive properties of 3-, 4-, 6-, and 9-poly[(butoxycarbonylinethyl
urethane)-diacetylenes] that result from changes from rod (red or blue) to coil
(yellow) conformations of thepolymer backbone. Photoexcitations of the
solutions of these polymers in the rod state result in a large transient
5.4.2. Photoconductive Polymers that Are Not Based on Carbazole
one of the unpaired electrons in a typical photoreduction reaction to the
anion of the polymer and the radical cation of the donor .
carbonyl group. The reaction is reversible and the photoconduction is by a
Light-Associated Reactions of Synthetic Polymers
297
photoconductivity, while only very small conductivity signals are observed in
the coil state. The thermochromic shift that occurs in going from the rod state at
room temperature to the coil state at 65 °C is accompanied by a decrease in the
photoconductivity. The large conductivity signal in the rod state is attributed to
the formation of mobile charge carriers possibly via interchain charge transfer
extends to microseconds.
Wong et al.,
128
reported that they prepared a soluble rigid-rod
organometallic polymer containing electron-donating and electron-withdrawing
trans-[-Pt-(tibutylphosphine)
2
-acetylene-R-acetylene-]
n
(where R = bithiazol-
ediyl) groups. The polymer was formed by cuprous iodide-catalyzed
dehydrohalogenation reaction. The electron-donating and electron-withdrawing
properties of the thiazole ring confer solubility to the polymer. This
polyacetylene is luminescent with a singlet emission peak at 539 nm and photo-
conducting. The glass transition temp. of the polymer is 215° and it shows
relatively good thermal stability. The t-conjugation of the ligands extends into
and through the metal core and the absorption peaks show a significant red-shift
of 17-26 nm compared to the bithienyl counterparts due to the presence of the
electron-withdrawing imine nitrogen atoms.
128
Kimura et al.,
129
reported applying organic photochromic compounds
to photochemical switching of metal-ion complexation and ionic conduction by
combining photochromism with metal-ion binding property of crown ether
derivatives. They synthesized vinyl polymers, incorporating a crown
spirobenzopyran moiety at the side chain:
O
OCH
3
O
N
CH
3
CH
3
O NO
2
1-x
O
O
N
O
The crown spiropyran in the electrically neutral form can bind an
alkali metal ion with the crown ether moiety. At the same time the
spirobenzopyran portion isomerizes to the corresponding merocyanine form
photochemically. The zwitterionic merocyanine form of crowned
spirobenzopyran moiety brings about a significant change in the metal-ion
binding ability. This prompted the authors to apply the compound to photo-
5. Photoresponsive Polymers
within aggregates. The decay of the photoconductivity is nonexponential and
298
responsive ion-conductive materials. They observed that the ion-conductivity
was increased by ultraviolet light and decreased by visible light.
129
Chan and coworkers
130
prepared polystyrenes and poly(methyl
methacrylate)s that contain metal complex cores:
n
O
M
n
O
O O
H H
Re
Cl
OC
OC CO
M
=
O
H H
Ru
O
N N
2PF
6
or
M =
When the polymers are doped with a hole transporting triphenylamine, an
enhancement in photoconductivity in the visible region is observed. This
suggests that the metal complexes serve as photosensitizers instead of charge
carriers.
150
Chan and coworkers
130
observed an electric field dependent charge
separation process in these polymers. It is described well by the Onsager's
theory of charge germinate recombination. This theory assumes that some
fraction of absorbed photons produce bound thermalized electron-hole pairs that
either recombine or dissociate under the combined effects of the Coulombic
attraction and the electric field. The photogeneration efficiency is given as the
Light-Associated Reactions of Synthetic Polymers
299
product of the quantum yield of thermalized pair formation and the pair
dissociation probability:
where I
g
is a recursive formula given by
where I
0
(x) = 1 - exp(-x), u is the primary yield of thermalized bound pairs, r
0
is the initial thermalization separation between the bound charges, e
r
is the
relative permeability, and E is the applied electric field strength.
Jenekhe et al.,
132
reported exciplex formation and photoelectron
transfer between several n-type {electron accepting) t-conjugated rigid-rod
polymers and donor triarylamine molecules. In particular they reported an
ladder).
132
No evidence was observed by them of a ground state
charge transfer or any strong interactions between the conjugated
polymer pairs
Transient absorption spectra of a blend of thin films in the 420-730 nm region
region was observed. Jenekhe and de Paor propose that they observed enhanced
electron transfer.
132
The electron transfer was illustrated as follows:
N
S N
S
n
N
N
N
O
O
N
n
UV light
5. Photoresponsive Polymers
investigation of an n-type conjugated polymer poly(benzimido azobenzophe-
nanthroline
were obtained at various time delays following photoexcitation at 532 nm.
Dramatically enhanced photoinduced bleaching in the 430-480 nm
photobleaching in the blends and that it is a consequence of photoinduced
300
N
S N
S
n
+
N N
N
N
O O
n
Molecular materials, such as 2-(2-hydroxyphenyl)benzoxazole and 2-(2-
hydroxyphenyl)-benzothiazole, which contain intramolecular hydrogen bonds
are known to undergo excited state(charge transfer) intramolecular proton
5.5. Proton or Electron Transfer in the Excited State
In 1966 Conwll and Mizes
131
observed that exposure to light frequency
beyond the absorption edge in polymers such as poly(p-phenylene vinylene),
and polythiophene is expected to create excitons, some of which decay
radiactively. Based on the similarity of the emission from thin films and
oligomers of poly(p-phenylene vinylene), it was concluded that the exciton is a
single chain. Polyimides like Kapton owe their resistance to degradation at least
in part to charge transfer character. This generated considerable interest in the
role of various types of charge transfer complex states in the photostabilization
polymers are currently of wide interest in view of their importance to the
fundamental understanding of the electronic structure and properties of the
materials and applications such as photodiodes, photovoltaic cells, electro-
photographic photoreceptors, and molecular electronic devices.
Jenckhe at al.,
133
explored the effects of molecular size, extent of
conjugation, concentration quenching, and competition with excimer formation
on intramolecular proton transfer as well as on the electro-luminescent device
potential of polymeric materials. Materials like 2-(2-hydroxyphenyl)-
benzoxazole and 2-(2-hydroxyphenyl)benzothiazole contain intramolecular
hydrogen bonds and are known to undergo excited state charge transfer
reactions and intramolecular proton transfer upon excitation. They reported,
however, that the results of their studies with model compounds and several
polymers, whose structure:
transfer upon photoexcitation.
of polyimides The photoinduced electron transfer processes of t-conjugated
Light-Associated Reactions of Synthetic Polymers
301
N
O O
N
O H
n
N
O
F
3
C CF
3
O
N
O
H
n
suggest that incorporation of such compounds into the backbones of stiff-chain
conjugated polymers does not ensure the occurrence of intamolecular proton
transfer upon photoexcitation.
133
Chang et al.,
134
noted from the literature that the excited-state
intramolecular proton transfer is a form of phototautomerization occurring in
the excited states of the molecules possessing cyclic intramolecular or solvent-
bridged hydrogen bonds. Since this process is fast enough to accompany the
short-lived first excited singlet state, the electronic excitation of a normal form
(N) in the ground state yields a proton-transferred excited-state tautomer (T*) of
the much lower energy. This T* relaxes radiatively or nonradiatively to the
metastable ground state T, which reverts to the normal form (N) via reverse
proton transfer. Therefore, the different absorbing and emitting species result in
a large Stokes shift. Chang et al.,
134
pointed out that until now, the phenomenon
has been studied mainly in the solution systems for small organic molecules like
pyridine derivatives, etc. In most cases, however, phototautomeric fluorescence
is rather weak for practical applications at ambient temperature due to more
effective internal conversion or broken hydrogen bond by torsional motion. To
address these limitations, Chang et al.,
134
have considered a polymeric system
with semirigid prototype polyquinoline groups that contains intramolecular H
bonds between the enol and imine groups. The polymer was illustrated as
follows:
5. Photoresponsive Polymers
302
N
O X
N
OCH
3 OCH
3
O
n
Where the substituent X on the polymer is an OH group with an intramolecular
H bond, the polymer in solution shows dual blue and red fluorescent bands . The
authors claim that a semiempirical molecular orbital calculation of this
emission supports the phenomenon of excited-state intramolecular proton
transfer.
Earlier, Nishijima and coworkers were able to generate hydrogen by
visible light irradiation with the aid of ruthenium complexes and colloidal
platinum stabilized by viologen bearing polymers in aqueous media.
124
The
polymer was prepared as follows:
CH
2
N(C
2
H
5
)
3
Cl
n
+
N N C
4
H
9
Br
polymer with
1% viologen groups
Hydrogen generation requires a photosensitizer, an electron donor, an electron
mediator and a multi-electron redox catalyst. To obtain the polymer the reaction
mixture must be refluxed in methanol for 20 hours. This yields a polymer with
1% viologen groups. In the system, water donates the protons and electrons are
supplied by ethylenediamine tetraacetic acid disodium salt.
124
The viologen
groups transport the electrons to the multi-electron redox catalyst (2,2'-
bipyridine)ruthenium(II), Ru(bpy)
++
.
5.6. Reversible |-Sheet Transitions
A convenient,
ligonucleotides was reported by Saito and co-authors.
135
5- vinyldeoxy -
fully reversible method for ligation of deoxyo-
Light-Associated Reactions of Synthetic Polymers
303
uridine at the 5'-end of the DNA strand and a thymine residue at the 3'-end were
used to form a cis-syn [2+2] adduct between the vinyl group and the 2,3-double
bond by simple irradiation at 366 nm. This adduct formation is completely
reversible by irradiation at 302 nm to restore the original compounds
N
N
N
NH O
NH
2
O
O
N
N
N
NH O
NH
2
O
O
The authors demonstrated this coupling principle by simultaneous ligation of
several single-stranded deoxyoligonucleotides on a DNA template to produce a
longer DNA. The process is then quantitatively reversed to give the original
oligonucleotides.
5.7. Polymers that Shed Small Molecules, Ions, or Free-Radicals
Upon Irradiation
Into this category of materials belong polymers that shed molecules,
length. One such material is poly[p-(formyloxy)styrene]. It can be prepared from
in ultraviolet light
136
:
O
n
C
O
H
UV light
n
OH
The reaction can take place in solid state or in solution. It was reported that the
material can be used in photolithographic processes and that it produces sharp
images.
136
Such images can be developed positively or negatively.
Crivello and coworkers
137
prepared aromatic polyimides bearing
sulfide linkages in the main chain by condensing sulfur containing dianhydride
with aromatic diamines. They also condensed sulfur containing aromatic
diamines with dianhydrides. Phenylation with diphenyliodonium salts converts
5. Photoresponsive Polymers
ionic species, or free-radicals when irradiated with light of the appropriate wave
poly(p-hydroxy styrene). The polymer was reported to decarbonylate smoothly
304
the diarylsulfide groups into triarylsulfonium salts. The resultant photosensitive
polyamides undergo main chain cleavage during photolysis with ultraviolet
light. These polymers are offered as positive high temperature photoresists.
137
The decomposition upon UV light illumination can be illustrated as follows:
O N
O
O
S
O N
O
O
AsF
6
n
O N
O
O S
O
N
O
O
n
UV light
+
+ H AsF
6
The details of the decomposition mechanism of sulfonium salts upon irradiation
with ultra-violet light are described in Chapter 2. The illustration above is a
simplified version.
Preparations of multifunctional photopolymers with both pendant
phenacyl ester and vinyl ether groups were reported.
138
These materials were
synthesized by one-pot method for the reaction of poly(methacrylic acid) with 2-
chloroethyl vinyl ether, This was followed by the reaction with phenacyl
bromides using l,8-diazobicyclo-[5.4.6]-undecene-7. It was found that the
pendant phenacyl ester groups cleave upon photoirradiation to give pendant
carboxylate groups. The produced carboxylate groups react with pendant vinyl
ether groups to form acetal linkages.
138
5.8. Color Changes
Two distinct triplet excimetric emissions were observed in the solid
films of poly[N-(vinyloxy)-carbonyl)-carbazole].
139
Phosphorescence spectra of
this polymer and its monomers in solutions are essentially the same as those
observed for poly(N-vinylcarbazole). The fluorescene spectrum, however,
shows a significant shift to the blue.
139
Light-Associated Reactions of Synthetic Polymers
305
Copolymers of vinyl viologens, such as N-vinylbenzyl-N'-alkyl and
benzyl and N-(_-methacroyloxy)propyl-N'-propyl-4,4'-bipyridinium dihalides
and polar aprotic comonomers, such as N- vinyl-2-pyrrolydone or
N.N'dimethylacrylamide exhibit a strong color formation upon irradiation.
140
One such copolymer can be illustrated as follows:
CH
2
CH
CH
2
CH
2
CH
N
O
N
N CH
2
X
X
where, x - Br, BF
4
(SO
4
)
1/2
copolymers in the film state are completely reversible and faster than in
corresponding copolymers with protic comonomers, such as acrylamide. A
characteristic absorption spectra of the copolymer is attributable to single radical
cations. The mechanism of reversible color development was shown to be as
follows
140
:
N N
light
O
2
N N
X X
viologen ion pair in copolymer
(colorless) (highly colored)
radical cation-anion pair
Photochromic compounds based on l,2-bis(3-thienyl)-cyclopentene
derivatives undergo reversible photocyclizations between their colorless ring-
open and colored ring-closed forms when irradiated with light of appropriate
wavelengths
141
:
5. Photoresponsive Polymers
. The photocolor developments of these aprotic
306
S S
R
R
X
X
X
X
X
X
UV light
visible light
S S
R R
X X
X X
X X
where X = F or H
This was utilized to form several novel homopolymers with l,2-bis(3-
thienyl)cyclopentene derivatives using ring-opening metathesis polymerization
techniques.
141
The color forming cyclization reaction in the polymers can be
illustrated as follow:
S
S
R
X
X
X
X
X
X
O
O
N
O
O
O
H
Ph
n
X = H R = Cl
n
O
O
N
O
O
O
H
Ph
S
S
X
X
X
X
X
X
R
UV light
visible llight
colorless colored
Lim, An and Park
166
synthesized polymers with similar photochromic
groups for use in erasable optical memory and fast optical switching. The strong
fluorescent of the polymer in a neat polymeric film shows that it can be
photoswitched through highly efficient bistable photochromisms. They also
demonstrated erasable fluorescence photoimaging on a spin coated film. The
photoreaction of the polymer was illustrated as follows
142
:
Light-Associated Reactions of Synthetic Polymers
307
S S
F
F F
F F
F
R
n
S S
F
F F
F F
F
R
n
UV light
visible light
(>350 nm)
R =
NC
CN

Eisner and Ritter reported that they were able to form photoresponsive
membranes.
167
The polymer was illustrated as follows
143
:
C
C
C
O H
H
O
(CH
2
)
9
O
C
C
C
O
O
H
H
n
alcohol) and poly(m-phenylene-isophthalamide) and formed into membranes,
the permeation of gases through the membranes can be controlled by ultraviolet
light irradiation.
143
5.10. Photoisomerizable Rotaxanes
Okada and Herada reported formation of photoresponsive poly-
ethylene glycol rotaxanes with anthracene derivatives stopper groups and
cyclodextrin cyclic components.
99
Light-associated reversible changes of these
polyrotaxanes were observed.
99
Thus, light irradiation with ultraviolet light or
heat causes a rearrangement to a mixture of polyrotaxane together with a
catenane.
5.11. Photoresponsive Shape Changes
Landlein, Langer, and coworkers,
144
reported grafting photoresponsive
groups to copolymer films. The photoresponsive groups can be illustrated as
follows:
5. Photoresponsive Polymers
5.9. Photoresponsive Gas Barrier Films
By incorporating photolabile groups into the polymeric backbone
When this polymer as well as its precursor are blended with poly(vinyl
308
O
O
O
O
When the copolymer films are stretched and then illuminated with ultraviolet
light, the light responsive groups crosslink, maintaining the elongated state of
the films after the removal of the external stress. Subsequent exposure of these
elongated films to ultraviolet light of a different wave length causes the cross-
links to cleave and the film returns to its original shape. Formation of other
temporary shapes is also possible.
144
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144. A. Landlein, R. Langer, et al., Nature, 2005, 434, 879
143. E. Elsner and H. Ritter, Makromol. Che., Rapid. Commun., 1987, 8, 595,
145. K. Abe, S. Haibara, and Y. Itoh, Makromol. Chem., 1985, 186, 1505
5. Photoresponsive Polymers

1
in an electrooptic material by internal electric fields produced by optical
redistribution of charge carriers. It is based on the combined effects of photo-
conductivity and electrooptic property.
2,3
Under the illumination of non-
uniform light formed by the interference of two coherent laser beams, a spatially
redistribution of photoinduced charges. To be more specific, in photorefractive
materials, the absorption of light is followed by diffusion and drift of the free
charges. This generates a space-charge field that modulates the refractive index.
1
The refractive index of material is subsequently modulated via an electrooptic
effect. Photorefractive materials exhibit unique features, such as
advantages in their applications in the fields of optical data storage and
information processing.
4
changes in the indices of refraction in response to relatively low power light.
This photorefractive effect, a persistent but reversible change in the refractive
index of an electrooptic material is caused by nonuniform illumination. It was
first observed as a detrimental “optical damage” in lithium niobate and in other
inorganic crystals used for second harmonic generation. Since the phenomenon
became understood, such materials found application in integrated optical
devices. Presently used inorganic materials are hard to process, however.
Extensive research is, therefore, being carried out to develop polymeric
materials that could replace inorganic ones, such as LiNbO
3
or BaTiO
3
.
5
As a
result, it was first reported in 1991 that it is possible to form polymers that
exhibit the photorefractive effect .6 Such polymers must have the ability to
convert electrical signals into optical output. In other words, they must function
electrooptically when changes in applied voltage result in changes in their
refractive index. Such changes are produced by optical redistribution of charge
carriers. In other words, in order for the molecules to exhibit second-order
optical effects, they must be “noncentrosymmetric” or not centrally
symmetrical
7,8,9
. These effects include the generation of second harmonics. This
generation of the second harmonics doubles the frequency of light while the
316
Chapter 6
photosensitivity, reversibility, and beam amplification. This provides important
Photorefractivity is defined as a modulation of the index of refraction
oscillating space-charge field is formed. This field forms from generation and
Photorefractive materials are unique in their ability to generate large
Photorefractive Polymers for Nonlinear Optics
6.1. Photorefractive Materials
317
electro-optical effects enable the electric current to control and modulate light.
To put this in other words, the electric field can alter the index of refraction and
thereby change the light propagating through polymeric materials. This in turn
Within a relatively short time, many polymeric materials were
10-14
These materials
consist of polymers with charge transport agents and photosensitizing dyes. The
quantity of change in a material’s refractive index that is altered by alterations in
an applied electric field is expressed as the electrooptic coefficient r. Lithium
niobate has an r value of 30 pm / volt. Several polymers are already known that
possess coefficients (at 1.3 Pm) greater than 30 pm/V and the aim now is to
develop materials with r values of 50 pm / volt or even higher. It is also known
that the photorefractive effect can also be observed in many organic materials,
such as polymer films,
15
liquid crystals,
16
and organic glasses.
17
Device-quality materials must possess: 1) large optical nonlinearity, 2)
high temporal stability of the dipole orientation, 3) low optical loss, and 4) good
processibility. The first requirement was addressed by a number of research
groups and various high PE chromophores have been developed. Some of these
exhibit large bulk nonlinearity in composite systems. Unfortunately, however,
the bulk nonlinearity of composite samples tend to decays rapidly, due to fast
relaxation of chromophore orientation. Long-term stability of dipole orientation
is a problem associated with this type of materials. To realize a stable dipole
alignment, chromophores have been linked to high-Tg polymers such as
polyimides, to lock the dipole orientation into rigid matrix after poling. This too
is a problem, because many nonlinear optics chromophores cannot survive the
high processing temperatures (ca. 220-250
o
C) and the harsh acidic environment
of polyamic acid during imidization. In addition, to be industrially useful, the
device-quality nonlinear optics polymeric materials must retain high optical
quality in thin films, high optical damage thresholds, and exhibit low optical
propagation loss. They should also lend themselves to device fabrication without
considerable difficulty and maintain sufficiently large and stable nonlinear
optics susceptibilities.
18
To be of practical use the developed materials must
also exhibit reasonable thermal stability (greater than 95% retention of optical
nonlinearity for 1000 hours at 100
o
C). Although it is very difficult to solve all
the problems, very impressive progress has been made to date.
19
This chapter
tries to illustrate what has been achieved so far.
In summary, the photorefractive polymers are required to do the
following:
1. Transport the charges through the material.
2. Trap the charges.
3. Provide nonlinear optical properties or changes in the index of refraction
of the material in response to changes in an applied electrical field (Exhibit an
electrooptic effect).
modulates the phase of light.
6. Photorefractive Polymers for Nonlinear Optics
developed that do exhibit the photorefractive effects.
318
4. Respond to light by generating electrons and positively charged vacancies.
Nonlinear optics effects are generally described by a polarization equation for
the optical response (P) of a material to an optical electric field (E)
20
:
P = F
(1)
E + F
(2)
E
2
+ F
(3)
E
3
+ ...
In this equation the F
(1)
term describes linear optics of such phenomena as light
reflection and refraction. The other terms, beyond the F
(1)
namely, F
(2)
and F
(3)
describe the second- and third-order optical effects, respectively.
The above equation is called the polarization equation. In order for the
materials to exhibit second-order effects, the S electrons must de-localize in
response to applied electric fields. This results in spatial asymmetry, as already
stated above.
8
Also, for the second-order effects to be large, there must be large
differences in the dipole moments between the ground state and the excited
states.
There are some essential differences between photorefractive polymers
and inorganic crystals. In the organic materials the quantum efficiency for
generation of mobile charge, ), is highly field dependent due to Onsager
germinate recombination.
21
High fields are, therefore, generally required for
facile charge generation. Also, the mobility is highly field-dependent.
21
It can
vary as log E. This has been widely observed in many molecularly doped
polymers.
22
This means that higher fields are required to increase the speed of
charge transport.
It was pointed out
23
that the performance of photorefractive polymer
composites is too large to be explained by the simple electrooptic
photorefractive effect alone. A theoretical model was offered
10
where both the
birefringence and electrooptic coefficient are periodically modulated by the
space-charge field due to the orientational mobility of the nonlinear
chromophores at ambient temperatures.
The methods that are used in preparation of the polymeric materials
with nonlinear optical properties can be as follows.
24
They include (1) doping or
simply dissolving in the polymeric matrix chromophores, (2) covalent
attachment of such chromophores
25
to amorphous and liquid-crystalline
polymers, and (3) assembling nonlinear optics chromophores into Langmuir-
Brodgett layers. The statistical center of symmetry in polymers is removed via
dipolar alignment by application of an external electric field (called poling). A
strong electric field is applied while the polymer is heated at, or preferably
below, T
g
, or glass transition temperature, of the material. The active molecules
become mobile and the dipoles are forced to line up. This is done, because the
chromophores must be aligned in such a way that the material has no center of
symmetry. While the electric field is still applied, the films are then cooled. This
locks in the asymmetry. The electrooptic response in these materials is,
therefore, a result of the electric field induced alignment of the chromophores,
Light-Associated Reactions of Synthetic Polymers
319
which are second order nonlinear. Due to strong interactions among the electric
dipoles, the poled structures are in a metastable state. This means that the poled
nonlinear optics chromophores that possess large dipole moments will tend to
relax back to the randomly oriented state.
26
The stability of the poled structures,
therefore, strongly depends on the rigidity of the overall material. To maintain
this rigidity, polymers with very high T
g
and thermal stability have been used
with a fair amount of success. Another approach is to crosslink the polymeric
matrix. This has also yielded fruitful results. To obtain large nonlinearities the
quantity of chromophores in the system must also be large. The problem is,
however, that chromophores tend to have high dipole moments, and above a
critical loading density, electrostatic interactions occur. Such interaction favor
centro-symmetrical ordering of the chromophores in the polymer matrix. As a
result, F
(2)
will not increase linearly with chromophore loading N, but it will
show a maximum at relatively low loading levels. This maximum is
approximately 15 wt % for dipole moments and decreases at higher
chromophore concentrations.
Several approaches to diminish the dipolar interactions were
investigated. Dalton et al.,
27,28
studied the influence of the shape of the
chromophore on their dipolar interaction. The conclusion that was reached was
that a spherical shape inhibits dipolar interactions. Another approach was to use
chromophore-functionalized dendrimers, where dendrons effectively decrease
the interactions among the chromophores due to steric hindrance.
29
6.2. Chromophores for Nonlinear Optics
A typical nonlinear optics material consists of an electron-accepting
group, a bridge, and an electron-donating group. The donor-acceptor charge
transfer groups are connected with and separated by a S-electron segment
(consisting typically of polyene, azo, or heteroaromatic moieties). Thus,
chromophores that are active in nonlinear optics are conjugated molecules that
contain electron-donating group on one end and electron accepting groups at the
other end. Applications of external electric fields cause the electric charges in
the molecules to separate. The resultant asymmetric distributions of charges
markedly affect the interactions of the chromophores with light. The function of
the conjugate bridge is to allow electronic communication between the donor
and the acceptor. Examples of the electron donors can be amino or methoxy
groups and of the acceptors can be nitro or cyano groups.
30,31
It was shown, that
large molecular nonlinearities can be achieved by using extended polyene
bridge systems.
32
For instance, one compound , a derivative of isoxazolone
exhibits PE value of 3156 x 10
-48
esu at 1.907 Pm and a low absorption
maximum of 562 nm in chloroform.
32
(where P is the dipole moment and E is
the molecular first hyper-polarizability). More precisely, the term E was defined
by Jen, Marder, and Shu
33
as:
6. Photorefractive Polymers for Nonlinear Optics
320
E v ( P
ee
- P
gg
)(P
2
ge
/ E
2
ge
)
where g is the index of the ground state, e is the index of the charge-transfer
excited state, and P is the dipole matrix element between the two states.
33
Unfortunately, the unsubstituted polyene segments of the above mentioned
chromophore make that compound thermally, photochemically, and chemically
unstable.
34
On the other hand, it was shown that thermal stability of many
chromophores can be significantly improved by using aromatic amino functional
groups in place of aliphatic amino functional groups as the electron donors.
35,36
The same is true when a simple polyene bridge is replaced with a thiophene
moiety.
Some examples of chromophores that were incorporated into side
chains and main chains of polymers are donor/acceptor substituted stilbenes
and azobenzenes.
37
Another example are the two compounds shown below:
N
CN
CN
CN
H
2
N NO
2
In some of the early preparations polymers and copolymers of poly(n-
vinylcarbazole) were used as the polymeric materials
38
:
N
n
The polymers were combined (or doped) with such diverse chromophores as
(diethylamino)benzaldehyde diphenylhydrazone:
Light-Associated Reactions of Synthetic Polymers
321
N
CH
3
CH
2
CH
3
CH
2
C
H
N N
or 2,5 dimethyl-4-(p-nitrophenylazo)anisole:
CH
3
O
CH
3
CH
3
N
N NO
2
For instance, one material was prepared from photoconducting
poly(N-vinyl carbazole) that was doped with a blue-shifting optically nonlinear
chromophore, 3-fluoro-4-N,N-diethylamino-p-nitrostyrene. This material was
sensitized for charge generation with 2,3,7-trinitro-9-fluorenone.
39
A material was reported recently that is claimed to be very efficient. It
transition temperature.
The T
g
. is below room temperature.
40
The material is prepared from
g
41
42
6. Photorefractive Polymers for Nonlinear Optics
plasticized guest-host polymer with a low glass is a
a photoconducting poly(9-vinylcarbazole), a plasticizer, 9-ethylcarbazole, a
nonlinear optical chromophore, 2, 5-dimethyl-4-(p-nitrophenyl) azoanisole,
and a sensitizer, 2,4,7-trinitro-9-fluorenone (2% by weight). The sensitizer
forms charge-transfer complexes with the carbazole moieties. If a periodic
light-intensity pattern is incident to the material, charges are generated in the
bright regions due to the optical excitation of the charge-transfer complexes.
The carbazole units act as hole-transport agents. This enables the holes
to move to the dark regions of the grating by diffusion or drift under the influence
of an applied external field. In most photorefractive materials, the space
charge field is produced by inhomogeneous charge distribution that
modulates the refractive index through the electro-optic effect. Because, the
material has a T below room temperature, the index modulation amplitude is
to 100% diffraction efficiency in a 105 Pm thick film with sub-second
response time and high resolution. Unfortunately, however, the polar dye in the
separation, thus reducing the dielectric strength of the material.
enhanced further by birefringence. This material was reported to combine close
nonpolar matrix tends to crystallize slowly and undergoes space separation
322
Another chromophore, 4-(4'-nitropnenyl)azo-1,3-bis[(3'- or - 4'-
vinylbenzyl)-oxy]benzene:
O
R
N
O
N NO
2
R
is claimed to exhibit very good phase stability and a nearly complete diffraction
at 633 nm.
42
Also, polymers that contain carbazole moieties in the backbone with
two acceptor groups as multifunctional chromophores were synthesized.
43
The
sytheses were carried out by a Knoevenagel polycondensation of
divinylcarbazoles with bis(cyanoacetate)s using 4-(N,N'-dimethyl)pyridine as a
base.
43
Second-order nonlinear optical properties of the polymers were
confirmed by second harmonic generation. The photorefractive optical gain of
these polymers was demonstrated to be high.
In 1996, work that focused upon the exploration of alkyl and aryl amine and
ketene dithioacetal donor groups together with a variety of electron acceptor
groups was reported.
44
The acceptor groups included thiobarbituric acids,
isoxazolones, cyanovinyls, sulfoximines, tetracyanoindanes, and a cyanosulfone.
Improvements in PE values of the order of 3-10, relative to the values observed
for commonly used stilbenes and azobenzene chromophores were readily
realized. More than one hundred such chromophores were incorporated into
processable polymer lattices and evaluated for stability in the polymers under
conditions of corona poling (explained above) and optical illumination (at 1.3
Pm). This led to a conclusion
44
that promising chromophore-containing
polymeric materials that can be poled to yield electrooptic coefficients greater
that 30 pm/V, are among those that contain isoxazole and tetracyanoindane
acceptors. They appear to exhibit the good stability at condition of corona poling
and optical irradiation (in the presence of atmospheric oxygen). A polymeric
material of this type can be illustrated as follows:
Light-Associated Reactions of Synthetic Polymers
323
O
O
S
CN NC
CN NC
n

nonlinear optics chromophores are intended for incorporation into polyimides,
polyurethanes, polyureas, and polyamides.
45
Among them are some promising
chromophores that were reported by Jen and coworkers .
Additionally, new thermally, photochemically, and chemically stable
chromophores were reported recently.
46
These were formed by incorporating
N
N
O
O
Ph
optical loss of 0.96 dB/cm with no loss attributable to intrinsic absorption of the
chromophore.
47
Table 6.1. Some Examples of Chromophores for Nonlinear Optics
a
NLO Chromophores PE(x 10
-48
esu)
N N
N NO
2
800 (1.6Pm)
N
S
CN
CN
CN
6200 (1.9 Pm)
6. Photorefractive Polymers for Nonlinear Optics
Table 6.1. gives examples of some nonlinear chromophores. These
33
isophorone moieties into chemical structure, such as:
The above shown chromophore, was reported to yield up to 30 pm/V at an
324

NLO Chromophores PE(x 10
-48
esu)
N
S
CN
NC CN
NC
6144(1.9 Pm)
N
NO
2
580
N
S
CN
CN
3450
N
S
N
N
O
O
S
5380
N
NO
2
580
a
from various literature sources
Another recent study reports
46
a preparation of two thermally stable
chromophores that have the following structure:
Table 6.1. (Continued)
Light-Associated Reactions of Synthetic Polymers
325
H
2
N
N
NH
2
N S
NO
2
H
2
N
N
NH
2
CN
CN
The trapping sites may be provided by additional doping materials. It is
trapping functions. This, for instance, was accomplished by reacting bisphenol
A diglycidyl ether with 4-nitro-1,2-phenelenediamine, a chromophore.
10
N
NO
2
N O
OH
CH
3
CH
3
O CH
3
OH
The crosslinked, optically nonlinear material was doped with a charge-
transporting agent, (dimethylamino) benzaldehyde diphenylhydrazone.
Subsequent dramatic improvement in performance was achieved in a similar
polymer by using nitroaminostylbene as the charge transport agent
48
.
49
reported that they developed a series of dendrized
chromophores and fluorinated chromophore-containing dendrimers that possess
molecular architecture, they claim to have achieved dramatically enhanced
poling efficiency in these materials. They incorporated these chromophores that
contain fluorinated dendrons onto a hydroxystyrene photoresist polymer to form
6. Photorefractive Polymers for Nonlinear Optics
also possible to have the nonlinear optics groups perform charge-generating or
nanostructures and electro-optic activities. By controlling their size, shape, and
You and coworkers,
326
side-chain dendrized nonlinear optics polymers. A large electrooptic
do not possess the thermal stability that is needed for practical applications. The
poling-induced polar order decays quite rapidly upon heating due to low glass-
transition temperature (Tg) of the polystyrene backbone.
49
synthesized a high-Tg
aromatic polyimide with pendant dendronized nonlinear optics chromophore
with a cardo-bisphenol linkage to a rigid aromatic polyimide backbone:
N
O
O
N
O
O
F
3
C
CF
3
OR RO
n
where R =
O
N
O
O
O
CN
O
CN
NC
O
O
O
R
R
3
where R =
O
F
F
F
coefficient (97 pm/V at 1.3 , um) was demonstrated. These materials, however,
Light-Associated Reactions of Synthetic Polymers
To overcome this, You and coworkers,
327
The authors claim to have successfully applied the site isolation principle to a
rigid 3-F cardo-type polyimide with very high T
g
. At the same time high poling
efficiency is also claimed to yield very large electrooptic coefficient (71pm/V at
1.3 Pm) More than 90% of this value is claimed to be retained at 85
o
C for more
than 650 hours.
et al.,
50
polymers, which are composed of a new type of nonlinear optical chromophore
attached to conjugated polymer, poly(p-phenylene-thiophene). Since the NLO
chromophore is labile in many reaction conditions, the Stille coupling reaction
was used to prepare these polymers. The resulting polymers exhibit high PR
performances. An optical gain coefficient of 158 cm ^ at a field of 50 V/^m and
a diffraction efficiency of 68% at a field of 46 V/^m for polymer PI were
obtained, which are among the best values for fully functionalized PR polymers
to date.
6.3. Polymeric Materials for Nonlinear Optics
Poling, as stated earlier, is applied to lock in asymmetry. This,
however, is very difficult to do permanently. With time and subsequent heating
the orientations of the polymers tend to become disordered. A slow decay of the
approaches were tried. One concept is to synthesize polymeric materials with
high T
g
, such as aromatic polyimides and polyamides. Other approaches to
preserve chromophore alignment in poled polymers involve restricting freedom
of movement of the chromophores by various crosslinking schemes as well as
by using liquid crystalline materials.
6.3.1. Crosslinked Polymeric Materials
The crosslinking process in some systems must be carried out at 200
o
C.
51
Also, the high T
g
approach required high poling temperatures, like 225 to
250
o
C and for integrated optic applications, poling temperatures above 350
o
C
might be necessary due to the high temperatures that are required during the
fabrication of the devices. These temperatures are extremely demanding for
organic molecules, particularly for chromophores with extended conjugation.
Many nonlinear optics chromophores just cannot survive the high processing
temperatures (ca. 220-250
o
C) or the harsh acidic environment of polyamic acid
(in preparation of polyimides) during imidization.
50
Polymer lattice hardening
under mild conditions is much desired for processing chromophores into useful
device-quality materials.
51
6. Photorefractive Polymers for Nonlinear Optics
describe the synthesis of several new photorefractive Marder
optical nonlinearity results. In trying to overcome the draw-back various
328
Dolton et al.,
52
pointed out that typical crosslinking processes to
achieve stability possess additional deficiencies. These are entanglements of the
difficulty in aligning dipolar chromophores. The result is lower electrooptic
activity of these poled thermoset materials. To overcome this nonlinearity-
stability trade off, Dolton et al.,
52
suggested that a new poling process is
Ideally, this process should be prior to and separate from any crosslinking
process. Moreover, to achieve and maintain polar order in the resulting poled
material, the reaction for subsequent crosslinking should be triggered only by
very mild conditions, preferably without further temperature elevation. By
taking into account all these requirements a lattice-hardening approach based on
a Diels-Alder [4 + 2] cycloaddition reaction was developed.
52
This is claimed
to provide significant advantages over the conventional nonlinear optics
thermosets. It consists of preparing linear polymers first with pendant protected
dienophile groups, These groups become unprotected under mild conditions and
subsequently undergo Diels Alter addition reactions with other polymer
molecules containing pendant diene groups. The process can be illustrated as
follows
52
:
N
O
O
+
N
O
O
6.3.1.2. Polyurethanes
Formation of urethane crosslinking linkage from terminal hydroxy
groups and isocyanates occurs at relatively low temperatures and essentially
neutral conditions. Polyurethanes are, therefore, suitable for the above described
purposes and received some attention. Linear polyurethanes with covalently
attached chromophores have lower T
g
(ca. 130
o
C) than polymers like
polyimides (ca. 250
o
C), and, consequently are less stable at higher temperature.
Many tried to overcome this by forming crosslinked three dimensional structure.
polyurethane polymers with the aid of free-radical photoinitiators.
53
By placing
trans-stilbene groups in the chromophore moieties, the photocrosslinking steps
are restricted to the methacryloyl double bonds, and proceed without concurrent
trans-cis isomerization of the stilbene. This polymer is illustrated as follows
53
:
Beecher et al. reported that they carried out photocrosslinking of
6.3.1.1. Polymers Crosslinked by the Diels-Alder Reaction
polymers during the lattice-hardening process that significantly increase the
required to increase rotational freedom of nonlinear optics chromophores.
Light-Associated Reactions of Synthetic Polymers
329
N
H
O
O
(CH
2
)
2
N
(CH
2
)
2
SO
2
N
N
O
O
O
NH
(CH
2
)
3
photoinitiator
UV light
crosslinked structure
For this reaction an organometallic photoinitiator was used that absorbs at 532
patterned material that exhibits a stable second-order nonlinear optics signal
that lasts for several weeks at 100
o
C . Addition of phenol is necessary to
prevent thermal crosslinking.
The following scheme was developed for forming polyurethane
thermosets
54
:
N
HOCH
2
CH
2
HOCH
2
CH
2
S
O
OCH
2
CH
2
OH
CN
NC
+
NCO
CH
3
NCO
'
H
CH
3
S
O
O
N
O
C
CN
CN
O
C
O
N
H
CH
3
OCH
2
CH
2
O
C O
N CH
3
H
6. Photorefractive Polymers for Nonlinear Optics
nm. Photocrosslinking of the oriented polymer can be used to produce a
N
330
Based on the absorption spectrum of the above material there is a strong charge-
transfer (CT) band at 626.6 nm. This is an indication of an enhanced charge
One can compare the above with another polyurethane preparation
where a structure with a hemicyanine dye is attached as a pendant group.
55
Following preparation procedure was used:
N
C
4
H
9
CH
2
CH
2
OH
HOCH
2
CH
2
B
4
CH
3
NCO
NCO
polyurethane
The polymer, with an M
n
= 12000, is soluble in dimethylformamide and can be
processed into optical quality films by spin casting. The T
g
= 121
o
C. The F
(2)
of
this polyurethane was reported to be in the range of 1.8 x 10
-7
to 5.0 x 10
-7
esu,
depending upon poling conditions. This high second-order activity is attributed
to the strong electrons accepting nature of the pyridinium groups. The alignment
of the nonlinear chromophore moieties induced by electric poling exhibits
temporal stability. This is believed to be due to the hydrogen bridges that form
between neighboring polyurethane chains. These bonds prevent relaxation of
oriented molecular dipoles.
55
In a different approach, a polyurethane was formed from a terpolymer
of methyl methacrylate that was functionalized with pendant hydroxy groups
51
:
and then reacted with a diisocyanate.
separation and greater nonlinearity.
Light-Associated Reactions of Synthetic Polymers
331
HOCH
2
CH
2
O O
O
OCH
3
O
O
N
N
O O
O
S
N(CH
2
CH
2
OH)
2
x y z
The technology involves combining the acrylic polymer with the
diisocyanate and then spin casting the material into films that are electrically
poled at T
g
to align the chromophores. The films are then heated to higher
temperature for crosslinking and “hardening” the lattices and locking in the
dipole alignment. The products exhibit electrooptic coefficients as high as 20
pm per volt and maintain their optical nonlinearity for several thousand hours at
high temperature.
A synthesis and characterization of an active styrylthiophene monomer
and formation of polyurethane with second-order optical nonlinearity was
56
This was carried out on (trans)-7-[4-N,N-
(dihydroxyethyl)aminobenzene-ethenyl-3,5-dinitrothiophene to form the
corresponding prepolymer, polyurethane.. The prepolymer and polyurethane are
claimed to exhibit good thermal stability and good solubility. in common
organic solvents. The d
33
coefficient of the dielectric polarized films was
reported. to be 40.3 pm/V.
56

51
described preparation of new trifunctionalized Disperse-
Red type chromophore, Disperse-Red Triol compound by reaction of this
chromophore with diisocyanate at 80
o
C. It resulted in formation of
soluble oligomers that were spin cast to form high optical quality films.
Concurrent corona poling and thermosetting of these films resulted in
polyurethane networks with electrooptic coefficients (r
33
at 1.06 Pm) of 14.5
prominent advantages in terms of simpler material processing, wider processing
window and higher temporal stability of dipole alignment
51
.
Dalton et al.,
reported by Wang et al.
6. Photorefractive Polymers for Nonlinear Optics
pm/V and good dynamic thermal stability. This system is claimed to offers some
332
HO
N
HO
O
O
NO
2
NCO OCN
OCH
3
CH
3
O
NH O O NH
O
N
N
NO
2
O
OCH
3
OCH
3
R =
Another, somewhat different preparation of a polyurethane was also reported by
51
Dalton et al. It is shown as follows:
Light-Associated Reactions of Synthetic Polymers
333
HO
N
OH
N
N
NO
2
OH
CH
3
NCO
NCO
N
N
N
NO
2
O NH
O
HN O
O
O NH
O
6.3.1.3. Epoxy Crosslinked Polymers
Thermal epoxy crosslinking, using relatively rigid reagents at
optimized stoichiometry substantially enhances the orientational stability of the
aligned chromophore substituents by forming ether linkages between polymeric
chains and reestablishing hydroxy groups for hydrogen bonding. This produces
a dense, three-dimensional network of covalent bonds that restrict the freedom
of chromophore motion, thereby enhancing temporal stability characteristics.
This was shown on orientational relaxation of the nonlinear optics
chromophores of polyamides with the following structure
57
:
N
NO
2
CON NCO (CH
2
)
x
NO
2
N
H
H
CON
H
(CH
2
) OCN
H
x
n
where x = 4,6,8,10,12.
These polymers were studied at different temperatures below the glass transition
by the decay of the nonlinear optical susceptibilities of corona-poled films. The
6. Photorefractive Polymers for Nonlinear Optics
334
time dependence of the decay was shown to be well represented by the
Kohlrausch-Williams-Watts stretched exponential function:
d(t) = d
0
exp[-(t/W)
E
]
The temperature dependence of the decay correlates with the glass
transition temperature, T
g
, using normalized relaxation law with (T
g
- T)/T as the
relevant scaling parameter.
6.3.1.4. Crosslinked Polyesters
Trollsas and coworkers
58
prepared a crosslinked polyester by in situ
photocrosslinking of the ferroelectric monomer, which was obtained via an 11-
step synthesis. The resulting polymer has a large electro-optical coefficient (15-
35 pm/V; in the range of organic single crystals), which means the material may
58
6.3.2. Polymeric Materials with High Second Order Transition
Temperature
Generally, above T
g
, thermoplastic polymers undergo cooperative
localized motions. Below the second order transition temperature there is not
enough energy in the system to enable whole segments of the polymeric chains
to move. In the attempt to lock in asymmetry, as stated earlier, one approach is
to synthesize polymeric materials with a high T
g
. Following is a description of
some these materials.
6.3.2.1. Polyimides and Polyamides
It was shown that the thermal stability of conventionally formed
polyimide polymers and copolymers (bearing nonlinear optical chromophores)
is adequate for numerous device applications. There is a problems, however,
with doped systems in that they tend to undergo phase separation. This limits the
amount of the nonlinear optics chromophore that can be incorporated into the
system. To try and make doping unnecessary, multifunctional polymers were
synthesized that contain all the necessary components. One limitation of this
technology, however, is the small nonlinear optical response (r
33
) values for
many such polyimides. This is not true of all of them.
One photorefractive polyimide 59 was formed by linking thee units, a
substituted porphyrin (charge generator), 4-amino-4’-nitrostilbene derivative
(the nonlinear optics molecule), and a charge transporting agent, pyromellitic
dianhydride. This polyimide retains its nonlinear optical properties even after
Light-Associated Reactions of Synthetic Polymers
be suitable for use in electro-optic devices.
335
heating at 170
o
C for extended periods. It works in the absence of an external
electric field. The optical gain coefficient is approximately 22 cm
-1
in zero field.
The absorption coefficient, however, is much higher. The polymer consists of
two sections AB :
A =
N
N
NO
2
N N
O
O O
O
0.9 n
N
C
6
H
13
N
N
C
6
H
13
C
6
H
13
M
N
C
6
H
13
N
O
O
O
O
N
0.1 n
B =
The approach by Drost, Jen, and Rao was to incorporate into typical
nonlinear optics materials
60
electron-rich five-membered heteroaromatic
groups, like thiophene as part of an all S conjugation between the donor and
acceptor substituents. The function of the conjugating unit is to transfer
electrons. In addition, they also incorporated a very active acceptor, a
tricyanovinyl group into the thiophene-based moiety
60
:
N
S
CN
CN
CN
Drost and coworkers
60
high T
g
. The considerations was that if these materials are poled at the glassy
temperatures (>250
o
C), then at operating temperatures of 80 to 120
o
C the
6. Photorefractive Polymers for Nonlinear Optics
also chose materials for nonlinear optics applications with
336
dipoles of the chromophores would not randomize, and the alignment would be
preserved. An example of such a polyimide can be represented as follows
60
:
O
N
O
N
O
O
O
NC
CN
CN
O
N
O
O
R
n
where R =
O
The above polyimide, one that contains 32 mol% of nonlinear optics
chromophore, was reported to have an r
33
of 16 pm/V (at 0.83 Pm) with the
electro-optical signal showing almost no change when the polymer is heated to
90
o
C for greater than 1000 hours
60
.
Polyimides with diamino chromophores were prepared with the aid of
the Misunobi reaction
61
:
H
2
N
N
NH
2
X
O
O
O
O
O
O
N
X
N
N
N
O
O
O
O
n
where, X = NO
2
, SO
2
CH
3
. Long term stability was observed at 170 - 180
o
C.
The optical loss and refractive indices of fluorinated polyimides and
copolyimides were investigated.
62
The materials for these investigations were
H
Light-Associated Reactions of Synthetic Polymers
337
pyromellitic dianhydride, and 2,2’-bis(trifluoromethyl)-4,4’-diaminobiphenyl.
They can be illustrated as follows:
N
O
O
C
CF
3
F
3
C
N
O
O
CF
3
F
3
C
n
N N
O
O
O
O
CF
3
F
3
C
n
A two step, generally applicable synthetic approach for polymers with non-
linear optics side-chains, aromatic polyimides was developed Chen, et al.
Following synthesis was used in the preparation of the polymers
63
HO OH
N N
O
O
O
O
n
N
O
O
N
O
O
CH
3
CH
3
O
N
A
O
N
A
6. Photorefractive Polymers for Nonlinear Optics
prepared from 2,2'-bis(3,4-dicarboxyphenyl)hexafluoro-propane dianhydride,
338
A =
NC
CN
CN
;
N NO
2
N
;
O
CN
NC
One-pot preparation of a preimidized, hydroxy polyimide was reported.
64
It is followed by a covalent bonding of a chromophore onto the backbone of
the polyimide via a mild postMisunobi reaction. Using this technique, aromatic
polyimides with different polymer backbones and different chromophores were
synthesized, and the chromophore loading level in these polyimides was
controlled efficiently from 0 to 50% by weight. These polyimides were reported
to have high glass transition temperatures (T
g
> 220
o
C) and are claimed to be
33
) value (11 pm/V
measured at 0.83 Pm and 34 pm/V at 0.63Pm) and long term stability (>500 h at
100
o
C) of the dipole alignment were observed. Earlier this group also reported
preparation of another polyimide by the same technique
64
:
N
O
O
CF
3
F
3
C
N
O
O
O
N
S
CN
CN
S
N
n
The advantage of this one-pot preparation method is that the chromophores are
attached to the polymer backbone at the last stage using a very mild
condensation reaction between the hydroxy substituted polyimide and a
hydroxy-substituted chromophore. This avoids the harsh imidization process and
the necessity of preparing the chromophore-containing diamine monomers. The
method also allows a wide variety of polyimide backbones.
Burland and coworkers
65
synthesized somewhat different types of
polyimides. They can be illustrated as follows :
thermally stable. Large electrooptic (E-O) coefficient (r
Light-Associated Reactions of Synthetic Polymers
339
N
O
O
CF
3
CF
3
N
O
O
N
N
N O
2
N
n
In this compound the electron donor is the diarylamino group and the acceptor
is the nitro group. They are connected by an azobenzene bridge. In the above
polymer the chromophore is present in every repeat unit and accounts for more
that 50 % of the polymer’s weight.
Yu and coworkers
66
prepared a similar polyimide that bears phenylene
diamine and a diazobenzene-type nonlinear optical chromophore:
N
F
3
C CF
3
N
O
O
O
O
O
N
x
N
N N
N O
2
N
n
This high glass transition temperature polymer exhibits large electrooptic
coefficients, r
33
~ 14 - 35 pm /V. The second harmonic measurements indicate
long-term stability of the dipole orientation (> 800h at 100
o
C) .
In still another report in the literature, the syntheses and
characterizations of two aromatic polyimides with nonlinear optical
chromophore side chains were reported through a two-step synthetic route
103
These two polymers were prepared by polycondensation of 4,4'-
(hexafluoroisopropylidene)diphthalic anhydride with 4-(4-amino,2-hydroxy)
phenoxyaniline and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane,
respectively. The resulting polyimides bearing hydroxy groups were found to
react easily with the terminal hydroxy group of the chromophore via the
Mitsunobi reaction. It was claimed that the resulting polyimides possess high
glass transition temps. (Tg > 185°C), excellent solubilities and process abilities
67
6. Photorefractive Polymers for Nonlinear Optics
even though the extent of chromophore grafting is up to 95 mol %.
340
Also, Zhu and coworkers
68
reported preparing of two high T
g
(250°
and 258°) polyimides embedded with triphenyl imidazole chromophores.
Simultaneous polymerization and poling was carried in situ. The second
harmonic generation measurements technology yielded moderate d
33
values of
15 pm/V and 16 pm/V. The signals of these poled polymer films were reported
to be without any decay at < 150°; The relaxation starts rapidly over 195°. The
half-decay temperatures, of the samples orientation are as high as 240° and 224°
respectively.
Yu and coworkers
69
describe a technique to retain stability and
maximize the electrooptic response. They preformed the imide structure with
an aryl dihalide monomer and incorporated highly efficient chromophore groups
before polymerization. This highly functionalized monomer was subjected to a
Pd-catalyzed coupling reaction with 2,5-bis(tributyltin)thiophene to give the
polymer
69
:
N
R
O
O
N
O
O
R
CF
3
F
3
C
S
n
where R =
(CH
2
)
2
COO N
C
2
H
5
S
N
N
O
O
O
The polymer, shown above is soluble in organic solvents, has a glass-
transition temperature (T
g
) of 170 °C and its electro-optical response is 33
pm/V.
69
Polycondensation and imidization of m,m'-diaminobenzophenone and
pyromellitic dianhydride under microwave radiation was also carried out.
70
The
product polyimide was obtained in a two-step process. It is claimed that this
product of microwave radiation polymerization compares favorably with a
product of conventional thermal polymerization, because it exhibits third-order
nonlinear optical coefficient of 1.642 x 10
-13
esu and response time of 24 ps.
The third-order optical nonlinearity of this polymer is dependent on the chain
length and the molecular structure.
Light-Associated Reactions of Synthetic Polymers
341
6.3.2.2. Polycarbonates
Polycarbonates are also high melting rigid polymers. They were,
therefore, also looked at for potential use in nonlinear optics. To achieve high
molecular weights, some attempts were made to prepare them via ring opening
polymerization. This, however, led to intractable materials.
66
The cyclic
structure can be shown as follows:
O N
O
O
NO
2
O
O
O
O
m
n
A copolymer, was, therefore, formed in the investigations
66
:
O
O O
m
n
O N
NO
2
O
O
6. Photorefractive Polymers for Nonlinear Optics
342
The above shown copolymer, after poling, had an electrooptic coefficient of 55
pm per volt at about 1.3Pm. The chromophore, not attached covalently to the
polymer, in this case is based on a heterocyclic acceptor that contains two
electron withdrawing groups, dicyanomethilidine and sulfone. The donor is a di-
n-butylamino moiety. This chromophore can be illustrated as follows.
(CH
3
CH
2
CH
2
CH
2
)
2
N
S
O
O
CN
CN
2
This chromophore was dispersed in a polycarbonate matrix and the composite
film poled at 80
o
C. The thermal stability of this material, however, does not
exceed 150
o
C.
Chen et al.
71
prepared polyquinolines with both aliphatic and aromatic
in-chain structures to provide sites far the side-chain nonlinear optics
chromophores. The aromatic ones are also be high melting, rigid molecules.
They can be illustrated as follow:
N
O
N
O
N
NC
CN
CN
O
n
6.3.2.3. Highly Aromatic Polyquinolines
Light-Associated Reactions of Synthetic Polymers
343
N O N
O
(CH
2
)
m
N
n
NC
CN
CN
These polymers were processed into optical-quality thin films for potential
device fabrication. The authors claim good solubility for several of these
materials in common organic solvents with molecular weights as high as 41,000.
optics applications due to combination of film forming ability, good thermal
stability, and high glass transition temperature. It is also claimed that when
chromophore dipoles are aligned by contact or corona poling, useful levels of
second order nonlinearity are induced that appear stable at temperatures
necessary for the fabrication of optical devices.
71
configuration. Due to the twisted configuration of the binaphthalene moiety, the
polymers that form through rigid groups with triphenylamine derivatives are
helices. It is the rigidity of the system that gives rise to rigid, rod like, helical
structures. All bonds that form the helix have the same configuration (either S or
R). As a consequence, if both R and S monomers are incorporated in the same
backbone, no helical configuration can be formed. The rigidity of the backbone
can greatly diminish unwanted dipolar interactions between the chromophores,
allowing a very high chromophore density.
72
In addition, when the polymers are
chiral, they can increase the nonlinear optical response.
72
Samyn et al.,
72
reported preparation of chiral chromophore-
Polymers containing binaphthalene units can adopt a helical
6. Photorefractive Polymers for Nonlinear Optics
6.3.2.4. Polynaphthalenes
functionalized polybinaphthalenes for nonlinear optics. These polymers were
These materials are reported to be especially advantageous for use in nonlinear
344
formed by direct polymerization, using Stille coupling between a
bis(trimethyltin) compound and dibromo-substituted binaphthalene monomers.
The chromophores were attached to the binaphthalene units via alkyl spacers:
OR
RO
S
OC
6
H
12
H
12
C
6
O
S
n
a
b
where R is ,
S
N
N
O
O
O
x
x is hexyl. The authors report that the typical tree-like macromolecular
architecture of these molecules gives rise to a unique behavior in the glass
transition temperature as well as in nonlinear optical properties. The nonlinear
optical response shows a continuous increase in function depending on the
chromophore content. In this way, the nonlinear optical properties can be
increased in a way that is not possible with other chromophore-functionalized
polymer materials.
72
By attaching chromophores as side chains to the rigid non
bendable backbone a treelike structure with flexible branches forms.
The same group reported
72
preparation of eight other chiral,
chromophore-functionalized donor-embedded polybinaphthalenes. The
polymers were prepared by direct polymerization, using Stille coupling reaction
between a chiral bis(trimethyltin) binaphthalene derivative and diiodo-
functionalized chromophores. They reported that use of diiodo-functionalized
instead of dibromo-functionalized chromophores results in a significant increase
of molecular weight. The reaction conditions allow use of a great variety of
architecture of the polymers is reflected in the behavior of the glass transition
temperature and, more clearly, in the nonlinear optical properties. The nonlinear
optical response shows a continuous, linear increase as a function of
chromophore concentration, indicating that the dipolar interactions between the
chromophores are eliminated. This group of polymers can be illustrated as
follows
72
:
chromophores with different structures. The typical tree-like macromolecular
Light-Associated Reactions of Synthetic Polymers
345
OC
6
H
13
H
13
C
6
O
N
O
OC
6
H
13
OC
6
H
13
N
A
where A ca be:
NC CN
;
S
N
O
O
S
N
N
O
O
O
;
6.3.2.5. Fluorinated Poly(arylene ethers)
Another approach, starts with preparation of two fluorinated
poly(arylene ether)s, containing perfluorophenyl moieties in the main chains and
73
The polymers were formed by Knoevenagel condensation reactions between
perfluorophenyl-containing poly(arylene ether) and cyano acetylated
chromophores. The molar percentages of the pendant chromophores were
estimated to be 162% (1) and 138% (2) for the two polymers, respectively, and
their weight percentages were both 42.3%. Both of the two polymers are
thermally stable and readily soluble in common organic solvents. The glass
6. Photorefractive Polymers for Nonlinear Optics
second-order nonlinear optical chromophores in the side chains.
346
transition temperatures (T
g
's) of the two polymers were determined to be 186
(1) and 192 °C (2), respectively. The in-situ second harmonic generation
measurement revealed the resonant nonlinear optics coefficient (dss) values of
60 (1)and 31 (2) pm/V for the poled films, respectively.
73
The polymer consists
of three sections. In section A both R groups are substituted, in section B only
one R group is substituted and the other one is an aldehyde, while in section C
both R groups are aldehyde.groups.
O
F F
F F F F
F F
N
N NO
2
section A
O
CH
2
R
R
where R =
N
COO
NC
x
the second copolymer is very similar, except that the R groups are:
N
OOC
CN
N
N
F F
F
F F
6.4. Polysiloxanes
The polysiloxanes are not noted for high grass transition temperatures.
Actually it is the opposite, and many have very low T
g
-s. If rigid moieties are
Light-Associated Reactions of Synthetic Polymers
347
introduced into the polymeric structures, however, they can form liquid crystals.
It was reported that siloxanes containing up to 20 % spiropyran groups
are liquid crystalline.
74
At higher compositions they are amorphous. With
increased spiropyran content, the selective reflection band characteristic of
cholesteric mesophases shifts to lower wavelength:
N
R
CH
3
O
CH
3
NO
2
N
O
NO
2
CH
3
CH
3
R
spyropyran "merocyanine" blue
O
Si
O
Si
CH
3
CH
3
(CH
2
)
2
N
O NO
2
CH
3
CH
3
O
Si
CH
3
The photochromic reaction leading to the blue merocyanine formation results in
a narrowing of the reflection bandwidth.
Sanchez and coworkers
74
obtained very high second order nonlinear
optical properties from materials derived from sol-gels and based on organic-
inorganic hybrid structures. These materials are formed by reactions of an
organic polyfunctional alkoxy silane derived from Red 17 dye with
tetramethoxysilane in the sol-gel formation. The Red 17 structure, 4-(amino-
N,N-diethanol)-2-methyl-4'-nitroazobenzene was reacted with 3-
(isocyanatopropyl)-triethoxysilane via urethane linkages to introduce the
alkoxysilyl reacting groups:
As such, they can maintain an orderly arrangement.
6. Photorefractive Polymers for Nonlinear Optics
348
O
2
N N
N
H
3
C
N
CH
2
CH
2
OCONH
CH
2
CH
2
OCONH
(H
5
C
2
O)
3
SiCH
2
CH
2
CH
2
(H
5
C
2
O)
3
SiCH
2
CH
2
CH
2
This structure, carrying the nonlinear optics chromophore, was co-hydrolyzed
with tetramethoxysilane in a tetrahydrofuran and water medium acidified with
HCI to form sols, which were subsequently aged 3 days. Transparent coatings
were then spin coated onto glass substrates and dried to prepare films for optical
property measurements. Chromophore orientation of these films by the standard
corona poling technique resulted in second harmonic generation responses as
high as 150 pm/V. It was claimed that thermally precuring the samples
75
On the other hand, formation of photorefractive silicone composite
with good performance was reported
. 76
A carbazole-substituted polysiloxane
that was sensitized by 2,4,7-trinitro-9-fluorenone was used as a photoconducting
medium and l-[4-(2-nitrovinyl)phenylpiperidine was added as an optically
nonlinear chromophore. The photorefractive property of polymer was
determined by diffraction efficiency using a 100 Pm-thick film. The maximum
diffraction efficiency (K max) of 71% was obtained at the electric field of 70
V/Pm.
76
6.5. Polyacetylenes
Cheong and coworkers,
77
demonstrated that a soluble, asymmetric
polydiacetylene can be used to form stable monolayers at the air-water interface
of a Langmuir trough. The monolayers of this amphiphilic polymer were then
repeatedly deposited onto hydrophobic substrates during every upstroke cycle of
the vertical dipping method to form Z-type monolayers. The second harmonic
generation increases in these films with the number of layers, and there are
indications of a high degree of orientation anisotropy of the backbone. The
33
) was estimated to be 1.52 pm/V at 1064
nm of Nd:YAG laser.
In addition, it was reported recently,
78
that a diacetylene monomer with
a rigid backbone and capable of forming hydrogen bonds was polymerized in
such a way as to form two-dimensional super-molecular assembly. The two-
dimensional structure self-assembles when UV light generates polydiacetylene
comb polymers, and hydrogen bonds are established within molecular layers.
The material forms blue solid thin films which generate third-order nonlinear
optical signals and exhibit photochemical stability to 1064 nm radiation from a
considerably improves their nonlinear optics response and thermal stability.
second order nonlinear coefficient (d
Light-Associated Reactions of Synthetic Polymers
349
Q-switched Nd:YAG laser. Heating the polymer to 62
o
C changes the color to
bright red. This is reversible. The two-dimensional structure is still maintained.
77
This thermochromic process is accompanied by endothermic and exothermic
signatures detected by differential scanning calorimetry. Third-harmonic
generation signals retain much of their original intensity through the
thermochromic transitions. It was observed, however, that the results do not
conform in a consistent manner to both the theory of third-order effects and to a
previously suggested connection between intramolecular conjugation and optical
absorption of polydiacetylenes. The explanation that was offered is that possibly
intermolecular interactions in these highly ordered structures play a role in
defining optical properties.
78
The acetylene groups containing monomer was
illustrated as follows:
O
O
O
O
O
OH
6.6. Polymers with Carbazole Structures in the Backbone
Zhang and coworkers
80
prepared carbazole group containing polymers
by the Knoevenagle reaction. The reaction was carried out in two stages, first in
THF and then as a solid state condensation. This yielded high molecular weight
polymers. Thin films of the polymers exhibit good optical quality. They can be
obtained from their chloroform solutions by spin-coating. After electric poling,
6. Photorefractive Polymers for Nonlinear Optics
Wang et al,
79
synthesized of a soluble polymer from diacetylene with
push-pull azobenzene and pyrimidine rings attached. The polymer was formed
from an asymmetric polydiacetylene having a pyrimidine ring and an
azobenzene chromophore directly linked to the two ends of a diacetylene
moiety. The material was polymerized thermally or under light illumination. The
resulting polydiacetylene with push-pull azobenzene chromophores as side chain
and a pyrimidine ring covalently bonded to the diacetylene conjugated system
was found to have nonlinear refractive index of 1.18 x 10
-11
esu. The macro and
microscopic susceptibilities X
(3 )
and y for the functionalized polydiacetylene;
X
(3)
is 1.01 X 10
-11
esu and y is 1.06 X 10
-30
esu.
350
the films are reported to show reasonable second-order nonlinear optical
responses
80
:
O
CN
H
N
(CH
2
)
6
H
CN
O
C
7
H
15
O
n
6.7. Liquid Crystal Polymers
Chiral smectic ferroelectric liquid crystals are liquids that possess
spontaneous polar order. Combined with their excellent processibility on silicon
to synthesis of materials for second order nonlinear optics, provided adequate
second order susceptibility X
(2)
can be obtained. Unfortunately, the second-order
nonlinear optical susceptibility (x
(2)
) of the ferroelectric liquid crystals are
usually low and their thermal stability is limited. Several, very interesting
approaches to utilization of liquid crystals, however, were carried out.
81
tried to create a "side-by-side" type dimer structure
where two conventional liquid crystal core structures that are covalently
connected by an azo link, and are appropriately substituted to afford a system
where the DR1 unit is essentially forced by the two liquid crystal cores to orient
normal to the liquid crystal director. While this strategy did indeed afford the
desired supermolecular stereochemistry, the dopants were only soluble up to
about 30% by weight in a standard ferroelectric liquid crystal host. Furthermore,
it was not clear whether the side-by-side dimer structure was compatible with
smectic mesogenicity. They reported instead preparation, structure and
properties of two similar side-by side dimers that possess good smectic liquid
crystallinity; structures A and B. Both materials possess a broad monotropic
smectic A* phase. While crystallization from this phase occurs eventually, both
structures can be kept in the A* phase at room temperature for days. The
polyunsaturated analog B possesses improved mesogenicity, showing a narrow
enantiotropic A* phase. Polarized light spectroscopy showed that the DR1 unit
makes an angle of about 60" with the liquid crystal director, in good agreement
with the expected super-molecular structure. Furthermore, compound B is
ferroelectric liquid crystal mixtures show a good linear relationship between the
maximum observed ferroelectric polarization and concentration of B, and most
integrated circuits, these liquid crystals provide an attractive potential approach
Walba et al.
the ferroelectric C* phase at concentrations up to 60% by weight of B . The
shown to mix in all proportions with a standard C phase host, showing
Light-Associated Reactions of Synthetic Polymers
351
importantly the expected sign of the polarization, demonstrating that compound
B "fits the C* binding site" in the desired manner.
81
synthesized a low molar mass ferroelectric liquid crystal
specially designed for second-order nonlinear optics that showed a second
harmonic coefficient (d
22
) of 0.6 r 0.3 pm/V in the chiral smectic C (SC*)
phase. The nonlinear optics-chromophores aligned in the direction of the
polarization, perpendicular to the long axis of the molecules were later
successfully varied.
81
This can be illustrated as follows:
O
NO
2
O
N
O O
O
OR
O
OR
where, R is decyl in A and 9,12-octadecadienyl in B.
The thermal and mechanical stability of nonlinear optics materials
were improved
82
when a polymer was synthesized with ferroelectric liquid
crystalline side-chain and then further improved by Keller et al
83
when they
formed a ferroelectric liquid crystalline main-chain polymer. The thermal and
mechanical stability and the long-term properties of nonlinear optics-materials
are known to be improved by crosslinking. The idea was therefore to synthesize
a crosslinkable monomer or a crosslinkable monomer mixture that possesses a
chiral smectic C (S
C*
) mesomorphism over a wide temperature range. This
ferroelectric mixture can then be aligned and photocrosslinked into a
pyroelectric polymer. The system, developed by Walba et al.,
81
is based on two
monomers, where only one is nonlinear optics-active81. The acrylate monomer
mixture displayed a ferroelectric SC* phase which could be photocrosslinked
into a pyroelectric polymer, shown below. The crosslinked material displays a
clear second harmonic signal (d-coefficient = 0.4 pm/V).
81
The molecular
structure of this polymer was later modified in order to increase the nonlinear
optics activity.
81
The possibility to modify the monomer system are strongly
limited due to the demands of ferroelectricity and possibility to crosslinking.
However, promising one single monomer system was recently developed.
81
The
new chiral monomer displays a large spontaneous polarization (175 nC/cm
2
)
Walba et al.
6. Photorefractive Polymers for Nonlinear Optics
352
in the chiral smectic C phase. And the photocrosslinked pyroelectric polymer
shows a considerably enhanced second-order nonlinear optical activity. The
modifications of the molecular structure was possible through the use of the
Kajzar and coworkers
1
reported forming side chain liquid crystalline
polymers with high T
g
containing maleimide units along the backbone. The
choice of maleimide was based on its high dipole moment at right angle to the
backbone and its cyclic structure imparting great stiffness to the chains, yielding
g
optics mesogenic moiety and an oligomethylene space was used to decouple the
chromophores from the main chain and to enhance the possiblity of self
organization into anisotropic mesophase
92
:
N
O O
n
(CH
2
)
n
O CN
These polymers were also reported to demonstrate good second-order nonlinear
optical properties.
49
describes the synthesis and physical study of several new
photorefractive polymers that consist of a nonlinear optical chromophore
attached to conjugated poly(p-phenylene-thiophene)s backbones. A Stille
coupling reaction was used to prepare these materials.
C
16
H
33
C
12
H
24
C
16
H
33
C
12
H
24
N
C
16
H
33
R
C
16
H
33
C
16
H
33
N
C
16
H
33
R
n
x y
enantioselective biocatalyst Candida antarctica lipase B.
S S S
a high T . A cyano-biphenyl-based chromophore was selected as an nonlinear
Light-Associated Reactions of Synthetic Polymers
You et al.
353
where: R =
O
C
4
H
9
C
4
H
9
NC
CN
CN
The resulting polymers exhibit high photorefractive performances. An optical
gain coefficient of 158 cm
-1
at a field of 50 V/Pm and a diffraction efficiency of
68% at a field of 46 V/Pm for polymer were obtained.
49
Barmatov and coworkers
84
took an approach of forming photo-
optically active polymers by using hydrogen bonding between functionalized
liquid crystalline copolymers and low-molecular-mass dopants. The
photochromic dopants used by them contain azobenzene components:
(CH
2
)
4
O
C N
(CH
2
)
4
O
COOH
O O O O
x
y
N
O
O N
N R
N
O
O N
N N
The formation of hydrogen bonds between the carboxylic acid groups of the
functionalized liquid crystal copolymers and the pyridine portion of the dopants
leads to stable, none separating mixtures. In mixtures containing up to 30 % of
the dopants no separation was observed. Induction of a nematic mesophase is
observed in the case of a smectic polymer matrix doped with low molecular
weight photochromic dyes.
6.8. Acrylic Polymers
Syntheses and characterization of three fully functionalized
photorefractive polymethacrylates containing different chromophores were
reported
85
Carbazole and nonlinear optics-functionalized methacrylate
6. Photorefractive Polymers for Nonlinear Optics
354
monomers in a 1:1 ratio were polymerized with 20 mol % of dodecyl
methacrylate to obtain photorefractive polymers. The resulting polymers had
glass transition temps, of 48, 47, and 52° C, respectively. These polymers, when
doped with 1 wt % 2,4,7-trinitro-9-fluorenylidene)malononitrile, showed good
photorefractive properties. A net two-beam coupling gain and a diffraction
efficiency of 60% were observed. at 58 V/Pm.
85
Hirai et al.,
86
reported synthesis and photochromic behavior of methyl
methacrylate copolymers that contain anil groups. These groups are pendant 4-
(methacryloyloxyalkyl)-N-(4-methoxysalicylidene)-aniline units. The molecules
contain 4-12 carbon alkyl chain spacers between the polymer backbone and the
pendant sallicylidene aniline units. The photochromic behavior was investigated
in the solid state. Photochromism was observed at 445 nm in five copolymer
films under UV irradiation. The color thermal decay reactions increased with
increasing temperature, and the rate was five to seven times slower than those of
monomers blended in with poly(methyl methacrylate). The rate of thermal
decay reactions depended on the alkyl chain length of sallicylidene aniline
units. It decreases with decreasing alkyl chain spacer because of restriction of
the thermal conformational change by the polymer backbone. The difference in
the thermal decay reaction is small when the carbon number of the alkyl spacers
was greater than 10, and contains more than 0.08 mol azo groups.
Chromophores with indole and nitrobenzene push pull groups were
reacted with methacroyl chloride and acryloyl chloride. The resultant acrylic
monomers were then copolymerized with methyl methacrylate and butyl
acrylate to yield photorefractive acylic copolymers that can be illustrated as
follows
87
:
N
X
NO
2
O
O
O
O
m n
These polymers are very soluble in organic solvents. They fabricate into
optically clear polymer films. The glass transition temperature, is 150 °C for
Light-Associated Reactions of Synthetic Polymers
355
the methyl methacrylate copolymer and 8 °C for the butyl acrylate copolymer.
Large nonlinear optical coefficients (d
33
as high as 49 pm/V) and
photoconductive sensitivity (on the order of 10
-9
S-cm
-1
/W-cm
-1
) were
observed for both copolymers.
6.9. Polyphosphazenes
89
reported a new post functional approach to preparation of
second-order nonlinear optical polyphosphazenes containing a sulfonyl-based
chromophores. The sulfonyl groups act as acceptors. Two polyphosphazenes,
one containing aniline and the other containing indole groups as side chains
were obtained from poly(dichlorophosphazene), by nucleophilic substitution
reaction. Then a postazo coupling of p-ethylsulfonylbenzenediazonium
fluoroborate or p-octylsulfonylbenzenediazonium fluoroborate was carried out
with the aniline or indole ring. This yielded sulfonyl-based chromophore-
functionalized polyphosphazenes. The polymers exhibit good solubility in
common organic solvents and are thermally stable. The maximum absorption in
one appeared at about 440 nm, while at about 393 nm in the other one. The
poled films of both exhibit a resonant d
33
value of 27 and 18 pm/V, respectively,
by second harmonic generation measurements.
These polyphosphazenes can be illustrated as follows
90
:
P N P N P N
m n o
OC
2
H
5
O
(CH
2
)
2
N
N
N SO
2
C
2
H
5
O
(CH
2
)
2
Qin et al.,
6. Photorefractive Polymers for Nonlinear Optics
The syntheses and nonlinear optical properties of methacrylate
polymers based on 2-[4- (N-methyl-N-hydroxyethylamino)phenylazo]-phenyl-6-
nitrobenzoxazole chromophores were reported.
88
Methacrylate polymers contai-
ning different molar contents of these nonlinear optical active molecular segm-
ents were synthesized. Polymers containing 6-17 mol % pf chromophore
segments yielded amorphous and optically clear thin films. Some mesomorphic
structural order was exhibited by a polymer with 33 mol % chromophoric units.
Values ranging from 40 to 60 pm/V were measured with increasing chromo-
phore molar contents.
88
356
P N P N P N
O
O
(CH
2
)
2
(CH
2
)
2
N
N
N
N
SO
2
C
2
H
5
OC
2
H
5
n
m
o
6.10. Miscellaneous Materials
91
found that molecules containing two 2,6-diacetamido-4-pyridone
groups and a nonlinear optical chromophore will self-assemble with diimides
or bis(uracil) structures, to yield polymer-like hydrogen-bonded assemblies.
HN
NH
O
O
N
C
6
H
13
CF
3
CF
3
C
6
H
13
NH
NH
O
O
N
N NO
2
R
NH
O
N
NH
R
O
(CH
2
)
2
N
2
The "lock" and "key" structure in these super-molecular assemblies is provided
g
Yu et. al,
by three hydrogen bonds per repeat unit. The nonlinear optics materials have T
Light-Associated Reactions of Synthetic Polymers
357
values in the 72-100 °C range and are stable up to 120 °C, at which point the
hydrogen bonds break and the structure is lost.
92
synthesized polymers bearing oligo-aromatic esters as
side chains to form second-order nonlinear optical active polymers on the basis
of architecture. The cut-off wavelength (O
co
) of these polymers is shorter than
the visible region, i.e., O
co
ca. 330-370 nm, which are much shorter than the
typical second order nonlinear optics polymer containing chromophores like
azobenzene. These polymer films exhibit good transparency in the visible
region. The second-order nonlinear optical coefficient, d
33
, is 2.2-9.8 pm.V
-1
.
Twieg and coworkers,
93
reported preparation of poly(norbornene)
copolymers functionalized with nonlinear optical chromophore side groups. Use
was made of (K
6
-toluene)Ni(C
6
F
5
)
2
, catalyst in the polymerization of
norbornene. The nickel complex used to polymerize the norbornene monomers
is tolerant to many functional groups found in nonlinear optical chromophores.
On the other hand, nitriles and amines other than trisubstituted amines strongly
inhibit the reaction. A copolymer of hexylnorbornene and a norbornene-
functionalized Disperse Red I chromophore was scaled up and studied in detail.
Initial studies indicate that electric field poling is effective but that relaxation of
polar order in the poly(norbornene) is faster than in a comparable methacrylate
copolymer. The copolymer can be illustrated as follows:
C
6
H
13
O
O
(CH
2
)
2
NO
2
N
m n
Katz et al.
94
utilized tetracyanoethylene to form polymers with tetracyano-
derivatives that are donor-acceptor molecules in a long S-conjugated system.
55
Tetracyanoethylene was reacted quantitatively with electron-rich acetylenic
polymers to form polymeric materials containing repeating nonlinear optics
chromophores. This [2+2] cycloaddition is followed by electrocyclic ring-
opening to give tetracyanobutadiene. Presumably, this reaction is initiated by
charge transfer followed by closure via a 1,4-dipolar intermediate to a
cyclobutene, which opens to give tetracyanobutadiene derivative:
C
6
H
13
n
CN
CN
NC
NC
Kimura, et al.
6. Photorefractive Polymers for Nonlinear Optics
358
NC
CN
NC
CN
C
6
H
13
n
The polymer is a film former and forms by this reaction in virtually quantitative
yields. The films can be cast from common organic solvents, like acetone,
tetrahydrofuran, toluene, etc.
95
describe photorefractive polymers with
performance competitive with available crystals. The materials are a mixture of
the electrooptic polymer based on bisphenol A and 4,4’-nitroaminostilbene with
29 % by weight of benzaldehyde diphenylhydrazone, a hole transporting agent:
O N O
NO
2
OH
n
A
N
C
2
H
5
C
2
H
5
C
H
N N
+
The stilbene dye substituent plays two roles in these polymers: It is a
source of charges and, when aligned in a static electric field, it produces the
necessary bulk linear electrooptic response. The transport agent transfers the
charge generated at the dye molecules to other parts of the material.
Also, Liphardt et al.
Light-Associated Reactions of Synthetic Polymers
359
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Yankelevich and A. Knoesen, Macromolecules, 2004, 37, 5163-5178
93. K.H. Park, R.J. Twieg, R. Ravikiran, L.F. Rhodes, R.A. Shick, D.
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Light-Associated Reactions of Synthetic Polymers
363
94. H.E. Katz, K.D. Singer, J.E. Sohn, C.D, Dirk, L.A. King, and H.M.
Gordon, J. Am. Chem. Soc., 1987, 109, 6561
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6. Photorefractive Polymers for Nonlinear Optics

110

5 Optical Plastics

This chapter compares the physical properties of some of the transparent plastic materials currently in use.

5.2

Quality Requirements for Optical Plastics
5.2.1

Transparency

The most required property of optical plastics is high transparency at specific wavelengths. The transparency of a plastic is determined by (1) molecular structure, (2) molecular conformation formed by molding or other causes, and (3) impurities.
5.2.1.1 Molecular Structure The transparency of a polymer is intimately related to its molecular structure. Various interatomic/intermolecular interactions in a polymer being exposed to light cause optical absorption in the ultraviolet to visible region due to electron transitions or optical absorption in the infrared region due to vibrational transitions. The absorption in the infrared region does not affect absorption in the visible region. For absorption due to electron transitions ae mostly in the ultraviolet region, Urbach’s rule is known [1, 2]:

ae ¼ A exp

B k

(5.1)

where A and B are inherent to each molecule and k is the optical wavelength. At 500 nm, ae of PMMA is reported as <1 dB/km whereas that of polystyrene is 98 dB/km from this formula [3]. The value of ae is high when a polymer has a benzene ring structure, as in the phenyl groups that are found in most polycarbonates and polystyrenes. On the other hand, PMMA is a typical transparent material with excellent transparency because its molecular structure has no group that absorbs within the visible region. Thus, materials that are barely affected by electron transitions are desirable in order to obtain high transparency. Light absorptions occur, for instance, in p fi p* transitions in double bonds as typified by azo or phenyl groups, or n fi p* transitions in C=O bonds. The reflectance (R) depends on refractive index (n) as follows: R¼ ðnÀ1Þ2 . ðnþ1Þ2 (5.2)

This formula indicates that materials with low refractive index show low reflectance and accordingly high light transmittance. Commonly, plastic lenses are coated with inorganic materials for which the refractive indices are lower than those of plastics. Figure 5.1 shows a comparison of light transmittance data for PMMA, PC, and COP.

5.2 Quality Requirements for Optical Plastics
100 90 80 70
PMMA Transmittance / %

111

60 50 40 30 20 10 0
250 350 450 550 Wavelength / nm 650 750

PC COP

Figure 5.1

Comparison of light transmittance of PMMA, PC, and COP. Sample thickness 3 mm. PC: Panlite AD5503, Teijin chem.; PMMA: Acrypet VH, Mitsubishi rayon; COP: Zeonex 330R.

Molecular Conformation Randomness of molecular chains is essential for polymer transparency. Crystal and non-crystal regions of a crystalline polymer generally have different refractive indices. This causes scattering of light at the boundary between two such regions. A multicomponent polymer such as polymer alloy behaves similarly. There is also light scattering loss caused by isotropic and anisotropic density fluctuations called Rayleigh scattering [2, 4].
5.2.1.2

Impurities Polymers may be colored due to various additives such as antioxidants, plasticizers, ultraviolet absorbers (UVAs), coloring agents (pigments and dyes), or oxidized resin damaged in thermoprocessing. Small amounts of residues such as catalysts that are added at the time of polymer synthesis may unintentionally cause coloring of the polymer.
5.2.1.3 5.2.2

Refractive Index

The refractive index varies depending on molecular polarizability and weight per unit volume (density) as in the Lorentz–Lorenz equation [5]:

as shown in Figures 5. COC(1): Apel 5104DP. F-line (486. 1. Alicyclic acrylate: Optrez OZ1330. and C-line (656.65 PC 1. PMMA: Parapet at 23 C. The higher the refractive index. .3) where n is the refractive index. (5.3 nm).40 70 60 50 40 30 20 Abbe number Figure 5. the refractive index values depend on molecular refraction and molecular volume of macromolecules as follows: sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1þ2½RŠ=V (5. COP(1): Zeonex 480R. As the result of Eq.60 Refractive index PMMA Alicyclic Acrylate 1.2 Relationship between refractive index and Abbe number for various polymers at 25 C.70 1.3 and Table 5. COC(2): Topas 5013. and N the number of molecules in 1 cm3. COP(4): Arton FX4727.3). nF ÀnC (5.5) This formula corresponds to Fraunhofer’s D-line (589.1 nm).55 COC(1) COC(2) COP(1) 1.112 5 Optical Plastics n2 À1 4 ¼ pNa n2 þ2 3 (5.50 COP(4) PSU O-PET 1.45 1. PSU: Udel P-1700. PC: Panlite AD5503 at room temperature.2 nm). O-PET: OKP-4.2 and 5. The Abbe number is expressed as VD ¼ nD À1 . Usually an almost straight line can be observed for all polymers when plotting refractive index against Abbe number. The Abbe number is the wavelength dependence of refractive index.4) n¼ 1À½RŠ=V where [R] is the molecular refraction and V the molecular volume. the smaller the Abbe number and thus the larger the wavelength dispersibility.1 [6–13]. a the polarizability.

COC(1): Apel 5104DP.460 300 PSU O-PET @30°C PC @room temp. COC(1) COC(2) COP(1) COP(3) Alicyclic acrylate PMMA @23°C 500 700 Wavelength nm 900 1100 Figure 5.500 1.634 1.5 52 56.523 1.520 1.0 52.3 Wavelength dependence of refractive index for various polymers at 25 C. VD 31.6 Table 5. COC(2): Topas 5013.5836 1. especially above the glass transition .5333 1. COP(3): Zeonex 330R.7 58.1 material polycarbonate poly(methyl methacrylate) alicyclic acrylate cycloolefin polymer polysulfone optical polyester Panlite Parapet Optrez OZ1330 Apel 5014DP Topas 5013 Zeonex 480R Arton FX4727 Udel P-1700 OKP-4 Plastics usually have a larger linear coefficient of expansion (5 ” 10–5–10 ” 10–5) than glass (5 ” 10–6–10 ” 10–6).5251 1. Additionally.540 1. D-line (587.5 27.5096 1.0 23.5434 1. Alicyclic acrylate: Optrez OZ1330.640 1. PSU: Udel P-1700.660 1.6070 Abbe number.6 nm) 1.580 1. PC: Panlite at room temperature.2 Quality Requirements for Optical Plastics 113 1.1 56. 23 25 25 25 25 25 – 30 refractive index.4913 1. the specific volume of plastics is strongly affected by temperature and pressure.480 1.2 56. PMMA: Parapet at 23 C. COP(1): Zeonex 480R.5.620 1.560 1. O-PET: OKP-4.600 Refractive index 1. Abbe numbers and refractive indices of optical polymers brand name temperature (C) room temp.

Because this melted plastic is cooled from the skin layer to core in the injection molding process. certain molding technologies have been under consideration in order to control refractive index distribution using molding techniques [14]. By this means.2E-03 1. Polymer: Zeonex E48R. melted plastic is pressed and flowed into the mold cavity and then cooled rapidly. certain density distributions. . In a certain molding process. refractive index distributions.0E-03 9. Commonly optical elements made from thermoplastics are fabricated by injection molding. temperature and pressure distributions occur in the molding..5E-04 8.1E-03 Specific volume m3/kg 1.4 Dependence of specific volume on temperature and pressure.114 5 Optical Plastics temperature (Figure 5. are generated in the molding.2E-03 1.1E-03 1. i. it is important to control optical properties by specifying mold designs and molding conditions.e. These distributions are affected by sprue/runner shapes and injection and cooling conditions. As mentioned above. Generally.4). Recently.0E-04 8. one way to avoid nonuniformity of cooling is to keep the mold temperature high and to fill the mold with melted plastic in the shortest possible time. 1.0E-04 20 120 220 Temperature °C 320 420 Figure 5.5E-04 0MPa 50MPa 100MPa 150MPa 200MPa 9.

If this phenomenon occurs in lenses. Table 5.0043 0. In these cases. .2.105 0.5.106 0.7) in which & is the density. velocities of light differ between two orthogonally arranged vibrating surfaces. they become sensitive to orientation when used in polarized light.2 and 5. There are several explanations for the cause of birefringence of polymers.044 polymer polystyrene PPEa PC PVC PMMA PET PE a Poly(phenylene ether). each polymer has characteristic constants of intrinsic birefringence and photoelastic coefficient.1 0.21 0. and Da the major difference of polarizability.027 –0. intrinsic birefringence. This is called birefringence. When light passes through a material. respectively.8) where C is the photoelastic coefficient and r the stress. M the molecular weight per unit. and Dn0 the intrinsic birefringence given by Dn0 ¼ 2p ðn2 þ2Þ2 & N Da 9 M A n (5. and (2) stress birefringence given by Dns ¼ Cr (5. or no image formation can be achieved around the focal area. Generally birefringence is categorized into: (1) orientational birefringence given by Dn ¼ f Dn0 (5. NA Avogadro’s number.3 Birefringence Another important property of optical parts is the birefringence that appears in a molding. of several polymers [15].2 Intrinsic birefringence of polymers. n the average refractive index.2 Quality Requirements for Optical Plastics 115 5. Tables 5.6) where f is the orientational coefficient. Dn0 –0.3 give the intrinsic birefringence and photoelastic coefficient.

R1 and R2 the radii of curvature of the lens.5 shows a comparison of the deflection temperature under load for various optical polymers [6–13]. 5.6). Optical polymers are required to have higher deflection temperature under load than 85 C.8). For automotive applications in the passenger area. various measures have been recently used such as the introduction of alicyclic structures into the main chain. because the temperature dependence of refractive index. Both lenses have a focal distance of approximately 20 mm and thickness of 2 mm with a temperature change from 20 to 80 C calculated by 5.4 Stability Heat Resistance Heat resistance may be required depending on the intended service environment of optical plastics. Normally stability to 85 C is required for laser beam printer (LBP). it is up to 150 C.2. In this case.116 5 Optical Plastics Table 5. In order to minimize the stress birefringence of Eq. the focal shift value of the plastic lens is approximately 19 times larger than that of the glass lens. CD/DVD.3 Photoelastic coefficients of polymers. the synthesis of structures with positive and negative constant birefringence within the same macromolecule has been reported. For instance. photoelastic coefficient. Table 5.2.4 gives a comparison of the focal shifts of plastic and glass lenses. C (”10–13 cm2/dyn) –6 72 6.9) where n is the refractive index. Figure 5. of plastics is about 10–100 times higher than that of glass. and d the thickness of the lens.5 –55 polymer PMMA PC COP (Zeonex 480R) PS As for a specific method to minimize the birefringence of polymers. and cameras for cellular phones. the temperature specification is up to 100–110 C. (5. (5. for applications in the engine area. It is necessary to consider this fact when designing optic elements made of plastics.1 f ¼ R1 R2 n ðnÀ1Þ½nðR1 ÀR2 ÞþðnÀ1ÞdŠ (5. . dn/dT. the refractive index or polarizability may be minimized using Eq. To minimize polarizability. Some plastics cannot be used in situations involving large environmental changes.4.

5273 2.0009 19. Comparison of focal shifts of plastic and glass lenses. COP(1): Zeonex 480R. O-PET: OKP-4.006 0. n thickness. COC(1): Apel 5104DP.02 80 34. plastic: Zeonex 480R glass: Schott N-BK7 8. f (mm) refractive index shift focal shift 6.0 ” 10–5 25 34 –15 1.98 Table 5.5.51872 2. PMMA: Acrypet VH.80MPa / °C 160 140 120 100 80 60 40 20 0 PSU PC COP(1) COC(1) COC(2) COP(4) O-PET Alicyclic PMMA acrylate Figure 5.3 ” 10–6 25 32 –15 1. Usually. 90% RH.0495 1.2 Moisture Absorption The influence of volume change on optical properties in high-temperature and high-humidity environments cannot be clearly expressed.31 –0.015 5. COP(4): Arton FX4727.0068 1.1122 –15.000 20.000 19.291 80 32.2.99 –0.5214 2.2 Quality Requirements for Optical Plastics 117 200 180 Deflection temperature under load 1.4 linear expansion coefficient temperature (C) r1 (mm) r2 (mm) refractive index. COC(2): Topas 5013. the reliability of an optical device is evaluated by accelerated tests in high-temperature and highhumidity environments. it is determined using the performance change of an optical device under conditions of 60 C.0002 0.5 Comparison of the deflection temperature under load for various optical polymers.51856 2. PSU: Udel P-1700.0416 –15. d (mm) focal distance. PC: Panlite AD5503. Alicyclic acrylate: Optrez OZ1330.4. For example.0066 20. and 500 h duration .

Alicyclic acrylate: Optrez OZ1330.5 COP 0.6 shows the water absorption of some major optical plastics [6–13].30 Water absorption rate % 0. PMMA: Acrypet VH.0004 0. measurement by V-block method at 23 C.5 Water absorption % 1. COC(1): Apel 5104DP. instrument: Kalnew precision refractometer KPR-200. 1. 24hr 0.0008 0.15 0. COP(4): Arton FX4727. water.00 PSU PC COP(2) COC(1) COC(2) COP(4) O-PET Alicyclic acrylate PMMA Figure 5.7 Change of refractive index due to water absorption for PMMA (Delpet 80NH) and COP (Zeonex E48R). In order to obtain optically stable materials various developments have been attempted to reduce the water absorption. Sample thickness 3 mm.05 0. the introduction of alicyclic structures and the use of a polyolefin with alicyclic structure (cycloolefin polyCondition 23°C. COP(2): Zeonex E48R.6 Comparison of the water absorption of some optical polymers. O-PET: OKP-4. PSU: Udel P-1700. From recent actual examples. COC(2): Topas 5013. condition: 50 C.118 5 Optical Plastics as a reference. .0004 0 5 10 15 Time (day) Figure 5. 50% RH.10 0.35 0.0000 PMMA COP -0.0012 0.0 0.0 0 0. 25°C 0.25 0. PC: Panlite AD5503. 90% RH.0016 PMMA 5 10 15 Change of refractive index d-line.20 0. Figure 5. Even a relatively small water absorption affects size distortion and density.

4 30 40 50 60 -0.4.5. 5. . Sample thickness 0.3 Immediate after molding 0.4 30 40 50 60 -0. minimize warp progression.8 Radius mm 0.2 Quality Requirements for Optical Plastics 119 mer) have produced good results.8 Radius mm Figure 5. diameter 120 mm. Figure 5.7 shows the change of refractive index due to water absorption for PMMA and COP.8 Change of radial deviation of optical disc.2. optical disc substrates made from COP (Zeonor 1060R).8). From these data it can be seen that the refractive index is much affected by water absorption. The details are discussed later. as a result. Large residual stress can also be removed by annealing below the glass transition temperature (see Figure 5. measurements at room temperature.8 Immediate after molding 1day 3day 6day 7day Mold temperature 80°C Radial deviation deg 0.6 mm. Residual Stress It is also important to prevent size distortion and tilt due to the residual stress at the time of plastic molding.4 3day 6day 7day 0 20 -0.8 1day Mold temperature 75°C Radial deviation deg 0. Optimization of molding conditions will minimize the residual stress of a molded item and.4 0 20 -0.

. .120 5 Optical Plastics 5. As for optical use.to medium-sized high-precision lenses such as optical lenses for LBP. projection TV lenses. Ltd. CH3 CH2 C C O CH3 Figure 5. PMMA is used in various transparent parts. and lenses for car lamps. and optical pick-up lenses. It is also used in cover materials for displays.3. outstanding hardness. . and for the covers of rear lights of automobiles. and gauges. With its high transparency it is also used in light guide plates for LCD backlights and in light diffusing devices for illumination in which elements are diffused. The chemical structure of PMMA is shown in Figure 5. Fresnel lenses. and high Abbe number. The material characteristics are as follows: .9 O n Chemical structure of PMMA.5 and 5. high transparency. It is made by polymerizing the monomer methyl methacrylate. With its high transparency and hardness. and Kuraray Co.1.3. . 16]. low birefringence.3 Plastics 5.6 give catalog values for PMMA polymers offered by Mitsubishi Rayon Co. high light deterioration resistance. instruments. Tables 5. . Ltd [7.1 PMMA This is one of the major materials used in optical plastics. lenses for disposable cameras.9. It is used as a pellet-shaped material for processing or offered as cast board manufactured by polymerizing the monomer by pouring it into a mold sandwiched between glass boards. PMMA is used in large lenses such as condensers.1 Acrylate Polymers 5. it is also used for small.

Ltd.3. CD pick-up lenses. The major physical properties are given in Table 5. and (2) heat resistance: glass transition temperature of 100 C is insufficient in some environments. low birefringence.10 Chemical structure of an alicyclic acrylate. CH3 CH2 C C O O CH2 CH3 C C O O m CH3 n Figure 5.7 and the chemical structure is shown in Figure 5. being similar to that of PMMA. the following properties have been obtained: 5. .5. It is used for similar purposes to PMMA. . Ltd [17]. . Water absorption is reduced. low water absorption. ideally to zero. The light stability remains high. and others. Alicyclic Acrylate By replacing some side-chain methyl groups with cyclic functionalities in PMMA.2 . being approximately half of that of PMMA. One well-known example is the development of an acrylate-containing alicyclic structure called Optrez by Professor Koike of Keio University and Hitachi Chemical Co.1. It has been already used in optical lenses. The development of various polymers is in progress to solve these problems. and high heat resistance.3 Plastics 121 The problems of PMMA as an optical material include (1) water absorbing property: change of refractive index and size due to water absorption.10 [18]. Optrez is now on the market from Hitachi Chemical Co. Various companies have shown good results of their own efforts to minimize birefringence. LBP lenses.

3 0.5 1.49 0.3 0.17 92 1.1 0.19 92.3 0.49 0.1 0.2 92 99 3.49 0.2 82 84 2.3 0.5 1.2 83 87 7.2 93 99 1.49 0.5 0.16 92 0.49 0.3 N 130 220 78 6 6 5 8 5 72 69 75 62 34 90 190 290 250 370 150 230 180 290 170 260 170 260 44 90 g/10 min 2 230 C 250 C mm mm 170 260 59 80 200 290 32 90 230 310 43 90 230 320 54 80 120 200 46 85 120 210 58 78 150 270 56 65 230 330 48 90 130 220 44 80 230 320 60 50 1A/5 MPa spiral flow length MRC (2 mm thickness) mechanical JIS K7162 tensile stress at load elongation JIS K7162 at break 1A/5 % .2 93 98 2.3 JIS K7136 JIS K7142 JIS K7209 3 mm nd 24 h % – % JIS K7123 JIS K7197 0.5 1.19 93 1.5 0.5 1.3 0.5 1.49 0.49 0.5 1.16 92 1.5 1.16 92 1. Vicat softening point melt flow rate JIS K7210 230 C.4 1.17 92 1.3 1.17 92 0.3 1.2 0.3 0.2 0.8 0.5 1.5 1.6 1.7 1.8 87 84 94 101 82 87 93 78 73 1.3 1.6 0.4 1.3 0.16 92 1.3 0.5 J/g/C 1/C 1.5 Typical properties of poly(methyl methacrylate): Acrypet (Mitsubishi Rayon Co.80 MPa C JIS K7206 50 N C physical density light transmittance haze refractive index water absorbance thermal specific heat coefficient of linear expansion heat conductivity heat deflection temp.17 92 3 mm g/cm3 % 1.49 0.3 0.3 94 88 100 108 78 88 98 1.3 1.5 1.3 0.2 85 90 4.2 0. 37.5 1.2 5.3 JIS A1412 W/m/C JIS K7191 1.16 92 0.5 1.49 0.3 0.49 0.8 1.3 1.3 1.14 92 1.6 1.5 1.49 0.3 0.2 0.49 0.49 0. Ltd).14 92 1.3 1.19 93 1.2 0.5 1. standard grade VH MD MF V VH5 IR H70 IR H50 IR H30 IR D70 IR D50 IR D30 high-impact grade IR IR IR IR VR G504 G304 K304 S404 L40 VR L20A 5 Optical Plastics property test method test unit condition JIS K7112 JIS K7361 1.19 93 1.17 92 0.5 0.5 1.49 0.2 0.5 1.49 0.2 101 108 6 14 2.2 95 104 4.19 93 1.4 1.2 0.5 1.5 1.5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 6 ” 10–5 0.6 1.122 Table 5.3 1.5 1.2 0.3 0.6 1.1 0.5 1.3 1.49 0.49 0.2 85 88 1.

05 no trace 3.9 66 2.3 92 JIS K7171 GPa JIS K7110 1A kJ/m2 tensile modulus flexural stress at yield flexural modulus at yield Izod impact strength Charpy impact strength JIS K7111 kJ/m2 kJ/m2 JIS K7202 1eU unnotched 1eA V notched M scale – JIS K6911 >1013 20 20 20 20 20 20 20 20 >1013 >1013 >1013 >1013 >1013 >1013 >1013 X >1016 >1016 >1016 >1016 >1016 >1016 >1016 >1016 >1016 >1013 20 >1016 >1013 20 >1016 >1013 20 >1016 >1013 20 >1016 >1013 20 >1016 >1013 20 >1016 >1013 20 >1016 >1013 20 >1016 >1013 20 JIS K6911 Xm JIS K6911 4 kV/s MV/m JIS K6911 0.6 1.7 0.7 0.5 89 2.9 2.7 0.4 1.7 0.9 2 6.5 90 2.6 66 4.05 no trace Rockwell hardness electrical surface resistivity volume resistivity dielectric breakdown strength dielectric constant dielectric loss arc resistance JIS K6911 JIS K6911 60 Hz – – 5.05 no trace 3.5 1.2 3.5 1.5 48 1.3 101 94 92 98 101 1.5 8.2 114 3.6 3.Table 5.5 8.3 127 3.7 3.7 3.05 no trace 0. standard grade VH MD MF V VH5 IR H70 1.7 0.05 no trace 0.5 90 1.2 11 140 8.8 111 6.05 no trace 3.9 49 3.3 Plastics 123 .9 2.05 no trace 3.9 2.3 126 3.2 21 20 22 21 1.5 1.05 no trace 3.5 69 test method test unit condition high-impact grade VR L20A 2.7 21 1.3 117 3.8 48 2.05 no trace 3.05 no trace 0.7 3.3 1.8 1.6 67 62 32 110 55 25 73 4.5 Continued.3 1A/1 GPa MPa 3.9 38 55 77 33 52 3.4 3.5 79 2 78 2 3.05 no trace 3.05 no trace 3.7 0.7 3.05 no trace 60 Hz – 3.2 1.7 3.7 0.6 1.5 3.4 43 2.9 80 2.5 93 1.7 0.9 85 JIS K7162 JIS K7171 3.9 2.7 3.05 no trace 3.3 3.3 3.2 71 2.5 45 1.9 70 2.4 2 5.1 70 property IR H50 IR H30 IR D70 IR D50 IR D30 IR IR IR IR VR G504 G304 K304 S404 L40 2.05 no trace 3.05 no trace 0.7 0.8 4.9 68 2.6 3.7 1.3 1.7 0.4 1.7 47 2.7 0.7 80 1.7 3.05 no trace 0.

3 100 95 1. unnotched Charpy impact ISO 179 strength.49 lt.49 <0.3 102 101 1.3 1.3 1.0. resistance good flow GH-S light conductor general purpose grade standard (heat resistance) grade optical grade GH-SN light conductor (UVA added) property test method condition 5 Optical Plastics ISO JIS JIS K7361-1 3 mm % – MPa MPa % MPa MPa kJ/m2 19 20 23 22 23 3300 108 3300 110 3300 125 3300 128 3300 126 3 4 7 5 7 3 3300 100 20 3300 67 3300 70 3300 75 3300 77 3300 78 3300 65 <0. notched Rockwell hardness ISO 2039-2 thermal temperature ISO 75-2 of deflection under load.3 1.3 1.6 Typical properties of poly(methyl methacrylate): Parapet (Kuraray Co.49 <0.3 1.3 1.49 3300 77 5 3300 114 22 % >92 >92 >92 >92 >92 >92 >92 >92 <0.3 1.49 3300 62 2 330 90 20 >92 <0.82 MPa C optical light ISO 13468-1 transmittance haze ISO 14782 refractive index ISO 489 mechanical tensile modulus ISO 527-2 tensile strength ISO 527-2 at break ISO 527-2 tensile strain at break flexural modulus ISO 178 ISO 178 flexural stress at break Charpy ISO 179 impact strength.4 1.49 <0.3 110 2 103 0.3 1.4 1.3 1.124 Table 5.3 1.49 <0.3 N .3 100 95 JIS K7202 M scale – JIS K7191 1.49 3300 62 2 3300 90 20 JIS K7136 JIS K7142 3 mm nd JIS K7162 JIS K7162 1A/1 1A/5 JIS K7162 1A/5 JIS K7171 JIS K7171 JIS K7111 1eU JIS K7111 94 86 93 93 98 99 102 101 1eA kJ/m2 1. annealed Vicat ISO 306 softening point melt flow rate ISO 1133 C g/10 min 15 8 92 99 101 1. 37.4 – B50 104 10 104 10 – 230 C.4 103 101 1.5 110 2.3 1. Ltd).4 99 94 1.6 108 5.49 <0. unit GF G high flow general purpose EH HR-L extrusion heat resistance HR-G heat and solvent resistance HR-F HR-S heat heat resistance.

6 HB HB HB HB 0.Table 5.19 0.2–0.6 HB ISO 1183 ISO 62.3 Plastics 125 .3 1.6 0. resistance good flow GH-S light conductor general purpose grade standard (heat resistance) grade optical grade GH-SN light conductor (UVA added) property test method condition ISO JIS JIS K6911 JIS K6911 JIS K6911 JIS K6911 X Xm MV/m – 4 kV/s 60 Hz >1016 >1013 20 4 >1016 >1013 20 4 >1016 >1013 20 4 >1016 >1013 20 4 >1016 >1013 20 4 >1016 >1013 20 4 >1016 >1013 20 4 >1016 >1013 20 4 >1016 >1013 20 4 electrical surface resistivity volume resistivity dielectric strength dielectric constant other density water absorption at 23 C shrinkage of moldings flammability g/cm3 1.2–0.6 Continued.6 0. unit GF G high flow general purpose EH HR-L extrusion heat resistance HR-G heat and solvent resistance HR-F HR-S heat heat resistance.19 0. Source: Molding Materials Sales Dept.6 1. 5.2–0. Methacrylate Company.19 0.2–0.2–0.6 HB 1.19 0.3 % class HB 0. Kuraray Co.2–0.19 0. Ltd.19 0.3 0.3 1.19 0.2–0.3 1.19 0.2–0.6 0.3 0. method 1 ISO 8328 JIS K7112 – 24 h 1.19 % 0.6 HB – UL 94 Note: Values reported are typical and should not be used for specification purposes.6 HB 1.3 0.2–0.3 1.3 0.

2 1.17 130 118 7 ” 10–5 0. 30 C C C 1/C J/m/s/C % % % MPa MPa g/10 min mm/mm g/cm3 1.4995 1. clear Ref. 90% RH ASTM D790 ASTM D790 230 C.6 nm) C-line (656. 3.5087 1.5053 1.2 115 105 7 ” 10–5 0. PMMA heat resistance 5 Optical Plastics property optical refractive index transmission refractometer. water 60 C.21 1.4 100 3000 2–3 2–6 ” 10–3 1. heat resistance OZ-1330 anti-birefringence.5 nm) 20–50 C proximity to gate cavity ASTM D1003 ASTM D1003 3 mm thickness 1/C nm nm % % % Abbe number.19 transmittance haze yellowness index thermal glass transition temperature heat distortion temperature coefficient of linear expansion heat conductivity moisture saturated water absorption saturated moisture absorption maximum change of dimension mechanical flexural stress at break flexural modulus melt flow rate mold shrinkage density 70 C.2 70 3000 3–4 2–6 ” 10–3 1.4858 58 –1 ” 10–4 50 –5 94 <1 <1 ASTM D648 TMA.2 1 0.126 Table 5. Ltd).5162 1.1 nm) 1.3 nm) laser diode (786.21 120 110 7 ” 10–5 0.2 50 3000 1–2 2–6 ” 10–3 >1.5064 1.8 kg ASTM D955 ASTM D792 .19 108 100 7 ” 10–5 0.2 1 0.9 0.4966 1.2 1 0. 90% RH 60 C.497 D-line (587.5027 1.4937 57 –1 ” 10–4 40 4 94 <1 <1 1.16 50 3000 1–2 2–6 ” 10–3 1.5031 52 –1 ” 10–4 4 2 93–94 1 1 1.5121 F-line (486.4997 54 –1 ” 10–4 4 2 93 1 4 1.2 70 3000 3–4 2–6 ” 10–3 1.4998 1.19 110 102 7 ” 10–5 0.5025 1. 25 C.2 1. VD temperature dependence of nd birefringence of molded plate 1.2 1 0.5096 1.4965 56 –1 ” 10–4 30 2 93–94 1 1 1.5059 1. test method unit OZ-1000 regular OZ-1100 heat resistance OZ-1310 anti-birefringence.4885 1.22 2. 50% RH 1.7 Typical properties of alicyclic acrylate: Optrez (Hitachi Chemical Co.4915 1.2 1.

11 O C O n Chemical structure of PC.3. DVD-ROM. The chemical structure is shown in Figure 5. Ltd [6]. It is also used for grading of building materials and for lenses for car lamps. and others. and DVD–R/RW. General PC is polymerized from bisphenol-A with carbonyl chloride or diphenylether.2 Polycarbonate Optical Polycarbonate Polycarbonate (PC) is the most commonly used optical material. A problem with PC is that it has large birefringence.5. 5. . the birefringence becomes large. It is mostly used for CD-DA. low levels of impurities.3 Plastics 127 5.3. MD. when the incident angle is large. Thus. improvement of fluidity. .8 gives the physical properties of Panlite AD-5503 offered by Teijin Chemicals Co. It is the most widely used material for optical disc storage.1 CH3 O C CH3 Figure 5. such as magnetic optical discs. The following measures can be taken to reduce the birefringence [19]: . high refractive index. introduction of monomer with structure different from bisphenol-A. heat resistance. Table 5. . Mitsubishi Engineering Plastics. and mixing with other materials. It has one of the best impact strengths among the various engineering plastics. such as polystyrene. Bayer. for high-density optical discs. transparency. CD-R/RW.11. high scattering. that off-set the large photoelastic coefficient. . It is also used for optical discs including CD-ROM. The photoelastic coefficient of PC is approximately 10 times greater than that of PMMA. Dow Chemical. Asahikasei. DVD-Video. Idemitsu Petrochemical. This may cause read errors. . . With these characteristics it is not only used for optical discs but also for optical lenses and optical films for liquid crystals.2. . and thus is used for multiple purposes. . The characteristics of PC are as follows: . moldability (transferability). and high intensity. Teijin Chemicals. The suppliers are GE plastics.

has been used as an optical material for parts that require high quality. It has also outstanding environmental durability and no hygroscopic property when it is composed only of hydrocarbons. Its main chain has a bulky cyclic structure. 25% lower water absorption than normal PC.7 0.80 MPa 0.8 Typical properties of polycarbonate: Panlite (Teijin Chemicals Ltd). . This polymer is amorphous and has high transparency and heat resistance.3 Cycloolefin Polymer Recently COP. a low-birefringence PC [20.3.585 30 2450 63 6 >50 2400 96 124 138 0.2 Low-Birefringence Polycarbonate: ST-3000 Teijin-Bayer Polytec Ltd. which was originally developed around 1990. Compared to conventional PC it is characterized by the following: .2.585 30 2400 62 6 >50 2350 92 128 141 0.7 1200 S0. 5. 50% lower birefringence than normal PC. COP is a polymer with an alicyclic structure synthesized using a cycloolefin as a monomer. This is a material that solves the problems of the large birefringence of conventional PC. unit kg/m3 % % – – MPa MPa % % MPa MPa C test method ISO 1183 ISO 62 ASTM D1003 ASTM D542 ASTM D542 ISO 527-1 and -2 ISO 527-1 and -2 ISO 527-1 and -2 ISO 527-1 and -2 ISO 178 ISO 178 ISO 75-1 and -2 condition – in water. .45 MPa parallel vertical AD-5503 L-1225Y 1200 0. 21]. 24 h 3 mm thickness – – 1 mm/min 50 mm/min 50 mm/min 50 mm/min 2 mm/min 2 mm/min 1. This material is used for some high-density optical discs and (optical) films that require a low birefringence. .2 89 1.128 5 Optical Plastics Table 5. jointly operated by Teijin Chemicals and Bayer.7 0.7 property density water absorption light transmittance refractive index Abbe number tensile modulus tensile yield stress tensile yield distortion tensile fracture designation distortion flexural modulus flexural strength load-deflection temperature coefficient of linear expansion ”10–4/C ISO 11359-2 5. 23 C.3.2 88 1. and high rigidity. which can be achieved using this new material. undertook a joint development and has now started marketing a new material called ST-3000.

Thus distortion or change of optical properties due to water absorption is a minimum (Figure 5. 23] The Zeonex materials are polymers obtained by ring-opening metathesis polymerization of norbornene derivatives and then complete hydrogenation of double bonds. almost the same transmittance as PMMA. although not a complete carbon hydride. and thus it has been used for optical discs (Figure 5. COP has the lowest water absorption among all transparent plastics. Zeonex/Zeonor [22. This plastic is suitable for optical devices such as lasers used for the visible region. Arton by JSR. No absorption in the whole visible region. The actual birefringence is higher than that PMMA and lower than that of PC. . Low birefringence. Topas by Ticona. . It is a transparent and colorless material with no light absorption in the visible region.14). Outstanding birefringence performance especially to diagonal incident light compared to PC. High fluidity and excellent and accurate moldability. The optoelastic constant is the same as that of PMMA.3.12 R2 n Chemical structure of COP. They are thus used in optical parts that would otherwise use PMMA. Low water absorption. . The major characteristics are as follows: . Glass transition temperature is 123–138 C. . Its transparency is outstanding even among COPs. Low scattering. High processability. .51–1.3 Plastics 129 It has already been commercialized as Zeonex and Zeonor by Zeon Corporation.1 CH2 CH2 R1 Figure 5. This is sufficient for normal use. . Refractive index is approximately 1. The photoelastic coefficient of Zeonex or other COPs is less than that of PC and the same as that of PMMA. This is less than that of PMMA/PC.0). 5. The dependence on the incidence angle of birefringence is less pronounced than for PC.5. The general physical properties are given in Table 5.53.12. Low specific gravity (approximately 1. Transparent.13). Heat resistance. The lowest water absorption among optical plastics.9. Apel by Mitsui Chemicals. . The catalyst and other impurities used in the polymer synthesis have been almost completely removed. These materials have high heat resistance and no property transformation due to moisture absorption. and.3. The chemical structure is shown in Figure 5. The wavelength dependence is relatively weak.

3 0.01 92 1. no anneal – 280 C.0002 94HB lenses. optical components 1.2 mm with notch – – Short-time method.525 138 123 6 ” 10–5 21 – 2100 94 2200 59 40 24 H >1016 40 2.01 <0.53 139 122 6 ” 10–5 25 – 2500 104 2500 71 10 21 H >1016 40 2.01 <0.0002 94HB lenses. unit ASTM D792 ASTM D570 ASTM D1003 ASTM D542 JIS K7121 ASTM D648 ASTM E831 JIS K6719 ISO 178 ISO 178 ISO 527 ISO 527 ISO 527 ASTM D256 JIS K5401 IEC 93 ASTM D149 IEC 250 IEC 250 UL standard – 5 Optical Plastics property method condition 480 480R E48R 330R RS820 specific gravity water absorbance light transmittance refractive index glass transition temperature deflection temperature under load coefficient of linear expansion melt flow rate flexural modulus flexural strength modulus of elasticity in tension tensile strength tensile elongation Izod impact strength pencil hardness volume resistivity dielectric breakdown strength dielectric constant dielectric tangent flammability major applications – % % – C C 1/C g/10 min MPa MPa MPa MPa % J/m – X cm kV/mm – – – – – – 3 mm thickness – – 1.18 N 260 C.01 92 1.525 138 123 6 ” 10–5 20 – 2100 94 2200 59 40 24 H >1016 40 2. 21.3 0. 21.80 MPa.0002 94HB medical equipment.0004 94HB lenses.18 N – – – – – 3. optical components 1. 1 mm 1 MHz 1 MHz – – 1.3 0.95 <0. optical components 0. platable .01 92 1.3 0. optical components 1.509 123 103 9 ” 10–5 – 15 3100 91 – 45 3 13 3H >1016 40 2.3 0.9 Typical properties of cycloolefin polymer: Zeonex (Zeon Corporation).01 92 1.01 white – 138 123 7 ” 10–5 9 – 1700 58 1900 43 100 350 B >1016 40 2.01 <0.0002 94HB high impact strength.130 Table 5.01 <0.

04 Astigmatism 0. Sample: optical disc storage with diameter 86 mm and thickness 1.14 Comparison of incidence angle dependence of birefringence (retardation) of COP (Zeonex 480R) and PC.13 Change of the spherical aberration of optical lenses made from PMMA (filled circles) and COP (Zeonex 480R. 15 20 25 100 Retardation (single pass) /nm COP PC Incident anglePC COP 0 0.5 10 20 4.00 -0.02 condition-A condition-B 0.875 Optical disc storage 80 60 40 20 0 0 5 10 15 20 Incident angle / ° 25 30 35 Figure 5.625 91.3 Plastics λRMS 131 0. 50% RH.04 0.25 30 10.02 0.00 0. measurement point: 30 mm distance from the center of the optical disc.75 41.04 Coma aberration condition-A condition-B 0.875 10 1.04 condition-A condition-B Spherical aberration 0. . 90% RH. 168 hours.2 mm.00 0 5 10 Time / day Figure 5.02 -0. condition B: 25 C.375 5. open circles) under the condition of high temperature and humidity. Condition A: 60 C.5.02 0.

01 92 100 99 7 ” 10–5 – 14 2100 76 53 2100 60 18 26 20 >1016 70 2.0002 94HB high fluidity 1/C ASTM E831 g/10 min JIS K6719 MPa MPa MPa MPa % J/m J – Xm kV/mm – – – – ISO 178 ISO 178 ISO 527 ISO 527 ISO 527 ASTM D256 – ASTM D785 IEC 93 ASTM D149 IEC 250 IEC 250 UL-94 – Data represent experimental results and do not guarantee specific performance levels in actual usage. and high heat resistance like Zeonex without refractive index or birefringence properties.3 0.3 0. a Heat-resistant grades are also available.80 MPa – 280 C. .0002 (94HB) good secondary molding processability 1020R 1. Table 5.01 <0. it is used for the transparent parts of optical discs and light guide plates for LCD backlights (Table 5. high strength 1060R 1.18 N – – – – – with notch – M scale – Short-time method. which is known to have the best light transmittance among transparent plastics. 21. Zeon Corporation also offers Zeonor.01 92 105 101 7 ” 10–5 20 – 2100 80 53 2200 90 60 36 20 >1016 70 2.01 92 70 68 7 ” 10–5 27 – 1800 55 42 2000 140 80 35 – >1016 70 2. unit – % % C C property specific gravity water absorbance light transmittance glass transition temperature deflection temperature under load coefficient of linear expansion melt flow rate flexural modulus flexural strength tensile strength modulus of elasticity in tension tensile elongation Izod impact strength Dupont impact strength Rockwell hardness volume resistivity dielectric breakdown strength dielectric constant dielectric tangent flammability characteristicsa method ASTM D792 ASTM D570 ASTM D1003 JIS K7121 ASTM D648 condition – – 3 mm thickness – 1.3 0.18 N 260 C.01 <0.01 <0. Thus.0002 94HB high moistureproofing. With these characteristics. high fluidity. 1 mm 1 MHz 1 MHz – – 750R 1.10 Typical properties of cycloolefin polymer: Zeonor (Zeon Corporation). with this property and also because of its dimensional stability it is used for the prisms of compact cameras. which is a polymer characterized by transparency. 21.10).132 5 Optical Plastics The transparency of Zeonex is at the same level or higher than that of PMMA.

. low specific gravity. .2 . Table 5. low scattering.5. Table 5. however. Figure 5. and high processability.3 Plastics 133 Cycloolefin Copolymer (COC): Apel/Topas As polymers synthesized by copolymerization of norbornenes and alpha-olefins.16 shows the chemical structure. In particular. respectively. .3. low water absorption. The birefringence is similar to that of PMMA. it is often used in DVD pick-up lenses.12 [25] gives the general physical properties and Figure 5. heat resistance. CH R n CH2 m Chemical structure of Apel. Apel is synthesized by copolymerization of tetracyclododecene (TCD) and alphaolefin. . . . . Apel and Topas have been commercialized by Mitsui Chemical Co. The characteristics are very much similar to those of COP: 5. The chemical structure of Apel is shown in Figure 5. Ltd and Ticona. transparency.15 Topas is a copolymer of norbornene and alpha-olefin.11 [24] gives the general physical properties.15. low birefringence. They are particularly known for their low birefringence and high fluidity. with a birefringence less than that of PMMA and transparency in the red laser region.3. Topas is used in various optical lenses. the transparency is outstandingly high.

04 7 135 60 3 3200 110 25 10 0.54 0.54 0.6 sheets.134 Table 5.6 hot-fill tainers 147 135 1.6 medical TMA glass transition temperature density melt flow rate (260 C.6 industrial components 135 125 1.09 90 3 1.6 con-optical 5 Optical Plastics property unit APL8008T APL6509T APL6011T APL6013T APL5014DP APL6015T 155 145 1.03 22 95 60 3 2700 110 25 15 0. (1.82 MPa) tensile strength tensile elongation flexural modulus flexural strength Izod impact strength.04 15 115 60 3 3000 110 25 15 0.09 91 2 1.09 90 3 1. films 90 80 1. unnotched water permeability light transmittance haze refractive index mold shrinkage applications . notched Izod impact strength.09 90 4 1.54 0.54 0.02 15 60 50 100 2400 90 45 33 0.09 90 4 1.11 Typical properties of cycloolefin copolymer: Apel (Mitsui Chemicals). 2. films 115 105 1.54 0.02 30 70 60 30 2700 100 35 20 0.54 0. method Mitsui Chemicals method Mitsui Chemicals method ASTM D792 ASTM D1238 ASTM D648 ASTM D638 ASTM D638 ASTM D790 ASTM D790 ASTM D256 ASTM D256 ASTM F1249 ASTM D1003 ASTM D1003 ASTM D542 Mitsui Chemicals method – C C – g/10 min C MPa % MPa MPa J/m kJ/m2 g mm/m2/d % % – % – 80 70 1.09 91 2 1.04 36 125 60 3 3200 100 25 10 0.6 sheets.16 kg) heat deflection temp.

Table 5.12

Typical properties of cycloolefin copolymer: Topas (Ticona). unit method 8007 6013 6015 5013 6017

property

g/cm3 % g mm/m2/d ISO 1183 ISO 63 DIN 53122 ISO 527-2/1A – ISO 527-2/1A – ISO 179/1eU ISO 179/eA ASTM D256 – – ISO 75/Bf – – DIN 53752 IEC 60250 IEC 60250 IEC 60093 UL-94 ASTM D1003 – – ASTM D1003 – – ml/10 min F 103 psi – % ISO 1133 – – – – 2.35 >600 >1016 75 85 0.16 0.7 ” 10–4 130 140 0.13 0.6 ” 10–4 2.35 >600 >1016 150 160 – 0.6 ” 10–4 2.35 >600 >1016 66 10 2600 – 20 2.6 – 113 130 66 4 3200 – 15 1.7 – – 184 66 4 3200 500 000 15 2 0.5 126 184 66 3 3100 – 13 1.7 0.4 119 184 130 135 0.13 0.6 ” 10–4 2.35 >600 >1016 1.02 <0.01 0.023 1.02 <0.01 0.035 1.02 <0.01 0.035 1.02 <0.01 0.03 MPa % MPa psi kJ/m2 kJ/m2 ft-lb/in – – C C W/m/C 1/C – V X cm class % – – % 10–6 mm2/N –

1.02 <0.01 0.045 66 4 3200 – 15 2 – 127 190 170 180 – 0.6 ” 10–4 2.35 >600 >1016

HB at 1/16 in HB at 1/16 in HB at 1/16 in HB at 1/16 in HB at 1/16 in 92 – – <1 – <1 92 – – <1 – <1 92 – – <1 – <1 4 I: 445–570 7–16 2:3 0.6–0.7 92 1.53 58 <1 2 to –7 <1 56 I: 445–570 7–16 2:3 0.6–0.7 92 – – <1 – <1 1 I: 480–570 7–16 2:3 0.6–0.7

5.3 Plastics

physical density water absorption immersion at 23 C water permeability at 23 C, 85% RH mechanical (at 23 C, 50% RH) tensile stress at yield (50 mm/min) elongation at break (50 mm/min) tensile modulus (1 mm/min) flexural modulus Charpy impact strength Charpy notched impact strength Izod notched impact strength Rockwell hardness, R scale ball indentation hardness thermal heat deflection temperature at 66 psi glass transition temperature thermal conductivity coefficient of linear expansion electrical dielectric constant at 1–10 kHz comparison tracing index specific resistivity flammability UL flammability rating optical light transmittance refractive index Abbe number haze stress optic coefficient yellowness processing melt flow index at 260 C, 2.16 kg processing temperature range 30 I: 410–500; E: 390–465 7–16 2:3 0.6–0.7 13 I: 445–570; E: 425–480 7–16 2:3 0.6–0.7

135

molding pressure range compression ratio mold shrinkage at 60 C, 2 mm thick

136

5 Optical Plastics

CH R m
Figure 5.16

CH2

n

Chemical structure of Topas.

Norborne Functional Polymer: Arton JSR offers Arton which is a COP with ester groups. The ester groups cause some amount of water absorption compared with other COPs, but lead to easy surface coating, adhesion, and other surface treatments. Table 5.13 [10] gives the general physical properties and Figure 5.17 shows the chemical structure.
5.3.3.3
CH2 CH2

CH 3

C O

O

n

CH3
Figure 5.17

Chemical structure of Arton.

The characteristics of this polymer are as follows:
. . . .

low birefringence; high fluidity; high heat resistance; and easy surface treatment and adhesion.

It is used in optical films, optical lenses, and light guide plates for LCD.

5.3 Plastics
Table 5.13

137

Typical properties of norbornene functional polymer: Arton (JSR). unit method condition F5023 FX4726 FX4727 D4531 D4532

property

optical refractive index – transmittance % haze % Abbe number – stress optic coefficient 10–8 cm2/N birefringence nm thermal glass transition C temperature heat deflection C temperature mold shrinkage % coefficient of linear 10–5/C expansion heat conductivity W/m/C melt flow rate g/10 min mechanical tensile stress MPa elongation at break % flexural stress MPa flexural modulus MPa Izod impact strength J/m Rockwell hardness – pencil hardness – electrical dielectric breakdown kV/mm strength volume resistivity 1016 X cm dielectric constant – dielectric loss – arc resistance s chemical resistance dilute sulfuric acid NaOH (10%) methyl alcohol isopropyl alcohol acetone toluene methyl ethyl ketone (MEK) other density – water absorption %

ASTM D542 ASTM D1003 ASTM D1003 ASTM D542 JSR method ellipsometer DSC ASTM D648 ASTM D955 ASTM D696 JSR method JIS K7210 ASTM D638 ASTM D638 ASTM D790 ASTM D790 ASTM D256 ASTM D785 JIS K5401 ASTM D149 ASTM D257 ASTM D150 ASTM D150 ASTM D495 ASTM D543

D-line, 25 C 3.2 mm thickness 3.2 mm thickness 25 C 546 nm 633 nm 20 C/min 18.2 ” 104 Pa MD direction

1.512 93 0.6 57 3 <20 167 162 0.5–0.7 6 0.17 8 75 15 125 3000 20 125 H 30 >1 3 0.02 190 1 1 1 1 2 3 2 1.08 0.4

1.522 93 0.6 52 1 <20 125 115 0.5–0.7 9 0.16 60 75 10 120 3000 20 125 H 30 >1 3 0.01 180 1 1 1 1 2 3 2 1.06 0.2

1.523 93 0.6 52 1 <20 120 110 0.5–0.7 9 0.16 120 70 10 120 3000 20 125 H 30 >1 3 0.01 180 1 1 1 1 2 3 2 1.06 0.2

1.515 93 0.6 57 4 <20 135 130 0.5–0.7 8 0.17 45 75 15 120 3000 20 125 H 30 >1 3 0.02 190 1 1 1 1 2 3 2 1.08 0.2

1.514 93 0.6 57 4 <20 145 140 0.5–0.7 8 0.17 40 75 15 120 3000 20 125 H 30 >1 3 0.02 190 1 1 1 1 2 3 2 1.08 0.3

100 C 260 C, 98 N

14

in notched R scale

1 mm

1 MHz 1 MHz 3 mm soaking, 23 C, 1 week 1, tolerant 2, limited tolerance 3, not tolerant

ASTM D792 ASTM D570

– 23 C, water, 1 week

5.3.4

Other Resin Materials

The challenges with optical plastics include the achievement of low birefringence, high refractive index, and high durability (low moisture absorption and high heat resistance).

15 90 1.138 5 Optical Plastics Optical Polyester (O-PET) A new type of polyester has been suggested for optical use [26]. Table 5.1 O CH2CH2 O O O CH2CH2 O C O C O O CH2CH2 O C O C n m Figure 5.7 property density water absorption light transmittance refractive index Abbe number tensile modulus tensile yield strength tensile yield distortion flexural modulus flexural strength heat distortion temperature coefficient of linear expansion water. The chemical structure of an example of such an optical polyester is shown in Figure 5. 23 C.14 Typical properties of optical polyester: OKP-4 (Osaka Gas Chemical).14 gives the catalog values of some of its properties. . unit kg/m3 % % – – MPa MPa % MPa MPa C 10–4/C method ISO 1183 ISO 62 ASTM D1003 ASTM D542 ASTM D542 JIS K7113 JIS K7113 JIS K7113 JIS K7203 JIS K7203 ISO 75-1 and -2 ISO 11359-2 condition OKP-4 1220 0.18 [27]. The characteristics of OKP-4 are as follows: .18 Chemical structure of an optical polyester.80 MPa .6).4.9-bis[4-(2-hydroxyethoxy)phenyl]fluorine (BPFE). Osaka Gas Co. Table 5.3. OKP-4. 5. ethylene glycol. and low birefringence. Ltd and Kanebo Ltd have co-developed an amorphous polyester material. and dimethylterephthalate (DMT). 24 h 3 mm thickness Abbe 1. This polymer is synthesized from 9.607 27 2000 60 4 2300 99 105 0. It is now available commercially from Osaka Gas Chemical. high refractive index (>1.

membranes. The general physical properties of the PSU Udel P-1700 are given in Table 5. .3. and outstanding rigidity and hardness.6 1. low birefringence.3.16 [29] and its chemical structure is shown in Figure 5. High intensity. named TI-160 [28]. chemicals. The general physical properties are given in Table 5.4.15 [29]. an olefin–maleimide copolymer. The heat deflection temperature is 343 F (174 C). Heat resistance. . PSU is stable as regards stress. unit % % – 10–12/Pa C MPa GPa kg cm/cm % TI-160 89 1 50 6 130 125 4.15 Typical properties of olefin–maleimide copolymer: TI-160 (TOSOH Corporation).6). Table 5. High refractive index (>1. plumbing fixtures. .3 Plastics 139 5.4 property light transmittance haze Abbe number stress optic coefficient heat deflection temperature flexural stress at yield flexural modulus Izod impact strength pencil hardness water absorption Polysulfone (PSU) PSU is an excellent engineering plastic with high heat resistance.2 75 B 0. Typical applications of PSU are in food service components. and laboratory animal cages.5 3H 0.4.5 PC 88 1 29 100 136 92 2. The characteristics of this polymer are as follows: 5.1 1 3H 0. The characteristics are as follows: . but it is used in heat-stable lenses.19.2 PMMA 92 1 55 –4 95 113 3. . PSU is not commonly used for optical purposes because it is colored yellow. and steam or gamma sterilization required for medical applications. This polymer is under development.3 .5.2 Olefin–Maleimide Copolymer TOSOH Corporation proposes a newly developed material.

methoda valueb valuec property general specific gravity water absorption.0007 0. 1.001 0.16 kg mold shrinkage mechanical tensile strength tensile modulus tensile elongation at break flexural strength flexural modulus tensile impact strength Izod notched impact strength thermal deflection temperature at 264 psi (1.8/2. 24 h melt flow at 343 C.1 0.2 kpsi 360 kpsi 50–100% 15.5/3.0/10/13% Abbe number light transmittance.5/3.6 nm 656.3 ft-lb/in 345 F 31 ppm/F 374 F 425 V/mil 3.650 1.30% 6.623 23 86/85/84% 1.48 GPa 50–100% 106.0/2.0007 0. 1.69 GPa 420 kJ/m2 69 J/m 174 C 56 ppm/C 190 C 17 kV/mm 3. 2. 1.006 3 ” 1016 X cm 1.5 g/10 min 0.24 0.5/2. c SI units.5% 7.30% 6.001 0.5/3.5 g/10 min 0.140 5 Optical Plastics Table 5. b US customary units.3 MPa 2.1 0. .9 4.3 2.9 4.006 3 ” 1016 X cm D149 D150 D150 D257 light amber very light amber nearly water white 486.8/2.007 in/in 10.007 mm/mm 70.3 mm thickness haze.3 2.634 1.2 MPa 2.4 kpsi 390 kpsi 200 ft-lb/in2 1.16 Typical properties of polysulfone: Udel P-1700.1 nm 587.3 nm D1003 D1003 D1925 1.3 mm thickness yellowness index.8/2.3 mm thickness a ASTM.8 MPa) coefficient of linear expansion glass transition temperature electrical dielectric strength dielectric constant at 60 Hz dielectric constant at 103 Hz dielectric constant at 106 Hz dissipation factor at 60 Hz dissipation factor at 103 Hz dissipation factor at 106 Hz volume resistivity color NT 11 (natural) NT 06 (natural) CL 2611 (clear) optical refractive index D792 D570 D1238 D955 D638 D638 D638 D790 D790 D1822 D256 D648 D696 1.24 0.

We select the materials that have characteristics in accordance with quality requirements.4 Summary Table 5. COP(2): Zeonex E48R. PMMA: Acrypet VH.20 shows the retardation data for various plastics.5.17 gives the physical properties of various plastics for optical use. size 65 ” 65 ” 3t mm. 40 30 Retardation nm 20 10 0 PMMA Alicyclic acrylate COC(2) COP(2) COP(3) Figure 5.19 O O S O n Chemical structure of PSU.18 gives the refractive index data reported by plastics suppliers. 5. COP(3): Zeonex 330R. .20 Retardation data for various polymers. COC(2): Topas 5013.19 gives a comparison of some optical plastics.4 Summary 141 CH3 O C CH3 Figure 5. Measurement point: diagonally 75 mm distance from the gate which is located at one corner of the sample plate. Table 5. Sample: injection molded plate. wavelength 590 nm. Measurement by minute area automatic birefringence analyzer: KOBRA CCD. Table 5. Figure 5.

01 1.02 <0.5 343 C 2.4 ” 10–5 g/10 min – birefringence nm temperature: load: Zeon method >80 2 230 C 37.19 0.53 56 136 123 1.4 25 280 C 21.01 <0. polymer: brand name (supplier) PMMA: Acrypet VH (Mitsubishi Rayon) PC: Panlite AD5503 (Teijin Chemicals) COP: Zeonex E48R (Zeon) COP: Zeonex 330R (Zeon) COC: COC: Topas 5013 Apel 5014DP (Ticona) (Mitsui Chemicals) COP: Arton FX4727 (JSR) alicyclic acrylate: Optrez OZ1330 (Hitachi Chemical) 1.142 Table 5.634 23 190 174 % 1.7 15 230 C 21.18 N 32.3 84 1.585 30 147 124 1.5 – – C C 1.0 56 260 C 2.01 1.22 0.04 <0.19 0.523 52 120 110 5 Optical Plastics property unit condition O-PET: OKP-4 (Osaka Gas Chemical) PSU: Udel P-1700 (Solvay) – % 89 1.3 N 13 1–2 230 C 3.8 120 260 C 98 N 42.01 <0.6 – 6.2 1.15 90 1.3 1.24 0.16 kg – * Measured by Zeon corporation.607 27 – 105 1.49 58 106* 101 3 mm thickness 92.2 0.14 93 1.05* 93 1.8 kg 2. .5 36 260 C 2.06 0.18 N 13.16 kg 14.80 MPa specific gravity water absorption light transmittance refractive index Abbe number glass transition temperature deflection temperature under load coefficient of linear expansion melt flow rate 6 ” 10–5 7 ” 10–5 7 ” 10–5 6 ” 10–5 9 ” 10–5 – – 1/C 6 ” 10–5 9 ” 10–5 7 ” 10–5 5.17 Properties of various optical polymers.01 1.54 56 135 125 92 92 90 92 1.53 56 139 1.16 kg 2.01 1.5096 52 110 102 122 103 1.509 56 123 1.

4966 1.1 1.5 temperature (C) wavelength (nm) 435.5059 1.4997 1.4 Summary Table 5. VD grade OZ-1000 OZ-1100 OZ-1310 OZ-1330 25 (50% RH) 25 (50% RH) 25 (50% RH) 25 (50% RH) 1.6 1.4937 1. VD 546.5027 1.4998 1.5 53.4972 Instrument: Kalnew KPR-20 precision refractometer.6 1.4933 587.8 23 1. temperature (C) wavelength (nm) F-line 486.1 D-line 587. Homogeneous light from JOBIN YVON H.5053 1.5019 486.5096 C-line 656.4193 656.8 52. Light source: Mitsubishi Rayon ELI-050 halogen lamp.3 1.4995 1.25–1. wavelength 400–700 nm.18b Refractive index of PC: Panlite (Teijin Chemicals Ltd). Abbe number.5064 LD 786.3 1.5. Conditions: range = no. 1 (1..1 1. intermediate solvent.4965 1.5162 Measurement: transmission refractometer.7).0 Abbe number.4888 827.5 1. VD temperature room temp.5031 57. theoretical wavelength (nm) 486 nF 587 nd 1. mode = auto stand. Ltd).4848 58. Table 5. Table 5.5966 Measurement: Atago 2T Abbe refractometer. nd = 1.5025 1.5087 1.4 56.20 UV.3 1.18a 143 Refractive index of PMMA: Parapet HR1000S (Kuraray Co.7 Abbe number. .49.5782 31.5836 656 nC 1. 1.5121 1.18c Refractive index of alicyclic acrylate: Optrez (Hitachi Chemical Co. Ltd).

5320 1.5250 1.18f Refractive index of cycloolefin polymer: Zeonex 330R (Zeon Corporation).5300 1.3 56.5094 1.5402 1.5136 1.1 824.5025 1. Abbe number.2 1083.5250 1.9 56.5352 1.5317 1.5116 1.5141 1.1 1.5293 1.1 55.5130 h 404.9 Table 5.5040 1.5359 1.5369 1.5004 1.5 wavelength (nm) LD 780 LD 830 s 785.5251 1.5031 1.5204 1.50895 1.2 1083.5286 1.5440 1.5152 1.4960 1.5184 1.5273 1.6 58.4913 56.51225 1.5 57.5371 1.5413 1.5169 1.5306 1.5126 1.5094 1.1 1.5268 1.5417 1.5211 1. Abbe number.1 wavelength (nm) t LD 1310 LD 1550 1013.5179 1.1 –15 0 25 40 60 80 1.1 824.5250 1.4970 1.1 824.5143 1.5079 1.3 56.6 C 656.5230 1.4993 1.5157 1.8 f 486.5236 1.5 LD 780 LD 830 s 785.5036 1.5290 1.0 1.1 t LD 1310 LD 1550 1013.1 1548.5251 1.5209 1.5308 1.8 f 486.18d Refractive index of cycloolefin polymer: Zeonex 480R (Zeon Corporation).1 5 Optical Plastics –15 0 25 40 60 80 1.5052 1.5397 1.5157 1.5141 1.5237 1.5514 1.2 56.5195 1.3 r 706.5273 1.5217 1.5334 1.5024 h 404.8 55.5078 1.5396 1.5375 1.5276 1.5067 1.7 55.5153 56.5265 1.5217 1.5278 1.5412 1.4973 1.5145 1.5456 1.5170 1.5214 1.5182 1.7 56.5151 1.5477 1.0 852.5200 1.5050 1.5348 1.5234 1.7 g 435.5200 1.Table 5.3 56.5179 1.2 –15 0 25 40 60 80 1.0 1.5293 1.5079 1.5311 1.6 C 656.5189 1.5094 1.1 780.5240 1.5053 1.1 t LD 1310 LD 1550 1013.5299 1.0 1310.0 852.8 f 486.5296 1.5432 1.5283 1.1 780.1 780.5343 1.5208 wavelength (nm) d 587.5214 1. VD 144 temperature (C) e 546.5276 1.5253 Table 5.5268 temperature (C) d 587.1 1548.5118 1.51123 1.5132 1.0 57.3 r 706.5334 1.1 1548.5232 1.5161 1.0 1310.5094 .5234 1.1 h 404.5 56.4923 1.5194 1.5501 1.5278 1.5185 1.5247 1.5077 1.5342 1.5260 1.5299 1.5121 1.5234 1.5319 1.5257 1.18e Refractive index of cycloolefin polymer: Zeonex E48R (Zeon Corporation).5159 1.5101 1.3 r 706.5275 1.5065 1.5228 1.5456 1.2 1083.5191 1.6 6.7 g 435.5211 1.5185 1.5224 1.5320 55.5277 1.5234 1.4997 1.5469 1.5234 1.5109 1.5395 1.5415 1. VD e 546. Abbe number.50993 1.5019 1.5253 1.5031 1.5192 1.5235 1.5164 1.5217 1.5056 1.5363 1.5062 1.4947 1.5030 1.5329 1.3 1.0 1.5 LD 780 LD 830 s 785.5052 temperature (C) d 587.5378 1.50752 1.0 1310.5016 1.5254 1.5194 1.5454 1.5250 1.5304 1.5004 1.5207 1.5208 1.5247 1.5219 1.5315 1.5045 1.0 852.1 1.6 C 656.4969 1.7 g 435.5191 1.5446 1.5174 1.5421 1.5378 1.5357 1.5169 1. VD e 546.5355 1.4999 1.4 56.5147 1.50669 1.4937 1.

5367 1.4 Summary Table 5.5518 1.5428 1.5532 1.4 56.6 656.8 486.6070 656 1.1 55. VD temperature (C) 15 25 50 75 dn/dT (”10–5/C) 1.5 55.6 C-line 656.535 –10.6 Abbe number.6 1.5275 1.0 1.7 d-line 587.1 Abbe number.6 1. wavelength (nm) g-line 435.5410 1.5253 1.5 1.2 56.5289 1.5 LD 786.4 1.5263 1.54 1.5255 –10.6 Table 5.3 1.5403 –10.18g 145 Refractive index of cycloolefin copolymer: Apel 5014DP (Mitsui Chemicals Inc.5305 –10.5285 1.623 23.5.5344 1.).5450 1.650 .5308 1. wavelength (nm) 436 486 1.5383 –9.5451 –9.1 1.5556 1.5 Table 5.5 1.5465 1.7 56.5 Abbe number.6010 27.0 56.5355 –9. VD temperature (C) 25 1.5354 1.1 587.6230 546 1.5331 1.5302 1.5371 1.6130 589 1.18i Refractive index of optical polyester: OKP-4 (Osaka Gas Chemical).5305 1.5455 1.5503 1.5571 1.3 706.8 F-line 486.5 768.1 587.18h Refractive index of cycloolefin copolymer: Topas 5013 (Ticona).5218 1.524 1.5347 1.528 1.5315 1.18j Refractive index of polysulfone: Udel P-1700.1 546.2 1014 Abbe number.7 1.5191 –10.634 656.5411 1.4 56. wavelength (nm) 435.5385 1.5505 –9.5421 1.5374 1.525 1.5283 –10.5406 1.6370 Table 5.5225 –10.5320 –9. wavelength (nm) 486.5333 1.1 1.5238 –10.5434 1.1 1.5478 1.1 56.5382 1. VD temperature (C) 30 1.0 1.6 1. VD temperature (C) 5 25 50 75 dn/dT (”10–5/C) 1.

a Glass COP: Zeonex E48R (Zeon) COP: Zeonex 330R (Zeon) COC: COC: COP: Apel Topas 5013 Arton 5014DP (Ticona) FX4727 (Mitsui (JSR) Chemicals) O-PET: OKP-4 (Osaka Gas Chemical) PSU: Udel P-1700 (Solvay) property PC alicyclic acrylate: Optrez OZ1330 (Hitachi Chemical) polymer: brand name (supplier) 5 Optical Plastics PMMA 5 4 high low 3 3 4 4 4 4 4 5 3 4 3 4 4 5 2 3 5 3 5 3 5 3 5 3 low high medium high low high medium high medium high 3 2 4 5 5 3 5 4 4 5b 5 4b 5 3b medium high 4 3 3 5 3 4 high low 3 3 3 – 2 1 high low 2 3 5 3 5 5 high–low high–low 5 5 5 1 low high 1 3 optical light transmittance birefringence (retardation) refractive index Abbe number stability water absorption coefficient of linear expansion. b Gathered from catalog.146 Table 5. . good.19 Comparison of various optical polymers. 5. dn/dT deflection temperature moldability flowability/injection molding 3 4 a Score: 1. bad.

pp. [19] H. In the future. JSR. Kakezawa. Kaino. [4] T. 99–103. [28] Optical Plastics. 191 (1998). Kougaku-you-toumeijusi (Gijutu-jouhou Kyoukai. [13] Catalog of OKP-4. Minami. Kawai. [21] Optical Plastics. 3. Funct. [27] M. 63–67. enabling more applications in various fields. 46. however. . 133 (1998). mainly heat resistance. et al. Kikan Kagaku Sosetsu 39. Kougaku-you-toumeijusi (Gijutu-jouhou Kyoukai.  [6] Catalog of Panlite AD5503 furnished by Teijin Kasei. [14] JP2002–283426. Inonu and H. Recent Transparent Plastics and the Market (CMC Publishing.. Kohara. 118 (1998). Saito.  [12] Technical data of Udel furnished by Solvay Japan. Broc and F. 2001). Matsui and T. These polymers are very good as regards mass-productivity compared to glass. Koubunshikakou 46. 92. Refractive index control of transparent high polymers. JP7–325206. et al. improved polymers are now under consideration as a result of various recent technology developments.  [7] Technical data of Parapet furnished by Kuraray. Kawaki. Rev.  [11] Catalog of Optrez . Makimoto. Refractive index control of trans- high polymers. [3] T. Technology and Application of Plastic Lens System (CMC Publishing. 478 (1984). Fujiki. Yoshida.  [9] Technical data of Topas furnished by Ticona. Rev. [26] Y. MetCon ’98. 122 (1998). 2001).  [8] Technical data of Apel 5013DP furnished by Mitsui Chemicals. parent high polymers. [23] K. 2003). Mitsui Chemicals. Refractive index control of transparent high polymers. pp. [17] H. Polymers in Transition. Osan. appropriate materials are selected for each use. Fuji. Currently.  [10] Catalog of Arton . Appl. 80–86. further developments of materials are expected. low-birefringence materials. ECL 32.  [24] Catalog of Apel . References [1] F. Mater. The main areas of research and development concern . Osaka Gas Chemical. . high-refractive-index materials.  [16] Catalog of Acrypet .  [25] E. Kikan Kagaku Sosetsu 39. et al. . Ide. 1998. Recent Transparent Plastics and the Market (CMC Publishing.. they do not necessarily reach the same level of environmental stability and variety of refractive index as glass. 70–80. JSR Tech. 39. and K. 2001). [15] T. Yoshioka. pp. Polym. JP8–015503. 210 (1997). Jinguji. 25 (1987). JP7–281003. Kikan Kagaku Sosetsu 39. M. pp. 1835 (1992). [5] N. [20] E. [22] T. Tanio. 2001). Rev.. 23–37. 3 (1998). and materials with higher environmental stability. Topas : cyclo-olefin copolymers. 1324 (1953). Hitachi Chemicals. J. Refractive index control of transparent high polymers. 103. Ubrbach. Kikan Kagaku Sosetsu 39. [2] F. Mitsubishi Rayon. Solvay. 34 (1996).References 147 As stated previously. Phys.  [29] Catalog of Udel . Kikan Kagaku Sosetsu. pp. Refractive index control of transparent [18] H.

Chapter 1 Introduction
Photoresponsive and photocrosslinkable polymeric materials are important in many industrial applications. These range from photolithography to light curable coatings and inks, to holography, and to numerous other applications. In order to adequately describe the chemistry of these materials, it is necessary to first explain the manner in which polymers interact with light. This chapter is an attempt to present some of the background and aid in understanding the discussions of light-associated reactions of polymeric materials for readers not familiar with the subjects of photochemistry and photophysics. The information presented in this introduction was obtained from the fundamental sources listed in the references. What is presented here, however, is not a thorough discussion of the subject. For a detailed discussion the reader is encouraged to go to the original sources in the references.

1.1. The Nature of Light
All electromagnetic radiations travel in vacuum at the speed of C= 2.9979x1010 cm /sec. 1,2 Light is a form of electromagnetic radiation and, therefore, also travels at that speed. The fact that light travels at the same speed as other electromagnetic radiations leads to the assumption that light is wavelike in character. Our concept of light, however, is that it also consists of packets of energy that have wave like properties. In each packet there is a range of energies.2 These cannot be represented by one wavelength, but rather by a whole spectrum of wavelengths. The energy of each particular wavelength in the wavepacket is a discrete unit, a quantum. Electromagnetic radiation is described in terms of a transverse plane wave involving associated electric and magnetic fields. It is supposed that the electric vector E and magnetic vector H which describe the respective field strengths are aligned in planes at right angles to one another, with both planes perpendicular to the direction of propagation of the wave.1 A convenient model for the variation of the field strength as a function of time t and distance x along the axis of propagation is given in Cartesian coordinates by the sinusoidal functions in the following equations 1: Ey = A sin 2 (x / Hz =( - t) t)

)1/2A sin 2 (x/ -

1

2

Light-Associated Reactions of Synthetic Polymers

In these equations Ey is the electric field strength vector lying in the xy-plane and increasing along the y-axis, Hz is the magnetic field strength vector lying in the xz-plane and increasing along the z-axis, A is the amplitude of the electric vector (the intensity of the wave is proportional to A2), is the dielectric constant, and is the magnetic permeability of the medium through which the wave is transported. In a vacuum and they are approximately unity in air. The length of the wave, that is, the distance between adjacent maxima in the vectors measured at any instant along the direction of wave propagation (the xaxis) is , while is the frequency or number of complete cycles of vector position change per second. The relationship between and is 1,2 : C/ =

where, C is the velocity of the radiation. The frequency is independent of the medium through which the radiation passes. Wavelength and velocity C, on the other hand depend on and of the medium. Ordinary light is not polarized. It consists of many electromagnetic vectors that are undulating in fixed, though randomly oriented with respect to each other, planes. When the light is polarized in a plane, it is believed that all the waves have their electric vectors oriented in the same direction. When the light is polarized elliptically then it is believed that two plane waves of equal wavelength and frequency and with identical directions of propagation have the electric vectors perpendicular to one another and out of phase. The above described model is incomplete and, even called naive by some.1 Mathematically, however, it can successfully account for many observations concerning light, and this theory has been used successfully to explain many practical phenomena associated with optics.

1.2. The Energy of Radiation
It is possible to calculate the energy associated with any particular wave length of radiation from the following relationship: E = h = hC / where h is a proportionality constant, called Plank's constant, equal to 6.625x10-27 ergs second /quantum. The velocity of light, designated by C, in vacuum is 2.9979 x 1010 cm./ sec, and is the wavelength of light, expressed in centimeters. In a medium containing any matter the light will propagate at a different speed. In this case, the velocity of light, C' is expressed by an equation C' = C / ( )1/2

1. Introduction

3

where is the dielectric constant of the matter and represents the magnetic permeability. The energy associated with one mole of quanta is known as an Einstein. It is equal to the energy associated with a particular wavelength multiplied by the Avogadro's number, 6.023 x 1023 (the number of molecules contained in one mole of matter). As an example we can take ultraviolet light with wavelength equal to 300 nm. The energy or an Einstein of light of 300 nm will be 1,2: E300 = h C / = 6.67x10-27 x 3.0x1010 x 6.023x1023 x 1010 / 300 x 10-7 x 4.20 = = 95.7 Kcal / mole

The above calculation shows that at the wave length of 300 nm there is enough energy in an Einstein to rupture carbon to carbon chemical bonds of organic molecules.

1.3. Reaction of Light with Organic Molecules
If monochromatic light passes through a uniform thickness of an absorbing homogeneous medium with the absorbing centers acting independently of each other, then the energy of light that is absorbed follows the Lambert-Bouguer law. According to this law of physics the light absorbed is independent of the intensity of the incident light and the intensity of radiation is reduced by the fraction that is proportional to thickness of the absorbing system. In addition, Beer’s law states that absorption is proportional to the number of absorption centers. The two laws are usually combined and expressed as follows 1,3-6: dI/dl = kcI where I is the intensity of the radiation, l is the length of the optical path, through the absorbing medium, c is the concentration of the absorbing centers, and k is proportionality constant. While there are no know exceptions to the Lambert-Bouguer law, there are deviations from Beer’s law due to partial ionization, molecular association and complexation and fluorescence. Portions of organic molecules or whole molecules that have bonds can absorb light radiation, provided that it is of the right wave length. Particular groupings or arrangements of atoms in molecules give rise to characteristic absorption bands. Such groups of atoms, usually containing bonds, are referred to as chromophores. Examples of such molecules with bonds are compounds that contain carbonyl or nitro groups, and aromatic rings. A molecule that serves as an example of carbonyl arrangement, one that is often quoted, is a molecule of the formaldehyde. In this molecule, the carbon atom is linked to two hydrogens and to one oxygen by bonds. The hybrid sp2 orbitals

the fourth quantum number. must be different. * level require the least amount of energy. shown above. Also. The total spin quantum number of a molecule is designated by a letter J and the sum of the spins of the individual electrons by a letter S. in a second sp orbital of a pair of unbonded n electrons on oxygen point away from the carbon atom. as one might deduce. The Pauli exclusion principle states that no two electrons can have all quantum numbers identical. Promotion of electrons out of the bonding orbitals to the excited states requires a large amount of energy and rupture of bonds in the process. The carbon atom is attached to two hydrogen atoms by single and to oxygen atom by double bonds. In this state the formaldehyde molecule is planar. Such light may be in the ultraviolet or in the visible region of the electromagnetic spectrum. The Orbitals of Formaldehyde ( from Orchin and Jaffe 18) As described above. This arrangement of electrons in the p orbital can generate bonding and * antibonding. The spin quantum number of a molecule J is equal to |2S| + 1.1. is a type of orbital where the electrons make no contribution to . Absorption of light energy by a chromophore molecule. Figure 1. the molecule has a and bonded skeleton. in the range of 200 mµ to approximately 780 mµ. This bonding of the carbon to the two hydrogens and one oxygen atoms is by means of sp2 hybrid orbitals. 7 as shown in Figure 1. results in formation of an excited state and an electronic transition from the ground state to an excited state. the electronic transition to promote one of the n electrons on the oxygen atom in formaldehyde to the antibonding or the nonbonding orbital. The orbitals of formaldehyde. That means that if two electrons are in the same orbital and three of their quantum numbers are the same.4 Light-Associated Reactions of Synthetic Polymers bond one electron of carbon with a second electron of oxygen in an sp orbital.orbitals. the spin quantum number. On the other hand.1. The name. the simplest of the carbonyl compounds were illustrated by Orchin and Jaffe. The orbitals are approximately at 120 o angles from each other. In the ground state of the molecules the pair of electrons that form a bond are paired and have opposite or antiparallel spin.

After absorbing the light energy. While the intersystem crossing is a forbidden transition (see above) it can actually occur with high frequency in certain molecules like aromatic or carbonyl compounds. Illustration of the Singlet and the Triplet States The intersystem crossing from the singlet to triplet states can occur with high efficiency in certain kinds of molecules.1. can lead to two excited state. The pairing means that these electrons have opposite or anti-parallel spins. 1. Intersystem crossing to a triplet state from the singlet results in a reversal of the spin of one of the electrons and an accompanying loss of some vibrational energy. It is referred to as a symmetry forbidden transition. The chemical mechanism of photoexcitation of organic molecules has been fully described in various books on photochemistry1. be discussed here only briefly. The transitions are illustrated here in a very .) The n electrons in the py . particularly in aromatic and carbonylcontaining compounds. rather that it is highly improbable). however. In formaldehyde this n * transition to the excited state gives rise to an absorption band (at about 270 m ). This is illustrated in Figure 1. As stated above. a singlet (S1) and a triplet (T1) one with an absorption band (at about 250 m ).orbital are in the xz plane and perpendicular to the * orbital.3-5 It will. Electron-electron repulsion in the triplet state is minimized because the electrons are farther apart in space and the energy is lower in that state than that of the corresponding excited singlet one. energy ground state singlet excited state triplet excited state Figure 1.1. therefore. The reason for it being forbidden is crudely justified by the fact that the * is in the xz plane (see Fig. in the singlet excited state the two electrons maintain anti-parallel spins. Introduction 5 the binding energy of the molecule. the likelihood of an electronic transition from one to the other is quite low. This is a relatively weak band and it suggests that the transition is a forbidden one (forbidden does not mean that it never occurs. the spaces of the two orbitals overlap so poorly. Because. The n * excitation.2.2. Solvents can exert a high influence on the n * transitions. in the ground (normal) state of the molecules two electrons are paired.

where the electrons are spin paired and the lowest triplet state T1.9 What it means is that electronic transitions are much more rapid (10-15 sec. and i the energies of internal conversion.3. where the electrons are spin unpaired. 1. The excess energy is dissipated by vibrational interactions giving rise to evolution of heat.3.3. The Franck-Condon principle helps the understanding of the electronic transitions. Diagram depicting excitation and relaxation pathways of an electron . At the S1 level there are three possible ways that the excited state becomes deactivated. The electron is excited by light of a particular wavelength into an upper singlet level..6 Light-Associated Reactions of Synthetic Polymers simplified energy diagram that shows the excited singlet state and the various paths for subsequent return to the ground state in Figure 1. S1 and S2 are the singlet excited states. In simple terms. b.) so that immediately after the transitions the nuclei have nearly the same relative positions and velocities that they had just before . The above diagram shows the lowest singlet state S1. Relaxation follows via an internal conversion process to S1 level. Solid lines represent electronic transitions. They are accompanied by absorption or emissions of photons. The return to the ground state from the triplet one requires again an inversion of the spin. what it states is that during an electronic transition the various nuclei in the molecule do not change their position or their moment.) represents energy states of a molecule that possesses both n and * electrons. a and a’ represent the energies of light absorbed .) than nuclear motions (10-12 sec. (singlet) S2 b (singlet) S1 e f T1 (triplet) T2 (triplet) a enrgy a' c h i d ground state Figure 1. In Figure 1. h. T1 and T2 are the excited triplet states. The energy diagram (Fig. S2. Radiationless transitions are represented by doted lines. c represents return to the ground state by way of fluorescence and d return by way of phosphorescence.3.

the highest filled orbitals in the ground state are generally nonbonding. By comparison. From purely theoretical approach. the triplet state is relative long lived. in the triplet state the spin of the excited electron becomes reversed. n orbitals.7x10-3 seconds. such as oxygen or nitrogen. however. in benzophenone at 77 oC the lifetime can be 4. This is discussed further in Chapter 2. This results in both electrons having the same spin. * transitions can also take place. Also.1. This results in a higher localized site for photochemical activity at the orbital of the oxygen. all transitions in these systems are *. for instance. This is due to the fact that the electron-electron repulsion is minimized. tend to stabilize the excited state more than the ground state. For instance. The carbon atom has a higher electron density in the excited state than in the ground state. Introduction 7 the transitions.2. n In molecules with heteroatoms. the excited states of molecule are more polar than the ground states. it reacts similarly to an electrophilic alkoxy radical. Polar solvents. essentially atomic. because they do not share each other’s orbitals as stated by the Pauli exclusion principle Thus less energy is required for the triplet state. Orchin and Jaffe wrote 7 that the triplet state has a lifetime of 10-3 seconds. The energy of various bonding and antibonding orbitals increases for most molecules in the following order. if the light energy is sufficiently high. therefore. This is a case with ketones and aldehydes. the triplet state is lower in energy that the corresponding singlet state. At higher frequencies (shorter wavelength) of light. Because there are no n electrons. in the triplet state the molecule behaves as a free-radical and is very reactive. the lifetime of a singlet state is about 10-8 to 10-7 seconds. the n-electrons n-electrons H C H O Whether n electrons will be promoted to either * or * antibonding orbitals depending upon the structure of the carbonyl compound. As shown in Figure 1. All aromatic compounds and all conjugated diene structures possess delocalized systems. . In general. It can. react with another molecule by abstracting hydrogen. such an electronic configuration is not allowed. As explained above. Because the carbonyl oxygen in the excited state is electron deficient. Due to the fact that the excited electron cannot take up its original position in the ground state until is assumes the original spin. These molecules possess electrons that are associated with oxygen that are not involved in the bonding of the molecule.

3 Another fundamental law of photochemistry was formulated by Grotthus and Draaper. The number of molecules involved in a particular photoreaction can be established by an analytical kinetic process and the number of quanta absorbed can be measured with the aid of an actinometer.8 Light-Associated Reactions of Synthetic Polymers The chemical reactivity of organic molecules is determined principally by the electron distribution in that molecule. The quantum yield of photochemical reactions is important because it sheds light on the mechanisms of reactions. formation of the excited states and subsequent reactions obey four laws of organic photochemistry. There is also a fundamental law of photochemistry that states that the absorption of light by a molecule is a one-quantum process. as was outlined by Turo 3: 1. the law of conservation of energy requires that the sum of the primary quantum yields of all processes be equal to unity. In solution the lowest excited singlet and triplet states are the starting points for the photochemical process. The quantum yield can also be expressed in general kinetic terms1: i = ES R Pi or I = j i ES j R P ji The above equations signify that a quantum yield of a particular photoprocess is the product of two or three distinct probabilities. Photochemical changes take place only as a result of light being absorbed by the molecules. as a result. due to absorbtion of light and subsequent transitions. The phenomenon of light absorption. that. undergo a reaction. 4. Only one molecule is activated by one photon or by one quantum of light. 3. When the electron distribution changes.12 It states that only the light that is absorbed by a molecule can be effective in producing photochemical changes in that molecule. . 1. 12 Also. These are: ES . 2. Each quantum or photon which is absorbed by a molecule has a given probability of populating either the singlet state or the lowest triplet state. so that the sum of the primary processes. The probability that any metastable ground state intermediate will proceed to stable products is Pi and the probability that the . photochemical reactions take place while the molecule is in an electronically excited state. the quantum yield must be unity. is the probability that the excited state will undergo the primary photoreaction necessary for the process. The relationship between the amount of light or the number of photons absorbed and the number of molecules. It is defined as the number of molecules involved in a particular reaction divided by the number of quanta absorbed in the process. is defined as the quantum yield. Mathematically this can be expressed as : total = i i =1 Where is the quantum yield.

In other words. can take place by one of three processes 3-5: (1) The molecule returns directly to the ground state. The concept that matter can only acquire energy in discrete units (quanta) was introduced in 1900 by Max Planck. .Em. If we designate the wave functions of the states m and n as m and n respectfully then the transition moment integral that may not equal to zero. All reactions that are photochemical in nature involve electronically excited states at one time or other. This requires two conditions.1. The property of each state may differ from one to another and the excited states are different chemical entities from the ground state and behave differently. where e is the electronic charge and ri is the vector that corresponds to the dipole moment operator of an electron i. where the electron reverses its spin. in addition to electronic levels.3. (2) there must be specific interaction between the radiation and the light absorbing portion of the molecule that results in a change in the dipole moment of the molecule during the transition. It has the form of = e ri. The return to the ground state from the excited state. lifetime.. These are: (1) for a molecular state m with energy Em there must be a state n of higher energy En so that h = En . and structure. is: Rmn = ( m / n) where is the electric dipole operator. shown in Figure 1. Introduction 9 excited state will undergo the primary photoreaction necessary of the process is R. (2) An intersystem conversion process takes place to the T1 state. The increase in the energy of a molecules as a result of absorbing a quantum of radiation can be expressed in the relationship3-5: E = hC / where is the wavelength of the interacting radiation. modes of vibration and rotation that are also quantized.2 The corollary of the quantization of energy is that matter itself must be quantized i. The slower decay of excitation from the triplet state to the ground state is accompanied by emission of phosophorescence. This process is accompanied by emission of light of a different wavelength in the form of fluorescence. Each one of these states has a definite energy. In a molecule the intramolecular motions of the electrons and the associated molecular electronic levels must be taken into account. Occupying these particular levels are electrons that obviously possess the energy of the level which they occupy. There are.e. the absorption of a photon of light by any molecule is a reaction of light with an atom or a group of atoms that must promote transitions between quantum states. constructed of discrete levels having different potential energies.

This dissipation of the excitation energy can also be illustrated as follows: A0 + fluorescence A0 + light A* A0 + heat chemical reaction where. And. may also. the chemical reactions can be rearrangement. dimerization (or coupling).10 Light-Associated Reactions of Synthetic Polymers (3) The molecule uses the energy of excitation to undergo a chemical reaction. however. the light emission by fluorescence is at a different wave-length than that of the light that was absorbed in the excitation. In the process of energy dissipation from the singlet and return to the ground states. Some examples of such reactions are: h h h . also. fragmentation. Depending. a third form of energy dissipation can occur when the molecule undergoes a chemical reaction. or attack on another 9-11 molecule. isomerization. AO represents any organic molecule and A* represents the same molecule in an excited state. be dissipated in the form of heat. as shown above. depending upon the structure of the molecule. The energy. again on the molecular structure. This is because some energy is lost in this process of the electron returning from its lowest excited state to the ground state.

provided that it occurs above the glass transition temperature of the polymer. shown above. Ketones and aldehydes cleave by the mechanism of the Norrish reaction. . it was also found that in a polymeric matrix the photoisomerization is not inhibited. Introduction 11 UV light h 2 NO2 H3C CHO light dark N R R O NO2 H3C CH3 O Many other examples can be found in the literature.1. An example of a fragmentation of a molecule is the decomposition of disulfides upon irradiated with ultraviolet light of the appropriate wavelength: h S S 2 S The same reaction takes place in peroxides. Most familiar isomerization reaction is that of cis-stilbene to trans-stilbene. 8 In addition. It was observed that the quantum yield of stilbene cis-trans isomerization decreased with an increase in viscosity of the medium.

there are two a priori requirements for efficient energy transfer: (1) the process must be thermoneutral or exothermic to occur with highest efficiency. Transfer of singlet to singlet energy should be possible. because the activation energies have to be low due to short lifetimes of electronically excited state. and (2) no net spin changes should occur. Energy transfer is further categorized as involving singlet (paired electron spins) or triplet (unpaired electron spins) states.13 Energy transfer. require a singlet S* to produce a singlet Q* and a triplet S3+ to produce a triplet Q3+ . often referred to as a sensitizerand in this case designated as S*. Thus. The quenching reaction of the excited state is expressed in a equation by Stern-Volmer. 12. the acceptor molecule is then also promoted to the triplet state. S* returns (or relaxes) to the ground state S. in this case designated as Q. acceptor molecule. trivial energy transfers that result from the donor emitting light that is subsequently absorbed by an acceptor.13 refers specifically to onestep radiationless transfer of electronic excitation from a donor molecule to another. The reaction shown below is based on a quenching reaction that is accompanied by a release of heat: S* + Q S* Q* + S0 (k2) S0 + heat (k3) . In the process of energy transfer. qualified. from one chromophore to another one.4. the term energy transfer12. because of the shorter life times of the singlet states. often referred to as a quencher. Energy Transfer Process The energy of excitation can transfer from an excited molecule to another molecule. is thus the process by which excitation energy passes from one photoexcited molecule. The quencher must have a thermodynamically accessible excited state. Based on the energy and spin conservation laws.12 Light-Associated Reactions of Synthetic Polymers 1. If a donor molecule was in the triplet state at the time of the energy transfer process. Symmetry rules. but it occurs less frequently. one whose energy is lower than that of S*. to another adjacent molecule in its ground state. The reaction of energy transfer can be illustrated as follows: S*+ Q S + Q* S* S0 + h where * designates an excited state. This excludes what is referred to as. as explained above. A donor molecule must possess sufficiently long lifetime to be an efficient sensitizer.

Two processes were proposed to explain the mechanism of energy transfer. Only when the two molecules are in very close proximity to each . This is referred to as the resonance transfer mechanism. 0 / Q = 1 + kq [Q] where 0 is the quantum yield for a particular process in the absence of a quenching molecule. (up to 15 Å) such that their electronic clouds overlap slightly. concentration depolarization of fluorescence. When the dipolar interactions are large. Introduction The equation is written as follows: 0 13 / Q = {k1 + k2[Q] + k3} / (k1 + k3) In experimental studies of energy transfer it is convenient to express the experimental results in an other form of the Stern-Volmer equation. Should the pair separate when the excited electron is on the acceptor molecule. described above: 1. It may be at any one instant on either the donor or acceptor molecule. energy transfers result from the interactions of the dipole fields of the excited donors and ground state acceptor molecules (longrange: Forster (dipole-dipole))5. the excited donor and acceptor are in very close proximity to each other. In the first one. resonance transfers are possible over distances of 50-100 Å. It is equal to 1 / (k1 + k3). and [Q] is the concentration of the quenching molecules. Close proximities of donors and acceptors. theoretical and empirical considerations suggest two modes of transfer. however. photoconduction. In the region of the overlap. and can take place in solid.1. and formation of triplet acceptor molecules. as follows. Q is the quantum yield of the quenched process kq is the bimolecular rate constant for the quenching process is the lifetime of the state in the absence of a quenching molecules. the location of the excited electron is indistinguishable. are required for weakly absorbing molecules. energy transfer has been achieved by the mechanism of electron transfer. localized in a single molecule. Such transfer is rapid when the extinction coefficients for absorption to the donor and acceptor excited states involved in the process are large (104 to 105 at the maximum). On the other hand. In summary. In the second mechanism 9 (short-range: Dexter (exchange)). the sensitized excitation of Q by S* has to take place within the time that the molecule S remains in the excited state. In addition. 9. liquid and gaseous phases. Both absorption and emission processes may be intramolecular. Intermolecular energy transfer can be electronic and vibrational. they can also involve whole crystals that may act as absorbers and emitters. Such energy transfers can manifest themselves in different ways that include sensitized fluorescence or phosphorescence.

Such a dimer bonds only in the excited state and promptly dissociates in losing its excitation energy. or long range electronic excitation takes place though Coulombic interactions. on the other hand. Transfers by mechanism 2. should be much less sensitive to the viscosity of the medium It was shown by Foster5 that the rate constant of resonance-energy transfer (mechanism 1). When the two molecules are at distances that exceed their collision diameters. 2. is the critical separation of donor molecules and the acceptor molecule. Molecules that undergo intersystem crossing with high efficiency. an acceptor. are efficient triplet sensitizers. R is the separation between the centers of S* and Q. One of the components of the exiplex. and R. resonance transfer. which subsequently dissociate in a deactivation process. The two types of intermolecular energy transfers can be expressed as follows: Forster (dipole-dipole) long-range: Dexter (exchange) short-range: kSQ (R) = kS0(R0SQ /R)6 kSQ (R) = kSQ0 exp(. it is more probable to be the one to participate in energy transfer. and Weiss13 as follows: et = ket[S*][Q] / {ket[S*][Q] + kd[S*]} The transfer by long range excitation or mechanism 2 can be in the form a singlet-singlet transfer. like benzophenone. acceptor or donor are is in the ground state. is in excited state while the counterpart. An eximer is then just a special case in which the two constituent . The efficiency of energy transfer is expressed by Turro. one a donor and the other one. Dalton.R) The nomenclature that was developed in connection with energy and charge transfer processes is as follows.14 Light-Associated Reactions of Synthetic Polymers other and their centers are separated by the sum of their molecular radii will transfer take place. The term exiplex was explained by Birks11 to describe a complex between two molecules. Such molecules must possess high energy in the triplet state and a life time of at least 10-4 seconds. a triplet-singlet transfer. an eximer is a transient dimer formed by the combination of an excited (usually aromatic) molecule and a second similar (usually unexcited) molecule. is: Rate Constant (S* Q*) = 1(Ro/R)6/ S where S is the actual mean lifetime of S*. either the donor or the acceptor. Due to the fact that the lifetime of triplet state of molecule is longer than the singlet one. and a triplet-triplet transfer. The transfers that take place by mechanism 1 are limited by diffusion of molecules in solution and should be affected by the viscosity of the medium. as a function of distance.

It was observed that exiplex emission spectra from a chromophore is usually broad. The maxima of the emission spectra are temperature dependent. This is particularly true of carbonyl compounds. the chemical properties of the molecules change. structureless. in polystyrene it is shifted to 400 nm. The exiplex emission spectra in a copolymer of styrene with 4-N. The excited states of both phenol and benzoic acid can be illustrated follows 12: .12 An exterplex is composed of three molecules and often takes an important role in pbotophysical and photochemical processes. a number of compounds can form only charge-transfer complexes when either the donor or the acceptor is in an excited state . Chemical and physical changes take place in molecules when they absorb energy and reach and excited state.. While the maximum band of the emission spectra in toluene at 30 oC is at 616 nm. In carbonyl compounds this change is particularly large. the acid strength of benzoic acid is less than in the excited state because the charge in this case is transferred to carbonyl group..N. This can be attributed to the * transition where one of the pair of electrons is promoted to an anti bonding orbital. Similar results were reported by Farid et al. such as polystyrene. Formation of eximers was observed in a number of aromatic polymers. In addition. poly(vinyl toluene) and others. While numerous charge-transfer complexes can form between certain molecules in the ground state. The maxima shifts in toluene solution to shorter wave length and in polystyrene it is the opposite. The extend of such a shift is a function of the distance between the two components of the complex. Thus phenol. By the same reason. it shifts to longer wave length with an increase in temperature. 15 who studied formation of exiplexes of 4-(1pyrenyl)butyrate in different solvents and in polymers. for instance. Martic et al. dimethyl-p-toluidine in toluene and in polystyrene.1. There is a change in the dipole moments of the molecules. It is also strongly affected by the polarity of the media. Introduction 15 molecules are identical.N-diaminostyrene is at 480 nm. Polymers with pendant aromatic chromophores and dimeric compounds often show efficient exterplex formation due to high local chromophore concentration in their structure. This is due to the fact that dipole moments depend upon the distribution of the electrons. poly(vinyl naphthalenes). and red shifted to the corresponding monomer fluorescence. is a weak acid. 14 obtained emission spectra of the exiplexes of anthracene and N. The maxima approaches common value at the glass transition temperature of polystyrene. but in the excited state it is a strong acid. Also the geometry of the molecule changes from the ground to the excited states.

however. 12 This reaction is substantially accelerated when the donor or acceptor is excited. It allows the excitation energy deposited at a site in a solid or in a concentrated solution to move to another position by transferring the excitation energy in the absence of an intermediate quencher. storing a substantial fraction of the energy absorbed from the photon. The resulting radical ion pair exists as a charge-separated pair of ions: D* + A D+ + A The oxidized and reduced species are usually highly energetic.16 Light-Associated Reactions of Synthetic Polymers OH OH + light O C OH O C OH + light 1. D* and a reduced acceptor. Electron transfer from an excited-state donor molecule D* to a ground-state acceptor A generates a radical cation D+ and a radical anion A .5. The charge separation that occurs in such a photoinduced electron transfer provides a way to convert the excitation energy of the excited molecule to a chemical potential in the form of a radical ion pair. permit further spatial charge separation between an excited donor. This separation is beyond one that is initially produced in an ion pair by photoinduced electron transfer. Electron transfer. that are called hole and electron migrations. is a process by which an electron is passed from an electron-rich donor to an electron-deficient acceptor. A . respectively. Electron migration can also be a movement of an electron either to a neutral electron donor from an oxidized one (D + D D + D) or from a reduced acceptor to a neutral one (A + A A + A ). After the absorption of light by A to Asensitizer. Electron Transfer Process Simple migration of energy is a thermodynamically neutral process. the energy migrations or the energy transfer moves the excited state .12 These thermoneutral processes.

consists initially of a “prompt” component.16 There is a major difference between eximers of polymers and those of small molecules. 1.13 As one might expect. the excited states cannot be considered as localized. 12 Also. One type is conduction due to diffusion of electrons that are not localized on any particular molecule (this is usually found in liquids or in gases). Thus. The other type can be by conduction due to positive or negative charges that are localized on any particular part of the molecules.12. called backelectron transfer. 9.7.10. A kinetic competition then takes place between the rates of several possible next steps. This continues until terminated (after 1 ) by trapping in deep traps or by recombination.12. either in the backbone or as pendant groups. when photons are absorbed. This can occur without any net energy loss (resonant charge transfer).6. conformation. Such charges can be exchanges between like polymeric molecules (or between segments of single polymeric molecules). it is possible to distinguish between two different types of energy transfers in polymeric materials In the first one the transfer of excitation can take place either from or to large molecules from small ones. excimer formations in polymers depend upon the properties of the chromophores and upon their location on the polymeric chain. 9. and distance between chromophores can greatly affect the formation of eximers.1. In simple cases of rigid lattices the excitations are distributed over the entire volume of the material as a wave-like linear combination of local excitations. The movement of the charge is then terminated as a result of trapping in “shallow” traps. or they can be further charge migrations by sequential electron or hole transfers.10.9. That means that very rapid transfer of a considerable amount of charge takes place over a comparatively short distance ( 100 Å ). or actually nonproductive charge recombination. Introduction 17 site where the excitation energy is converted to a radical ion pair by photo induced electron transfer. These steps can be chemical reaction of the radical ions. subjected to short irradiation pulses. The back-electron transfer regenerates the ground states of both the donor and the acceptor. 9. Electronic conduction can be also of two types.13 They are referred to as tight-binding excitations.16 This is followed by a “delayed” component that is very temperature dependent and probably indicates a thermally activated charge-hopping process between the shallow traps.9 In addition. a polymer transfer of the excitation energy can be localized from a chromophore on one . The difference is that at least in some polymers a large part of the excitation of the excimer site appears to be a result of singlet energy migration. It was shown experimentally that the electrical conductivity in many polymeric materials. The Charge Transfer Processes in Polymeric Materials Charge transfer in polymers is either electronic (transfer of electrons or of positive charges alone) or it is ionic (transfer of protons or larger charged species). polymer tacticity. in polymeric materials with a number of identical chromophores. Also. for instance.

17 This was demonstrated on an intramolecular excimer and exiplex formation in solutions of polyesters containing naphthalene or carbazole moieties in their chemical structures 17: O O C O C O CH2 CH3 C CH2 O n (CH2) x N In general. to another one located at another section of the same polymer. the energy absorbed by one group of chromophores can be transferred to the chromophores from the other group. the migrations of energy in polymers is somewhat more complex. This can take place by either Foster or exchange mechanism. Thus. or from a chromophore. like 1. the geometry of the polymeric chains. intramolecularly.12.18 . The separation between interacting units can be affected by the composition of the polymer. and the flexibility of the backbones. transfer can also take place from one group of atoms. For this reason the most readily observed form of energy migration is one that occurs through the mechanism of the triplet. in copolymers from monomers with two different chromophores groups. because chain folding and conformations are additional factors that enter into the picture. The possibility of energy transfer from one chromophore to an adjacent different chromophore in polymeric chains depends to a large extent upon the lifetime of the excitation and its alternative modes of deactivation. like polystyrene to a scintillator molecule. 7.16 Intermolecular energy transfer from one polymeric material to another while the molecules are in solution or in the melt can also take place.9. located on a polymeric chain in one section of the molecule.4-bis[2-(5-phenyloxazolyl)]benzene shown below14: O O More than that. An example of a transfer to a small molecule is an energy transfer from a polymer.18 Light-Associated Reactions of Synthetic Polymers polymeric chain to another.

Also. 12 If the polymers are flexible. they can also bend after photoexcitation to bring otherwise distant chromophores close enough so that energy can hop from one to the other. Such folds can be the result of packing into crystalline domains or simply from temporary collisions. Introduction 19 There are two limiting cases for the effects of polymer folding on energy-transfer efficiency. 12 For flexible polymers in solvents that promote folding. while one that involves several or more chromophores as “energy migration”. Through-space interactions between pendant chromophores are also common in polymers with large numbers of absorbing units. as mentioned earlier.18 One should also include movement of excitation across folds or loops that can form in polymeric chains. polymers with multiple sensitizers offer several routes for energy migration This can be illustrated as follows 18 : Route A Route B A very common arrangement is for the photosensitive groups to be aligned outside of a spiral arrangement of the polymeric chain in close enough proximity to each other for energy transfer. Folding of a polymer before excitation into a conformation in which the sensitizers are held within a hydrophobic pocket improves the efficiency of energy migration when a large number of intramolecular hops or through bond interactions intervene between the sensitizer and the ultimate trap. the excitation can be localized for some finite time (however small) on a particular chromophore before it is transferred to another one in the chain. the excitation energy migrates without directional control. In principle.18 Intramolecular singlet energy migration can also proceed via electronic coupling through the bonds that form the polymer backbone. moving back and forth along a chain or across space. Guillet defines intramolecular energy migration as any process that involves more than one exchange of excitation energy between spetroscopically identical chromophores attached by covalent bonds to a polymeric chain. skipping intervening units and thereby considerably shortening the effective migration distance along an individual polymer chain.1. In a random walk. this motion can take place even faster than excited-state decay. however. folding of a polymer before excitation into such a conformation that the sensitizers are held within a hydrophobic pocket improves the efficiency of energy migration with .12 The. 12 He further terms “energy transfer” as a single step migration between two chromophores.

singlet energy transfer between a sensitizer and its nearest quencher (perhaps on another chain) dominates. the rotational freedom of the polymeric chain is considerably reduced. Large scale conformational changes are unlikely. or intermolecularly along the chromophores. 13 The carbazole molecule is a good example of a chromophore that readily forms excimers. . Turro and coworkers investigated inter. In such cases the lifetimes of any particular conformation is limited by the collision processes as well as by the magnitude of the rotational barriers with respect to thermal energy.and intramolecular energy transfer in poly(styrene sulfonate). If the polymer is in solution and viscosity is low. 12 In the solid state. as mentioned before. this motion can be even faster than excited-state decay. It is described in Chapter 5. This is followed by intramolecular singlet energy migration. In such a case the energy migration can skip intervening units and thereby considerably shorten the effective migration distance along a single polymer chain. 18 Webber reports that he uses the following equation (that he calls crude but useful) to obtain rough estimates of the energy migration diffusion rate along the polymer backbone 18 : kq = 4 N0 (DQ + ^g)PR / 1000 where DQ is the normal diffusion constant of the quencher and kg is the energy migration diffusion rate along the polymer. interconversion of chain conformations proceeds fairly rapidly. This makes polymers that bear carbazole moieties useful as photoconducting materials . whereas at high excited state densities. flexible polymer frameworks can bend the polymeric chains in such a manner as to bring otherwise distant chromophores close enough together so that after excitation the energy can hop from one to another. The process generally continues until the excitation is trapped at some chain conformation that is suitable for excimer formation. Thus. 13 At low densities of excited states. however. In some aromatic vinyl polymers excimer emission can occur after an initial excitation of an aromatic chromophore. energy migration takes place through the series of donors. 18 Intermolecular energy migration can also occur between two different polymeric molecules. There still is the possibility. They found that excimer formation between adjacent phenyl groups is a dominant reaction both along a single chain and between two different chains. Such a chain conformation is referred to as eximer-forming site. Efficiency of energy migration is also helped through-bond interactions that intervene between the sensitizer and the ultimate trap. either along the polymer chain.20 Light-Associated Reactions of Synthetic Polymers a large number of intramolecular hops. it can be to different chains in a polymer that is in bulk and the chains are in close proximity to each other. for instance. that adjacent chromophores will be in a marginal eximer forming site. however. 18 Also. for flexible polymers in solvents that promote folding. As stated above. Here too.

Benjamin/Cummings. 1978 . Work by Guillet demonstrated that the effect is not entirely due to energy migration among the chromophores that form the antenna. It was. Pitts. therefore.K. New York. 5. Introduction to Modern Physics.H. Richtmeyer and E. The emission of naphthalene fluorescence is much higher than from solution of a mixture of the two homopolymers. New York Cowan and Drisko. Molecular Photochemistry. J. Elements of Organic Photochemistry.J. Fundamentals of Photochemistry. Wiley. 12 This effect is similar to one observed in ordered chlorophyll regions of green plant chloroplasts (antenna chlorophyll pigments). Guillet and coworkers carried out quantitative studies of this phenomenon with various polymers that contained naphthalene or phenanthrene as the donors and anthracene as the trap. Calvert and J. 3. 1947 N. The Antenna Effect in Polymers It was originally observed by Schneider and Springer 19 that efficient fluorescence occurs from small amounts of acenaphthalene that is copolymerized with styrene. 1967 F. named the antenna effect. Photochemistry. The antenna effect permits collection of the photon energy from the entire region of space (the hydrodynamic volume of the polymer) and transmitting it to the traps located on the polymer chain. 1978 Rohatgi-Mukherjee. NewYork. It was suggested by both groups that this phenomenon is due to energy migration between styrene sequences to the naphthalene moieties. but rather a combination of migration and direct Forster energy transfer to the trap.G. Turo. 12 References 1. McGraw-Hill. Introduction 21 1. New York. In the presence of a singlet energy trap. the lifetime of the excitation will be reduced and the length of energy migration will be reduced.J.N.7. W. Wiley. New York. Fox and coworkers 18 observed the same effect in a copolymer of styrene with small amount of vinyl naphthalene. 12 Guillet concluded that energy migration and transfer in such systems are primarily due to long-range Forster transfer by dipole-dipole mechanism (discussed earlier). The efficiency is relatively independent of concentration and can be very efficient even in dilute solutions. The difference between this form of energy transfer and one observed in solid aromatic polymers is that the photon energy is collected within a single polymer molecule and all energy transfer is intramolecular. 4. 2. Plenum. Kennard. In the absence of any trap in the polymer the energy will migrate along the backbone of the polymer chain until it is deactivated by some other processes.1.

86. 615. 18 F. 1971. Davydov. 2. Supplement. Soc. 8. Dalton. S. Daly. Photophysics of Aromatic Molecules. 18. Soc. Sec. Makromol. Lett.C.. Boston. Polymer Photophysics and Photochemistry. 3157. R.Thompson. 17. Am.B. 51.A.L.R. 1993. J. Fischer. D. Highlights of Organic Chemistry..H. "Photoinduced Electron and Energy Transfer in Soluble Polymers. 1968. J. Chem. Wiley-Interscience. Chem. 1. Watkins. Dekker. D. K. Dekker. 241 T.A.E. Tazuke and Y.L. 90." Coord. Chem. and Eng. Turro. Macromolecules.H. 1985 N. Guillet. Kaplan. Dekker... K. and S. New York. Chem. Ann.. J. P. 114 A. Polym. 10. 1974 M. 1969 P. Wilzbach and L.. Chem. ed. Birks. 1460-1482 W. Rev. and E. Pure. McGraw Hill. 1959.L. 15. 12. Disc. 86. Am.J. 14. Light-Associated Reactions of Synthetic Polymers T. 326 (1960). London.A. New York. 1967 D. 8. 20. The Importance of Antibonding Orbitals. A.C. 1964. 1958.. 1991. Fox. Martec. and J. New York. 1990. 181 6. J. Chem.. Schneider and J.S. Herkstroeter. 86. Farid. Hartman. Hammond. Theory of Molecular Excitations. Muszkat. Chem. 1970 J. S. Martic. Rev. J. 12 R. Cambridge University Press.J. Polymer Sci. Liu and G. Schulte-Frohlinde. Cambridge . 295 S. R. Weiss in Oranic Photochemistry. J..S. Chapman. 146. D.. 27. Gegiou.G. Chapter 1. 111. J. D..E. Farid. Springer.S.Y.R.. 1975. 1977. O.. 1971 S. Soc.A.. Am Chem. 11. (March 15). ed. 16. Lamola. and D. 1964. 1964. Ed. .M. Orchin and H. 1962. 215 M. W.S. 19. New York. 3318 .J. 1892 J. Srinivasan. Williams. 9. 1979. 13. Meyer.. Matsuyama. ibid. Jaffe. Chem. Williams. Foster.22 5. Radiation Research. Webber. Specht. 90.A. W.. 7.P. Appl. Faraday Sec. 47. le Noble.E. Houton Miffin Co. Jones Jr. 1960.E. 1977. Am. 10. News.R. 15. Creation and Detection of the Excited State.

The location of the chromophores on the polymeric chains and the tacticity of the polymers are also very important. 2 At present. that noncompare in efficiency to naturally occurring photon harvesting polymers for photosynthesis. structural changes due to isomerization are employed to align liquid crystals and photoconductivity is utilized in xerography. that among a number of chromophores attached to polymeric chains naphthalene and carbazole form very stable eximers. the choice of chromophores is the most critical variable. and then release this absorbed energy in a rearrangement back to the original structure. 1 There are many ways in which the photoresponsiveness of polymers can manifest itself. rearrange.1. for instance. is to utilize pendant groups that reversibly absorb light energy. however. Another interesting manifestation of photoresponsiveness in some special polymers is a change in the permeability to gases in films. in contraction of polymeric chains. 3 5. These changes can and are utilized in many ways. Among these. photochromism refers to the photoinduced reversible transformations in chemical compounds between two electronic states characterized by different absorption spectra. Thus. In such materials. Weber points out. Fox and coworkers concluded. in electrical conductivity. photorearrangements from norbornadiene to quadricyclane are back are 246 . in sol-gel transitions.1. remote sensing.Chapter 5 Photoresponsive Polymers Photoresponsive polymers are materials that are able to respond to light irradiation by undergoing reversible changes in their chemical structures and / or their physical properties. Also. One might observe changes in viscosity of polymeric solutions. research is going on in various laboratories to develop systematically derivatized polymer arrays than can collect and convert light energy. because such materials are useful in many applications. or even in color changes as a result of irradiation with light of an appropriate wavelength. To that end. for instance. however. many polymeric materials are known and utilized in the vast areas of nonsilver based imaging. information storage. while phenanthrene and diphenyl anthracene do not. the photoresponsive materials have grown in practical and scientific importance. Over the last two decades. Polymers with Norbornadiene Moieties A different approach to harvesting light energy. Polymers for Harvesting Sun’s Energy The goal of harvesting light energy has led to research in polymeric materials that could potentially mimic photosythesis.1. electroresponsive materials for displays and others. 5.

It is a reaction in which electron reshuffling occurs and the nuclei move to make or break new and bonds.5-norbornadiene-2. This preparation of such polymers and the accompanying photorearrangements can be illustrated as follows: R'" R' COOH + R" R'" COOH O O R"" O O R" R'" R' R'" O O O O O OH R"" O OH n R" R' R'" R'" O O O O O OH R"" O OH n .6-bis(4-methoxyphenyl)-7. therefore. with bis(epoxide)s.7-dimethyl-2.4.7-pentamethyl-2.3-dicarboxylic acid or 5.5-norbornadiene-2.3dicarboxylic acid. because photoenergy can be stored as strain energy (about 96 kJ/mol) in a quadricyclane molecule and later recovered 4 ultraviolet light > 310 nm 250 nm This photoisomerization reaction is referred to as a valence isomerization. prepared with the norbornandiene moieties either in the backbone or as pendant groups.6.7. Among them are polyesters that were synthesized with donor-acceptor norbornadiene residues in the main chain 53 by polyaddition of 5-(4-methoxyphenyl)-l. A number of polymers were.5. Photoresponsive Polymers 247 of considerable interest.

5 Nagai and coworkers synthesized five different polymers with trifluoromethyl-substituted norbornadiene moieties in the side chains and in the main chain 5: n CF3 O S O CF3 CF3 OH n O O O S O CF3 CF3 CF3 CF3 n O O S CF3 O CF3 O O S S NH O S S O O (CH2)6 n H N n . 4 The goal to utilize photochemical valence isomerization between norbornadiene and quadricyclane for solar energy collection and storage was reported by others.248 Light-Associated Reactions of Synthetic Polymers The photorearrangements of the norbornadiene residues in the resulting polyesters were observed to proceed smoothly to the quadricyclane groups. Also. it was found that the norbornadiene residues in these polyesters show resistance to fatigue in repeated cycles of the interconversions.

6 synthesized styrene polymers with pendant norbornadiene groups attached via amide linkages: CH2 CH n O O NH C R C where R is a methoxy or a ring substituted aniline group attached through the nitrogen or through another position. the rate of the photochemical reaction in films of these norbornadiene polymers increases efficiently by an addition of 4. The stored thermal energy of the irradiated polymers was found to be 32-52 kJ/mol.4'—bis(diethyl-amino) benzophenone photosensitizer. Benzyl esters were also prepared. As a result. 7 Kawashima.3dicarboxylic acid diglycidyl ester to adipoyl chloride gave a polyester containing norbornadiene residues in the polymer backbone and in the pendant groups. 5. the rate of the photochemical reactions in the polymer backbones was higher than that in the side chains.. and phenylcarbamoyl. In addition. Polymers with Pendant Spiropyran Groups An entirely different approach was taken by Rodriguez-Cabello and .5. In addition. Sampei et al. 8 reported preparation of donor-acceptor type norbornadiene carboxylic acids compounds with carbamoyl groups. Addition of these groups to polystyrenes formed polymers with pendant donor-acceptor type norbornadiene. Some were formed with 100% substitution.2.5-norbornadiene-2. When a photochemical rearrangement of norbornadiene residues took place in polymer films.1. These pendant groups also undergo reversible conversions into quadricycline units in polymer films when irradiated by ultraviolet light of two different wavelengths. 5 Kawatsuki et al. It was found that the polymers containing phenylcarbamoyl groups exhibits especially high photoreactivity. et al. methylphenylcarbamoyl. such as dipropylcarbamoyl.. Photoresponsive Polymers 249 All or the above polymers exhibit large absorption bands in the visible region of the spectra and the norbornadiene moieties in these polymers isomerize very rapidly. the norbornadiene moieties also exhibit efficient fatigue resistance. 7 reported that polyaddition of 2. The materials exhibit high photosensitivity as well as a large red shift in the absorption spectrum upon irradiation. all the norbornadiene groups of the polymers isomerize to the quadricycline groups in as little as 20 seconds. propylcarbamoyl.

The reactions are reversible in sunlight to reform the spiropyran ring structure. The reactions can be illustrated as follows: OH N O NO2 N NO2 O O O O Dark or UV sunlight Val Pro Gly NH O NH Gly Val Pro Gly NH O NH Gly 5.3.250 Light-Associated Reactions of Synthetic Polymers coworkers 5 They prepared a molecular-scale machine that converts light into mechanical work. The system uses a polypeptide modified by spiropyran and undergoes transitions from reversible coil to -helix when exposed to light. 9.-lactams when irradiated with UV light between 320 and 490 nm.6-dihydropyrimidin-3-ium-4-oleates. 10 An example of such copolymers and the rearrangement is shown below 10: .1. are light sensitive and undergo intramolecular photocyclization to bis. like 6-oxo-1. Novel Approaches to Light Energy Harvesting Polymers Groups.3 spiropyran groups per 100 amino acid residues allows clear photomodulation of the material. Attaching as few as 2. Irradiating this polymer with UV light causes ring-opening reactions of the spiropyran group and formation of charged species. R' R" N O R"" N O R'" h R" N N R'" O R' R'" O This was utilized to form copolymers of methacrylates with colesteric monomers.

This was done not just to mimic the natural light-harvesting process. Krebs and coworkers 17 reported a synthesis of a light harvesting material that consists of three structural domains. 15 It is speculated that a conjugated polymeric backbone. Considerable research has been carried out on means to develop the sequential multistep energy transfer systems. 12-14 but also for possible applications and use in optoelectronic and biological systems. might allow tuning the emission properties and by providing an alternate model. 12-14 Such an arrangement allows the energy to be sequentially transferred and efficiently funneled into reaction centers over small distances in the direction of decreasing band gaps. Photoresponsive Polymers 251 n O C O (CH2)4 O C O N O m O UV light n O C O (CH2)4 O C O O m O (CH2)4 S N O (CH2)4 S N N O (CH2)3 O O C2H5CH3 (CH2)3 C2H5CH3 CH3 C H (CH2)3 CH3 C H (CH2)3 It was found that the rate of photorearrangement is affected by the length of the alkyl side group in the 5 position of the pyrimidinium oleate and by the embedding of a mesoionic chromophore.5. 11 Different antenna chromophores that surround the reaction center are arranged morphologically in an order of energy gradient. with well-designed interruptions of conjugation by insulating spacers. as shown above. antenna pigments harvest energy and transfer it into a reaction center for redox reactions. 16 Based on this concept. Two of them . 10 In photosynthesis.

The ratio of zinc porphyrin to the polymer blocks can be varied in the material by varying the size of blocks A. it was observed that the light-harvesting properties of the three-domain structures depend on the chain lengths of the conjugated polymers. that introduction of an energy gradient with three welldesigned chromophores into a silylene-spaced polymeric chain may lead to sequential energy transfer. no conjugative interactions between the systems and the silicon moiety is observed. there is quantitative energy transfer in the solid state. 19 They believe. Also. therefore. when the silylene spacer contains only one silicon atom. Studies of energy transfer from the polymer to the zinc porphyrin showed that there is actually very little energy transfer when the material is in solution. The polymer has a constant ratio of the zinc porphyrin to the incorporated monomer units. 18 In general. On the other hand. regardless of the molecular weight. Cheng and Luh reported that they are also trying to develop polymers that would mimic natural photosynthesis with synthetic polymers. they carried out preparations of regioregular silylene-spaced copolymers composed of energy gradients with three different chromophores. 18 They point out that silylene moieties have been used extensively as insulating spacers. To achieve this goal.252 Light-Associated Reactions of Synthetic Polymers are conjugated homopolymers that are linked with a zinc porphyrin: A n B A m A = n B = N Zn N N N Sections A and B of the above block copolymer are illustrated above. One of the polymers prepared in this way can be illustrated as follows: .

This is quite encouraging. Photoresponsive Polymers 253 Si D2 Si D2 Si Si A n Their synthesis utilized rhodium-catalyzed hydrosilylation of bisvinylsilanes and bis-alkynes. Cheng and Luh found that upon excitation of the donor chromophore D1 only emission from the acceptor A was observed. corresponding to D1. 19 The chromophores and the acceptor were illustrated as follows: D1 = D2 = or or N N O A= OC4H9 or OC4H9 It has not been disclosed yet. respectively. how successful this whole approach is to actually mimicking photosynthesis.5. The ratio of the three chromophores in the above polymer is 1:2:1. at this time. 5.2. but it appears to be a very interesting concept. D2. Photoisomerization Reactions in Polymeric Materials A common photoisomerization reaction is intramolecularrearrangement that takes place in the nitro groups in poly( -nitrostyrene) and its dimeric model compound upon irradiation with UV light 20: . and A chromophores.

4'-diphenylmethanediisocyanate in one case or with 1. All of the copoly(amide-imide)s were found to be soluble in polar aprotic solvents and to yield transparent.4'-diamino-3. The photofries reaction. however. is completely suppressed in polymers that contain an aliphatic amide moiety.3'-dibenzoylstilbene. Among all the photorearrangements.4-phenylenediacrilic acid with either 4. perhaps. however.254 Light-Associated Reactions of Synthetic Polymers NO2 CH CH n h base CH O OH N n This reaction. This reaction has been described in many books. usually takes place to the more stable form. it is possible for either isomer to form. is accompanied by molecular weight loss and the molecular weight of the photoproduct is considerable lower than that of the starting polymer prior to irradiation.2. however. This means that in the excited state the cis-trans isomerism disappears. is not certain. respectfully. 20 Whether this photoisomerization reaction has practical utility. Generally. also undergo a photofries rearrangement. exhibit photoviscosity effects in dilute solutions due to cis22 . This may. 22 When the polymers are irradiated in solution the p-phenylenediacryloyl units undergo trans-cis photoisomerization and (2 + 2) photocycloadditions.6-diisocyanatohexane in another case. 22 The fully aromatic polyamides. This was followed by preparation of two series of photoreactive copoly(amide-imide)s by direct polycondensation of the bis(trimellitimide)s and 1. A well known example one is that of cis-stilbene to the trans isomer. 22 Polymers prepared by condensation of 4. photoisomerization of chromophores in dilute solutions is a first order reaction. 22 The same processes are also observed in the polymer films. who formed three bis(trimellitimide)s by condensing three aromatic diamines with trimellitic anhydride. 21 The isomerization reaction takes place because many olefins in the excited singlet and triplet states have a perpendicular instead of a planar geometry. however. a bi(amino ketone). The return.4'-diacetylstiblene as the bis(ketomethylene)monomer with 4. Upon return to the ground state. S0. Photoisomerization of the Olefinic Group An example of olefinic groups rearrangement is work by Onciu et al.1. flexible and tough films. be due to hydrolysis of the product with a trace amount of water in methyl alcohol/ammonia medium that is used during the irradiation.. a cis-trans isomerization reaction is the most useful one. 5.

2. Photoresponsive Polymers 255 trans isomerization. 23 The preparation of the polymers and the photorearrangements can be illustrated as follows: O CH3 CH CH H2N NH2 CH O O + CH CH3 O CH CH n N N UV light CH CH CH N N CH CH CH n The changes in viscosity can vary from 2 to 23% as a result of irradiation. 5. and its photoinduced and thermal geometric isomerizations have been extensively .5.2. Photoisomerization of the Azo Group Azobenzene is a well-known photoresponsive chromophore.

This was demonstrated on a polymer with azo linkages. Because. photochemical conformation changes were demonstrated in a copolymer of styrene. as for instance. 27 Reversible isomerizations between cis and trans structures are due to these transitions. As a result. Thus. Changes in the molecular structure. while the cis isomer shows a weak absorption of the n * transition. changes in the dipole moments. around 430 nm. the azobenzene functionality has been incorporated in wide variety of polymers. the trans isomer of azobenzene exhibits an intense absorption around 320 nm due to the * transition. Azo excitation and azo n excitation trigger trans-to-cis and cis-to-trans isomerizations. Also. Exposure from dark to light can result in a contraction of as much as 0.256 Light-Associated Reactions of Synthetic Polymers explored. Photoisomerization can proceed almost quantitatively. 29 The isomerization back to the trans configuration can be readily carried out either thermally. the thermal isomerizations from cis to trans configurations take place due to low activation energy of the cis-to-trans process. the azobenzene units are potentially useful components for photocontrol of polymer structures and properties. or by visible light irradiation. while the subsequent sections describe specific physical changes and possible utilizations. the isomerizations have a strong effect on physical properties. such as cis-trans isomerization in polymers can induce contraction and expansion of the polymeric chains on both microscopic and macroscopic scale. Isomerizations of the azo chromophore in compounds are often accompanied by drastic changes in a number of properties such. 24-26 The azo linkage normally exists in the more stable trans form. 28 By comparison. where azobenzene structures are attached in the comonomer to the benzene portion through amide linkages 31 : .5 % 30: dark N N light N N Some interesting reports on photoisomerization of azo-polymers are presented below. 21 Azobenzene and its derivatives assume both trans and cis conformations with respect to the azo linkage.

n = 2-18.5. but is much faster when exposed to visible light. Polyesters based on this monomers are claimed to be useful for optical recording media such as hologram recording media with low light absorption or loss and wide range of working wave lengths.bis(6-chlorohexyloxy)diphenyl ether in the presence of Zn acetate in a vacuum at 160o to form a polyester.4'-. This compound is subsequently reacted with 4. Photoresponsive Polymers 257 n n heat or visible light NH = <380 nm O N N NH O N N After 10 minutes of irradiation with ultraviolet light the photostationary state is reached. consisting of 79% of the cis isomer. m = 1-3. 31 A Japanese patent 32 describes preparation of isophthalic type polyesters that include monomers with pendant azo groups: CO X CO X (Y)m O (CH2)n O N N Me where Y is a hydrogen or a lower alkyl group. The patent claims that coating the polyester on a glass plate and recording with either 532 . The preparation of the polyester consisted of first heating diethyl-5-hydroxyisophthalate with 4-(6-bromohexyloxy)-4'methyl-azobenzene in acetone at reflux to give diethyl-5-{6-[4'-(4"methylphenyl-azo)phenoxyhexyloxy}isophthalate. Back isomerization to trans of the sample is slow in the dark(less than 10% in 60 min).

R” = H or n-C6H13 . This is reported to be accompanied by changes in electrochemical properties. The product. 32 Izumi et al. In addition. These were formed by using palladium-catalyzed cross-coupling reaction of 4.4diethynylbenzenes and bis(trimethylstannyl)heteroaromatics.and poly(phenyl vinylene)-based polymers: R" R" N N R" R" R" R' R" N N R" R' R" n n R" R" R' N R" R" R' n N where R’. also carried out similar preparations of conjugated polymers with azobenzenes in the main chain. respectively. 33 prepared poly(p-phenyleneethynylene) and heteroaromatic-containing poly(phenylene)-based conjugated polymers with photoisomerizable azobenzene units in the main chain . a polymer with a low degree of main-chain conjugation shows reversible photoisomerization of azobenzene units. 34-36 Application of various palladium-catalyzed coupling methods such as the Suzuki coupling and the Heck reactions allowed formation of poly(pphenylene). Izumi and coworkers. in a earlier study.258 Light-Associated Reactions of Synthetic Polymers nm or 515 nm incident light gave a hologram.4'-diiodoazobenzenes with 1..

Also. Photoresponsive Polymers 259 The preparation of the poly(p-phenylene)-based conjugated polymers with photoisomerizable azobenzene units in the main chain can be illustrated as follows37: R' O B O R' R" B O O R" R" + I N N I R" R" R' Pd N Base R' R" R" n R" N where R' and/or R" can be hydrogens or n-C6H13 . The resulting polymers were found to possess high molecular weights (Mn > 7 x 103) and to be thermally stabile (to > 350 °C). With each azobenzene capable of cis-trans isomerization. and tetrahydrofuran. 37 Synthesis of a series of azobenzene-cored polyphenylene dendrimers was reported. these polymers are soluble in common organic solvents. 39 The materials were also demonstrated to exhibit a photoresponsive behavior upon UV and visible light irradiation. such as chloroform. formation of polyphenylene dendrimers with azobenzene structures in the core was reported earlier. when either or both of the monomers possess nhexyl side chains on the aromatic rings. the .5. 38 The photoresponsive properties of these dendrimers were investigated by optical spectroscopy and gel permeation chromatography The polyphenylene dendrimers exhibit a photoresponsive behavior upon UV and visible light irradiation. Despite their stiff structures. toluene. photochemical trans-to-cis isomerizations in the solid state were found to take place at 20 °C. resulting in reversible and appreciable changes in the dendrimer structures. These isomerization processes are also accompanied by changes in the threedimensional hydrodynamic volumes of the polymers. resulting in a reversible and appreciable changes of the dendrimer structures. Junge and McGrath 40 reported studying photoresponse of dendrimers containing three interior azobenzene moieties that are radially configured about the core. they exhibit fluorescence. Yet. 38 Actually.

. The presence of sharp isobesic points in the absorption spectra during isomerization can be expected on the basis of the independence of the chromophores. On the other hand. Dark incubation in CH2Cl2 solutions of the dendrimers maximized the n * transition at 352-nm. 40 Nozaki et al. 1H NMR spectral data indicates independent. rather than simultaneous isomerization of azobenzene units. and irradiation with 350-nm light resulted in photoisomerization. the keto/spiroketal polymers drastically change in the main-chain conformations.260 Light-Associated Reactions of Synthetic Polymers dendrimers can exist in four discrete states. and trans-trans-trans. 42 . 42 synthesized photoresponsive -polyketones with azobenzene side chains: O (CH2)4 UV n O n N N (CH2)4 O N N Vis O and a ketone/spiroketal one: N N O (CH2)4 O (CH2)4 N N O x y O Vis UV N N O (CH2)4 O (CH2)4 N N O x O y They found that the conformations of the polymers that contain the ketone units only are not affected by the cis-trans isomerization. cis-transtrans. cis-cis-cis. as evidenced by a decrease in the absorbance at 352-nm and an increase in the n * transition at 442-nm. All states are detectable in solution and exhibit different physical properties. cis-cis-trans.

2. They also observed that this decrease in viscosity is reversible.V.1 Changes in Viscosity and Solubility of Polymeric Solutions Changes of viscosity in polymeric solutions that are associated with photoinduced conformational changes of the macromolecules were observed by Lovrien in 1967.5.4dioxane causes a decrease in specific viscosity between 24 to 30 % and in tetrahydrofuran between 1 and 8%. He also observed a decrease in the viscosity of a poly(methacrylic acid ) and chrysophenine solution in water under the influence of UV light. 43 He reported that solutions of a copolymer of methacrylic acid and N-(2. The magnitude of the effect was found to be related to the quantity of azobenzene linkages present in the polymer. U. 43 This was followed by various reports of photoviscosity effects in solutions of azobenzene based polymers. With . Hallensleben and Menzel 45 found that irradiation of poly(5-(4phenylazobenzyl)-L-glutamate in 1. light irradiation of a solution of this polymer in 1.4-dioxane solution with UV light ( > 470 nm) decreases the viscosity by 9% .2'-dimethoxyazobenzene)acrylamide exhibit an increase in specific viscosity when irradiated with UV light. The monomer was polymerized to yield poly[p-(phenylazo)acrylanilide] that undergoes photochemical interconversions between trans and cis isomers under UV or visible light irradiation. Matejka and Dusek 44 studied a copolymer of styrene and maleic anhydride with azobenzene in the side chains. Here too this change in viscosity is accompanied by a trans to cis isomerization that was estimated to be 23%. Photoresponsive Polymers 261 Condensation of acryloyl chloride with 4-(phenylazo)aniline was used to form a monomer p-(phenylazo)acrylamilide. This reaction is reversible and reproducible for the homopolymer and for a copolymer with methacrylic acid 43: CH2 CH n C NH O CH2 CH n C NH O N N N N 5.2.

CH3 CH3 CH2 CH2 C m n C O O O CH3 C O N N All the polymers exhibit a photoviscosity effect when exposed to UV irradiation at = 365 nm.N'-dimethylacetamide. Also. It was observed that the intrinsic viscosity is about 40% lower during UV irradiation than in the dark. All the polymers exhibit photoviscosity effects. a 60% reduction in specific viscosity can be achieved by UV light irradiation (410 > > 350 nm). Irie et al. 47 The irradiations were carried out at 35 oC with UV light between 410 and 350 nm.262 Light-Associated Reactions of Synthetic Polymers additional irradiation by 360 nm UV light. Changes in viscosity of solutions in dimethylsulfoxide of a range of polyureas with azobenzene groups in the polymer backbone were reported. Fernando and coworkers 49 prepared a series of copolymers of trans-4-methacryloyloxyazobenzene with methyl methacrylate. 48 Recently. toluene solutions of polydimethylsiloxane with azobenzene residues were shown to exhibit 20 % lower viscosity under UV light irradiation than in the dark. The initial viscosity is regained by storage in the dark at room temperature for 30 hours. 40 This conformational change might possibly be illustrated as follows: .. In solutions in N. 46 synthesized a number of polyamides with azobenzene groups in the backbone. the viscosity decreases an additional 9% and the isomerization to cis reaches 89 %. This effect was attributed by them to conformational contraction of the polymer chains due to dipole-dipole interaction between neighboring chromophores.

several hundred seconds after the flash there is evidence of polymer aggregation and precipitation. 50 This occurs at a high rate per second as a consequence of isomerization. 51 The conformational changes of the polymer can be illustrated as follows: . 50 In addition. when copolymers of polystyrene and 4-(methacryloylamino)azobenzene containing 2.5. when azobenzene residues are introduced into the main chain of poly(dimethylsiloxane). At a later stage. Photoresponsive Polymers 263 N N N N n UV light N N N N Also. of light.5% of the latter are irradiated in a cyclohexane solution with 15 flashes of 347 nm. reversible solution viscosity changes can be obtained by irradiation with ultraviolet light. the polymeric chains contract.2 to 6.

Isomerization from cis to trans and back of azo groups. is not the only mechanism that can affect photoviscosity change in polymeric solutions. This can be illustrated as follows: x O O NH2 NH y O light heat x O NH2 NH y N 2 C OH N 2 C OH . reversible solution viscosity changes were also observed 48 in solutions of poly(dimethylacrylamide) with pendant triphenylmethane leucohydroxide in methanol.264 Light-Associated Reactions of Synthetic Polymers O CH3 O CH2 Si CH3 CH3 CH2 Si N x CH3 C O C N N N n O CH3 CH3 O CH2 CH2 Si N x Si CH3 CH3 C N N O C N n A shown above. the conformational changes are confined to the isomerization of the azo group. Thus. however.

Also. 53 This is believed to be due to photoisomerization of the pendant spirobenzopyran groups to the polar merocyanine form with the resultant decrease in polymer-solvent interaction and subsequent precipitation of the higher molecular weight fractions of the polymer.4 in methanol and 0. from potential use in paints and coatings.3 mol %) performs as a negative photoresist with high contrast. Sol-Gel Reversible Conversions Gel systems that respond to external light stimuli are of considerable interest in many fields. A copolymer with a high content of spirobenzopyran groups (12. 53 5. 52 This increase corresponds to a decrease in polymer coil size in water. as shown. The quantum efficiency of this process was determined to be 0. is irradiated with light. when a terpolymer that consists of vinyl pyrrolidone.5. there is a viscosity increase 52: CH2 O CH N CH2 CH CH2 CH C NH x y z O C O NH COOH O O OH The absorption of light by the diphenylanthracene was found to result in efficient intracoil sensitization by fluorescene.2. Photoresponsive Polymers 265 So. and a flluorescein derivative of acrylamide. to personal . styrene that is p-substituted with 9. the viscosity changes are due to positive charges that form on the pendant groups.2.2.10-diphenyl anthracene.8 in water. Analysis of the fluorescence decay also demonstrates that the intracoil energy transfer is essentially a static process and that aggregation can result in nonexponential fluorescence decay that is interpreted as a dynamic equilibrium that takes place between diphenylanthracene and a nonfluorescent dimer state 52: The solubility of a copolymer of styrene in cyclohexane was found to change reversibly upon ultraviolet light irradiation when the copolymer contains small amounts (~2 mol %) of spirobenzopyran among the pendant groups.

1-x O ONa+ NH x O (CH2)11 CH3 hydrophobically modified poly(acrylic acid) . Smith. and Hatton observed 56 that the viscosity and gelation of mixtures of hydrophobically modified poly(acrylic acid) and a cationic photosensitive surfactant can be controlled reversibly by switching irradiation of the sample between UV and visible. Ire and Iga demonstrated that photostimulated sol-gel transitions are possible with gels of a polystyrene copolymer in carbon disulfide solution that carry some azobenzene groups. 54 The transitions are reversible and take place upon ultraviolet light irradiation. optical storage. The polymer undergoes cis to trans isomerization of the pendant azobenzene groups with a 62% conversion for polymers containing as much as 10. Applications might also include photonics.266 Light-Associated Reactions of Synthetic Polymers care items and drug delivery systems. Lee. and photoswitchable materials.5% of azo groups: n C NH O m n O NH m N N N N Irradiation with light of wave length between 310 and 400 nm converts the solution to a gel and visible light (>450 nm) reverts the gel back to the solution The process is a result the trans isomerizing to the cis form upon irradiation with UV light. 55 It suggests that cis azobenzene moieties in the pendant groups make interpolymer crosslinking junctions that are more stable than the interactions of the trans forms.

resulting in gelation at lower surfactant concentrations under visible light.6 x 104 cPa for the trans form and 2. because polymer chains form a network structure via hydrophobic associations of C12 side chains. Observed viscosity maxima of 5. and a photoresponsive competitive guest. micellar aggregates form on the polymer and solubilize the alkyl side chains grafted on the hydrophobically modified poly(acrylic acid). leading to physical crosslinking and gelation. the gel is converted to a sol mixture because hydrophobic interactions of C12 side chains are dissociated by the formation of inclusion complexes of cyclodextrin with the C12 side chains. has a lower critical aggregation concentration than the more polar cis (UV light) form.4’-azodibenzoic acid.5. Reversible viscosity changes of up to 2 orders of magnitude are observed upon exposure to UV or visible light.4’-azodibenzoic acid: HO N O O N + OH . with a planar azobenzene group in the surfactant tail. is more hydrophobic than the nonplanar cis conformation of the material that is attained by ultraviolet light irradiation. that is attained by visible light irradiation.2 x 103 cPa for the cis form of the surfactant suggest that the trans form surfactant micelles are more effective at solubilizing the alkyl side chains than are the more hydrophilic cis-form micelles. Upon addition of 4. At the critical aggregation concentration of the surfactant. 4. The hydrophobic trans (visible light) form. When -cyclodextrin is added to the gel-like aqueous solution. An aqueous solution of dodecyl-modified poly(acrylic acid) exhibits a gel-like behavior. dodecyl-modified poly(acrylic acid). the cyclodextrin interacts predominantly with 4.56 Harada and coworkers 57 reported forming a photoresponsive hydrogel system by combination of -cyclodextrin. Photoresponsive Polymers 267 CH3CH2 N N O(CH2)4N(CH3)3 Br surfactant The planar trans form of the surfactant.4’-azodibenzoic acid to the binary sol mixture of the modified poly(acrylic acid) and -cyclodextrin.

because -cyclodextrin formed inclusion complexes more favorably with C12 side chains than with cis-azobenzoic acid.3. when the ternary sol mixture is irradiated with visible light. This phenomenon received more attention recently 58-60 If the axis-selective reaction is accompanied by molecular reorientation. Changes in Birefringence and Dichroism Over the last twenty years there were reports that exposure to linearly polarized light of some photoreactive films can generate optical anisotropy in these films through an anisotropic polarization axis.. 131 reported that in axis-selective triplet phtotosensitized reactions of photocrosslinkable liquid crystalline polymeric films achieve molecular reorientation. As a result. resulting in a solto-gel transition. the azobenzene compound isomerizes from trans to cis. Four photosensitizers were used in this work.2. Irradiation is done with linearly polarized light at 405 nm. a large anisotropy can form. the mixture undergoes a gel-to-sol transition. These are as follows: O C2H5 N C2H5 N C2H5 C2H5 4. Kawatsuki et al.N’-bisdiethylamino)benzophenone .2. Harada and coworkers 57 reported that these gel-to-sol and solto-gel transitions occur repeatedly by repetitive irradiations of UV and visible light. the molecular reorientation is thermally enhanced. the azo group isomerizes back from cis to trans and the mixture undergoes a solto gel transition. 5. Also. On the other hand. When this ternary gel mixture is irradiated with UV light. Thus.4’-(N.268 Light-Associated Reactions of Synthetic Polymers 95 HO O NH 5 n O CH2 OH O + HO OH C12 H25 Hydrophobic associations of the C12 side chains are restored.

several types of polymeric films were used in this work that are liquid crystalline polymethacrylates with photocrosslinkable mesogenic side groups: O O CH2 n OCH3 (CH2)6 O O O In all cases the photoreactivity of the films was generated with less that 9% doping. 61 One such material can be illustrated as follows: m O O n (CH2)2 OCH3 NO2 N N N C2H5 This is due in part to a mechanism that allows anisotropy to be optically induced at room temperature in these materials.5. The axis-selective photoexcitation of the triplet sensitizers and the polarization-preserved energy to the photoreactive mesogenic groups determined the photoinduced optical anisotropy as well as the thermal enhancement of the molecular orientation. be eliminated by either optical or thermal means. The anisotropy can. Amorphous polymers with pendant azobenzene groups were demonstrated to be good candidates for optical data storage and other electrooptic applications. 62 The induced anisotropy manifests itself in birefringence and in dichroism of long-term stability. Photoresponsive Polymers 269 H2N NO2 p-nitroaniline O C2H5 NO2 N C2H5 4-nitroacenaphthene 4-(N-dimethylamino)benzophenone Also. however. The .

65 The conclusion is that there is some form of dipolar interaction between the azo groups on the side chains that are next to each other on the polymer backbone. Thus. 62 When the external electric dc field poling is done (see Chapter 6) at temperatures above the glass transition temperature. Linearly polarized light orients an excess of the azobenzene group perpendicularly to the polarization direction.270 Light-Associated Reactions of Synthetic Polymers mechanism by which anistoropy is induced involves selective photoexcitation followed by a spatial reorientation of the azo-aromatic side chain dipoles via trans-cis-trans isomerization. only the trans isomers remain present in the film. however. By selectively exciting only the dipoles possessing a sufficient dipolar component. 65 In addition. thus "erasing" the induced birefringence. indicate that the dipoles are associated in an anti-parallel fashion. 63 The literature indicates. This means that irradiation with an argon laser at 514 or 488 nm will photochemically activate both the trans-cis and cis-trans isomerization process. while circularly polarized light restores the original disorder of orientations. Absorption maxima shifts to higher energy with increasing azo concentration. 64. that the resultant orientation order is not linearly dependent on the chromophore content. It was demonstrated by Natansohn and coworkers 64. especially at high chromophore concentration. after the laser is switched off. a perfectly stable dipolar orientation is created that is perpendicular to this direction. This interaction reduces the mobility of the side chain but enhances the orientation stability. it was also reported that circular dichroism and circular birefringence can be induced in thin films of achiral polymer liquid crystals containing 7 to 15 mol % azobenzene chromophores by irradiation with circularly polarized light. 66 The polymer can be illustrated as follows: O O (CH2)11 CN O N nO x O (CH2)6 N CH3 N NO2 . or by absorption probability in a single direction. The cis isomers are relatively short lived even in the absence of irradiation. 65 how the transcis-trans isomerization cycles of azobenzene bound in high glass transition temperature polymers could be used to induce birefringence in the polymer films. the orientation of dipoles takes place (by the typical theoretical description of the process) in one of the independent dipole responses.

the amount of azobenzene units. This was done through the layer-by-layer adsorption process. the solvent effect on the hydrogen-aggregation in the multilayer films was determined by the structural details of the azo polyelectrolytes. due to a cooperative motion.Y is NO2 in one polymer and COOH in the other. optically induced surface modulation on the multilayer surfaces were observed. Upon exposure to an interference pattern of the Ar+ laser beam at modest intensities. When dissolved in an anhydrous dimethylformamide and also in a series of dimethylformamide-water mixed solvents of different ratios. employing horseradish peroxidase. Altering the water content of the dipping solutions of both azo polyelectrolytes was found to dramatically change the thickness of the sequentially adsorbed bilayers. The photoinduced circular dichroism can be erased by heating the films above the clearing temperatures or by annealing the films in the liquid-crystalline phase. significant dichroism was induced in the multi-layer films that were prepared from the dimethylformamide dipping solution.5. and the sample temperature. poly-[4-(phenylazo)phenol]. The level of photoinduced chirality depends upon incorporation methods (doped or chemically bound) of the azobenzene chromophores. Photoresponsive Polymers 271 Circular dichroism was observed not only for the azobenzene moieties but also for the nonphotoactive mesogens. Two newly synthesized polyelectrolytes functionalized polymers with branched side chains bearing electron donor-acceptor type azobenzene chromophores were used as polyanions to build up multi-layer films through an electrostatic sequential adsorption process 67: N OCH2CH2N m n COOH COOCH2 CH2CH3 N OCH2CH2N CH2CH3 N Y N Y where . chromophore orientation. and surface roughness of the multi-layer films. cyanobiphenyl groups. 68 Spectroscopic data show that the coupling reaction occurs . Circularly polarized light of the opposite handedness produces enantiomeric structures. was used to prepare a photoactive azo polymer. both azo polyelectrolytes formed uniform multilayer films. On the other hand. After the irradiation with a linearly polarized Ar+ laser beam at 488 nm. from 4(phenylazo)phenol. Poly(diallyldimethylammonium chloride) was used as the polycation. and a chiroptical switch can be achieved by alternating irradiation with left and right circularly polarized light. 67 Enzymatic synthesis.

Also. 69 The monomer used in the grafting reaction is 4-[N-(acryloxyethy)-Nethylamino]-4'-nitroazobenzene. This requirement. The polymer is a composite of poly(N-vinylcarbazole). This results in the formation of a branched polyphenylene backbone with pendant azo functionalities on every repeat unit of the macromolecules. It forms good optical quality thin films. The light gets diffracted by the reversible index modulation that. Polymer solutions show reversible trans to cis photoisomerizations of the azobenzene groups with long relaxation time. and ms response times can be prepated.70. There is considerable interest in using polymeric photorefractive materials for holographic recording. OH n N N This enzymatically synthesized azophenol polymer has an extremely high dye content (nearly 100%) and is soluble in most polar organic solvents. Such reversibility would make these polymeric materials suitable for real time optical applications. Blanche and coworkers 71 demonstrated that recording of volume holograms on such polymers with femtosecond pulses using two photon absorption coupled with a nondestructive readout using cw lasers of the same wavelength is possible. two-beam coupling gain coefficients. The photorefractive effect must be completely reversible so that the recorded holograms can be erased at will. it was demonstrated that polymeric composites with high diffraction efficiency. It was found that the azo groups through rapid cis-trans isomerization orient themselves perpendicularly to the polarization direction of the light. however. When the films are irradiated with polarized light of 69 488 nm this resulted in formation of anisotropic films. The poly(azophenol) films also exhibit photoinduced absorption dichroism and large photoinduced birefringence with unusual relaxation behavior. creates a real problem.272 Light-Associated Reactions of Synthetic Polymers primarily at the ortho positions. Earlier. simultaneously erases the hologram. 68 A photoresponsive azo-polymer was grafted onto polyethylene film. at the same time. and benzyl . because recording and reconstruction of the stored information is done by illuminating the material with a spatially homogenous light beam of the same wavelength. N-ethylcarbazole. with some coupling at the meta positions of the phenol ring as well.

5. this phenomenon and the quadratic nonlinear optical effects were extensively investigated in the last few years.2. 71 Particular emphasis was placed on the relationship between photoisomerization. an electrooptic chromophore was sandwiched between two coated transparent electrodes. and their molecular structure. It can be illustrated as follows 15 : F O O CN F The composite was fabricated into photorefractive samples by injection molding.2. 71 It was reported. A photosensitizer. The polymers used in one of these studies can be illustrated as follows 71: O N O R N O O N n O2N N N . a series of polymers containing azo dyes with large differences in the second order transition temperature were compared. Application to Optical Data Storage Due to possible utilization of photoinduced orientation in polymeric films in optical data storage. As a result.4. Photoresponsive Polymers 273 butyl phthalate. it was shown that light-induced nonpolar orientation in very high Tg polyimides (Tg up to 350 oC) can take place even at room temperature. that to study photoisomerization in a polymeric environment. for instance.5. Tg of the polymers.

From the behavior of the mean absorbance it was concluded that all the azo chromophores revert to the trans form on completion of a thermal back reaction. polyesters were formed by melt transesterification 73 of diphenyltetradecanedioate with a series of mesogenic 2-[-4-[(-4cyanophenyl)azo]phenoxy]alkyl]-l. completely erased on heating the samples above their Tg for 10 minutes.in another. The molecular weights of these polyesters ranges between 5000 and 8900: O (X) (CH2)m O O (CH2)12 O n (X) N O N CN (X) (X) . however. where the alkyl spacer is hexa. 72 Also. The observed increase in the dichroic ratio over the first 25 hours is believed to be due to the thermal back isomerization and not due to the relaxation of the induced orientation. or decamethylene.274 O N O Light-Associated Reactions of Synthetic Polymers R N n O N O N N NO2 where R = (CF3)2 -C < in one polymer and -COO-(CH2)2-COO. Irradiation of the films with incident light gives holograms. 71 Heating polymers at 170 0C for one hour fails to erase the green light-induced dichroism in the samples. This dichroism is.3-propanediols. octa.

Based on their findings. they reported that they have prepared a photosensitive polymer with a high two-photon absorptivity group: O N x O O y O O C H 14 21 C14 H21 S z Photophysical properties indicate. providing image contrast. 73 Belfield and coworkers 74 describe simultaneous two-photon absorption as a process in which the probability of a ground to excited state transition scales quadratically with incident intensity of the irradiation source. indicating the possibility of high optical data density storage in the organic material.74 . even though the glass transition temperatures are about 20 °C. Furthermore. A multi-layered assembly and bulk two-photon fluorescence lithographic imaging provided both negative” and “positive” contrast images. Previously. This nonlinear or quadratic dependence makes two-photon excitation attractive for use in several emerging technologies. and optical power limiting. the this polymer undergoes twophoton unconverted fluorescence. anisotropy and holography. such as two-photon fluorescence imaging. Of greatest interest is the possible development of organic three-dimensional optical data storage media and processes. It was also claimed that the films can be reused many times without failure.5. threedimensional microfabrication. Complete erasure of the information can be obtained by heating the films to about 80 oC. 75 reported the synthesis and characterization of organic fluorescent dyes with high two-photon absorptivity. Lifetimes greater than 30 months for information storage was obtained. Belford et al. the photosensitive polymer was also responsive to two-photon induced “writing” followed by “reading”. 74 Fluorescence properties of the polymer were modulated in the presence and absence of a photoacid generator. demonstrating the possibility of’ three-dimensional optical data read-out. A resolution of 5000 lines/mm and diffraction efficiencies of about 40 % were achieved.. Photoresponsive Polymers 275 Optical storage properties of these polyesters were studied through measurements of polarization.

Changes in Contact Angle of Water Wu et al. The precursor polymer was functionalized by the Schotten-Baumann reaction with several aromatic azo compounds containing hydroxyl end groups. azo polyelectrolytes showed a significant photochromic effect. A significant photochromic effect from cis-trans isomerization of the azo chromophores was observed for the multilayers. 76 A reversible photocontrol of wettability of polymeric materials is possible by a technique developed by Irie and Iga 54 When a copolymer of butyl methacrylate and (2-hydroxyphenyl). 76 reported syntheses of a series of novel azo polyelectrolytes. The contact angles of water on the surfaces of spin-coated films of two of the polymers decreased upon UV irradiation. The extent of the photoinduced contact angle changes depends on the type of the azo chromophores and the degree of functionalization. Photoinduced contact angle changes of water on the self-assembled multilayers were also observed. poly(acryloyl chloride). starting with a reactive precursor. This reverses back to the original structure in the dark 54: . there is a large increase in the contact angle and wettability of the material. n O Cl + HOCH2CH2O N N X n O N OCH2CH2O N X When irradiated by 365 nm UV light.276 Light-Associated Reactions of Synthetic Polymers 5.5..-(4-vinylphenyl)benzyl alcohol is irradiated with ultraviolet light.2.2. The degrees of functionalization were controlled by selecting suitable feed ratios between the azo reactants and poly(acryloyl chloride) The unreacted acyl chloride groups were hydrolyzed to obtain ionizable carboxylic acid structures. Self-assembled multilayers of the azo polyelectrolytes were formed by a layer-by-layer adsorption method.

low contact angle high contact Polyacrylamide gels that contain triphenylmethane leucocyanide groups (1-4 mol %) exhibit reversible photostimulated dilation 72 upon irradiation with ultraviolet light of 270 nm.5. Changes in Optical Activity Conformationally restricted copolyaramides containing a combination of 4. The weight of the gels increases as much as 13 times and the size expands approximately 2.2'-binaphthylene main-chain segments were demonstrated to exhibit photoresponsive chiroptical behavior.4-phenylene. is suppressed by addition of salts. such as NaCI or KBr.4'.2 times in each dimension as it swells with water. Photoresponsive Polymers m UV light O dark H9C4 O H9C4 O 277 n O n m C OH OH C O . The gel expansion.2.6. 77 This is due to multiple trans-cis-isomerization reactions triggered within the polymer backbones.azobenzene. This is produced by photodissociation of triphenylmethane leucocyanide groups contained in the gel network and is the main driving force of the photostimulated gel dilation angle. however.2. The cycles of dilation and contraction of the gel by photoirradiation can be repeated several times. and chiral 2. In contrast to the more randomly constructed counterparts. 1. Z UV light Z + C OH NC CN NC C OH CN 5. The dilated gel de-swells in the dark. . The salt effect and semiquantitative theoretical considerations of the behavior of ions suggests an osmotic pressure differential between the gel inside and the outer solution.

78 This monomer was illustrated as follows: CH3 O H The copolymers are capable of forming chiral nematic phases. they remain mobile after treatment and chain orientation. needed. 83 Several types of polarized-light-induced liquid crystalline aligning of molecules were reported in the literature.3. Other materials with higher Tg are. 5.77 Also a new chiral menthone-based acrylic monomer.. The polymer and its copolymers were reported to have the ability to align in thin films in the direction perpendicular to the axis of the linearly polarized ultraviolet light. Their bulk alignment or their texture is stabilized by a polymer network. wavelength-dependent inversions in their optical rotations in response to multiple UV. therefore. was synthesized and used to obtain a homopolymer and a series of comb-shaped copolymers with a nematogenic monomer. 89 One photoalignment material is poly(vinyl cinnamate). Among the . A draw back to using poly(vinyl cinnamate) and its copolymers is a low glass transition temperature. because in these displays films of polyimides are widely used .light/visible. It was influenced by need for alignment in liquid crystalline flat panel displays. led to development of molecular structures that undergo alignment upon irradiation with linearly polarized UV light.light illumination cycles. The treatments consisted of rubbing process with velvet fabrics. The surfaces are usually treated to produce uniform alignment of the liquid crystals into suitable "pretilt" angles. Search for new methods. 82. 79-81 Polymer-stabilized liquid crystals are low-molar-mass liquid crystal. Liquid Crystalline Alignment In the past ten or more years glass transitions and mobility in confined polymer systems aroused much interest. capable of transcis isomerization. Such polymer network is usually in low concentration. As a result. however.2.278 Light-Associated Reactions of Synthetic Polymers copolymers that possess periodic backbone structures undergo reversible. Similar behavior is also observed for smaller oligomers fitted with periodic arrangements of the monomer units. This photoalignment mechanism has not been fully elucidated at present. UV irradiation significantly changes the step of the helix in copolymer samples with planar orientation.

the light exposure induces anisotropic orientation of the polymer main chains and of the cinnamate side groups in the film. undergo both photoisomerization and dimerization. Photoresponsive Polymers 279 most promising ones are polyimides. Thus. Also. dimensional stability. Presumably this particular polymer can multi-photoalign the liquid crystal pattern without a change of the direction of the linearly polarized UV light. adhesion. There are various reports in the literature about preparations of soluble photoreactive polyimides with cinnamate chromophore side groups. and are good insulators. depending on the degree of the photoreaction of the polymers. upon irradiation with linearly polarized ultraviolet light. heat resistance. The irradiated films align homogeneously the nematic liquid crystal molecules along one direction at an angle of 107 o with respect to the polarization. In addition. The liquid crystalline alignment was found to be thermally stable up to 200 o C. The chemical structure of such an aligning polymer is depicted as follows: O CH3 C C CH2 p O(CH2)6O O(CH2) n C O CH CH where n = 2 or 6 . it was reported by Lee et al. They form liquid crystal alignment layers in flat-panel displays and possess good optical transparencies. 84 that they prepared a photoreactive polyimide with cinnamate chromophores side groups : O N O F3C CF3 N O O n O O O O This polyimide is claimed to be thermally stable up to 340 oC and has a glass transition temperature of 181 oC. it was demonstrated that the cinnamate chromophores..5. It was also reported 84 that photoreactivity of side-chain liquidcrystalline polymers can align liquid crystals both in a parallel mode or perpendicularly.

Linearly polarized visible or. and rotational diffusion within the steady state of the photoreaction. That can be controlled by irradiation time. respectively. a series of cis-trans photoisomerization cycles. They noted that the light-induced orientational order generated in the glassy state is significantly amplified by the subsequent annealing of the irradiated films at temperatures within the mesophases of co. This is a process that is reported to takes place via angular dependent excitation. 84 therefore. Gimenez. films of liquid crystalline copoly(methacrylate)s with photochromic azobenzene and benzanilide side groups and related terpolymers (containing additional dye side groups) are oriented by irradiation. A bias-tilt angle between the liquid crystals director and the substrate is also realized by controlling the irradiation angle of the light. alternatively. investigation of the use of azobenzene-containing polymers for liquid crystalline alignment became quite thorough because of the potential application in holographic storage as well as optical and photonic use.280 Light-Associated Reactions of Synthetic Polymers It was concluded. In addition.and terpolymers. an approach to photo aligning liquid crystals by a two step procedure was reported by Stumpe. UV light is used. This procedure results in anisotropic monodomain films of nematic and smectic polymers. By this technique. Another investigation also reported photo and thermal isomerizations of azobenzene based groups that are covalently bound to copolymers of methacrylates 101: . The light-induced ordering of the azobenzene group is connected with cooperative alignment of the nonphotochromic comesogenic and dye side groups even below the glass transition temperature. This results in the photochromic side group becoming oriented perpendicularly to the electric field vector of the incident light and establishing an oblate order in the films. the required dose or the irradiation time is significantly reduced by the optimization of light-induced and thermal processing. and coworkers. Amplification factors up to 30 were found in this series of materials. that the liquid crystals align both parallel and perpendicular to the incident E direction on the photocrosslinked polymer film by changing the degree of the reacted cinnamoyl group. 88-90 The photoalignment of liquid crystalline polymers containing azobenzene groups has an advantage of local variation of the orientation order due to pixel wise irradiation. 92 In this procedure. 84 Another approach to liquid crystalline alignment is based on photoisomerization of azo compounds in polymeric materials or as part of the polymer structure. 85-87 In recent years.

Photoresponsive Polymers X X C C CH2 n CH2 m O C C O OCH3 O (CH2) y O z N N 281 Here. when linearly polarized light with the electric vector parallel to the xz-plane comes along the z-direction. On the other hand. Examination of the three-dimensional alignment behavior by UV and FTIR spectroscopies. One is the uniaxial in-plane orientation of the azobenzene with a dipole moment parallel to the x-axis from the x. This is a photoselection process. 101 It was also reported that photoinduced alignment in cast thin films of liquid crystalline polymers. of 6-[4-(4-ethylphenyl)diazenylphenyloxy]hexyl methacrylate. biaxiality of the azobenzene moieties was induced during the in-plane alignment process. when they were exposed to unpolarized light at 436 nm. followed by out-of-plane orientations of azobenzenes.36). The induced anisotropy is large (an approximate order parameter as 0. 91 Two kinds of orientation modes were observed. and stable (more than 5 months at room temperature). and by polarizing optical microscopy techniques found that the azobenzene moieties become aligned along the propagation direction of the irradiation light through repetition of trans-cis-trans isomerizations. These are possibly extreme cases. kinetic data indicates that when these liquid crystalline polymers are exposed to visible light.93 When the polymer films with cis-azobenzenes were subjected to irradiation with linearly polarized light at 436 nm. 93 : Han et al. reversible.. the azo groups orient themselves from a more or less random arrangement to a perpendicular one. three-dimensional manipulation of the polymer liquid crystals was achieved. also underwent three-dimensional reorientation efficiently together with the azobenzene moieties due to the cooperative motion. 91 also studied exposure of films of liquid crystalline polymers with azobenzene side chains to linearly polarized light of 436 nm that results in successive occurrences of uniaxial in-plane orientations. cyanobiphenyl.to y-direction and the other is out-of-plane . O C CH3 C CH2 n O (CH2)6 O N N C2H5 and poly[4'-[6-(methacryloyloxy)hexyloxy]-4-cyanobiphenyl] were studied.5. A nonphotoactive mesogen.

94 reported that they prepared a liquid crystalline polyester with azobenzene side groups: O CH2 CH CH2 O O C (CH2)11 O C n N CN (CH2)8 N O They studied the effects of irradiation of the films of this polymer with linearly polarized red light after photochemical pretreatment. 91 These orientations can be illustrated as follows: N N N N N N in plane N N out of plane Zebger et al. or UV . gives rise to distinct transformations from in-plane orientation at the early state to successive out-of-plane reorientations.282 Light-Associated Reactions of Synthetic Polymers (homeotropic) one toward the z-direction. Conventional photoorientation processes are usually done with linearly polarized green. blue. In-plane orientation was generated in the glassy state. Marked dependence of photoorientation processes on film temperatures was observed. Photoorientation at higher temperatures.. slightly below the transition temperature between smectic and nematic phases.

The polyester is characterized by smectic and nematic phases and a strong tendency to form J-aggregates. whereas conventional photoorientation leads to a biaxial oblate order. These structures hinder photoalignment of the azobenzene mesogenic groups. or 351 nm). Very high values of dichroism of about 0. Photoresponsive Polymers 283 light of an argon laser (514. It requires a pretreatment by irradiation with ultraviolet light or an exposure to visible light of high power density to produce a certain concentration of the trans-isomer. The found that orientation of 4cyano-4'-alkoxyazobenzene side groups can take place parallel to the electric field vector upon irradiating of the films with linearly polarized red light. The process results in a uniaxial prolate order of the film. This was done by dissolving two chiral dimethacrylate and one chiral diacrylate monomers containing . The orientation process is cooperative.5. therefore..3 were generated as a result of this combination of the photoinduced orientation process and the thermotropic self-organization. the direction of photoinduced orientation and the type of the three-dimensional orientation order can be controlled by the wavelength of the irradiating linearly polarized light. whereas the lightinduced orientation of the photochromic moiety causes an ordering of the alkylene spacers and even of the main-chain segments into the same direction. it is interesting to note that in a diblock copolymer that contains azobenzene groups 94: Br m O O O OCH2(CH2)4CH2O N N OCH3 n O photoinduced birefringence shows microdomain structures. 488. which destroys any initial orientation order and J-aggregates. This can also be done in the same film of a smetic polyester with 4-cyano-4'alkoxyazobenzene side group.8 and birefringence of about 0. 94 It is important. which takes place simultaneously under the irradiation conditions. 93 Also. 94 concluded that the most probable mechanism of this two-step process is the angular-selective transformation of the bulky trans-isomers to the rod like cis-isomeric formed by the red light. characteristic of diblock copolymers. to take into consideration any possible steric hindrance that might occur in the preparation of the polymeric material. Zebger et al. 96 reported that an azobenzene polymer network can also optically align ferroelctric liquid crystals. The aligned cis-azobenzene side groups become strongly J-aggregated. 93 Thus. Zhao and coworkers 95.

while exposing the reaction mixture to linearly polarized irradiation. The monomers were illustrated as follows: O N O O N O N O O O N O O N O N O O methacrylate N O O O N acrylate O O O O The monomers were then thermally polymerized and simultaneously irradiated with linearly polarized light. In addition. Bulk alignment was achieved by polymerizing several divinyl ethers and diepoxide monomers bearing an azobenzene moiety. Two of the monomers were able to induce bulk alignment of the liquid crystals in direction perpendicular to the polarized light. Here too. thermal polymerizations were conducted in solution within the ferroelectric liquid crystals. Monomer #1 was effective in concentrations as low as 1%. Zhao and coworkers 97 reported photoinduced alignment of ferroelectric liquid crystals using azobenzene polymer networks of polyethers and polyepoxides. The monomers can be shown as follows: .284 Light-Associated Reactions of Synthetic Polymers azobenzene groups in a commercial ferroelectric liquid crystal host. It was also concluded from the experimental evidence that the photoinduced bulk alignment of the ferroelectric liquid crystals may take place by a mechanism that is different from one that takes place in achiral azopolymers.

Photoresponsive Polymers 285 O O O O O O O O N N O O N N CN O O O O O O O O N N N O O CN N Polymerization of these monomers was achieved by cationic mechanism. subsequent work. Zhao and coworkers 97concluded. In still another. The monomers were also found capable of inducing and stabilizing bulk alignment of the liquid crystals. Instead. Zhao and coworkers 98 used block copolymers composed of polystyrene and liquid crystalline azobenzenecontaining polymethacrylate copolymers as a model system: . the results suggest to them that the mechanism might be based on formation of an anisotropic azobenzene polyether or polyepoxide network. that the mechanism of action might be different from the one obtained with chiral azobenzene polymethacrylates. however.5.

and (3) severely reduced and even suppressed changes in the aggregation states of azobenzene groups on heating. 99 O Br O (CH2)6 CH3O N N O n/2 O O (CH2)3CH3 m/2 O O 2 It was found that when the solution-cast films are stretched at temperature greater than Tg .286 Light-Associated Reactions of Synthetic Polymers m O O n O O(CH2)6O N N OCH3 to investigate the confinement effects on the photoalignment. The confinement effects are manifested by (1) decreased photoinduced and thermally enhanced orientation of azobenzene mesogenic groups in different aggregation states. deform to result in a long-range orientation of azobenzene mesogens. The common cause of these confinement effects is the restriction imposed by the confining geometry on either an order-disorder or a disorder-order reorganization process involving the motion and rearrangement of azobenzene groups. the azobenzene polymer behaves differently than it does as a homopolymer free from confinement. and thermo-chromic behavior of the azobenzene polymer. 98 Synthesis of liquid crystalline photoactive triblock poly(butyl acrylate) thermoplastic elastomer copolymers with methacrylate-based azobenzenecontaining side-chain was reported. The study showed 98 that when confined in the microphase-separated domains in the diblock copolymers. (2) slower transformation from a liquid crystalline phase to the isotropic state triggered by the trans-cis photoisomerization and slower recovery of the liquid crystalline phase after the thermally induced cis-trans back-isomerization. at the same time. liquid crystalline microdomains can support part of the elastic extension and. which creates a thermoplastic elastomer whose glassy micro- . The liquid crystal orientation is retained in the relaxed film at T < Tg. which is at the origin of the thermo-chromic property. photochemical phase transition.

In-plane reorientation . copper ++. The spacer length and exposure dose significantly influence the reorientation direction. zinc ++. 101 described two different techniques for thermally enhanced photoinduced reorientations of liquid crystalline polymethacrylate films that contain 4-methoxyazobenzene side groups with various alkylene spacer lengths: O H3C C CH2 p C O (CH2) n O N N CH3 One is the classical method based on photoselection and rotational diffusion in the steady state of the cis-trans photoisomerization. Ionomers with zinc and manganese ions showed increased photoinduced birefringence and higher diffraction efficiency of birefringence gratings obtained by excitation with spatially modulated light polarization. ionomers with copper showed the opposite effect.. which includes irradiating with linearly polarized 365 nm light and subsequent annealing in the liquid crystalline temperature range of the film. They found that the metal ions exert a significant effect on the photoinduced orientation of azobenzene mesogens. and manganese++. On the other hand. The reversible trans-cis photoisomerization of the azobenzene chromophore can be used to modulate the mechanically induced orientation. Photoresponsive Polymers 287 domains contain oriented azobenzene mesogens. Also. The copolymers can be illustrated as follows 100: COO Cu 2 Zn 2 Mn 2 C O (CH2)6 O N N CH3 Kawatsuki et al.5. Zhao and coworkers 100 reported recently preparation of liquid crystalline ionomers with azobenzene mesogens and three metal ions.

but out-of-plane reorientation with a small degree of in-plane reorientation is predominant for polymer liquid crystals with long spacers.288 Light-Associated Reactions of Synthetic Polymers perpendicular to the electric vector of the linearly polarized 365 nm light generates polymer liquid crystals with short spacers. The other is an alternative technique based on an axis-selective trans to cis photoisomerization using linearly polarized 633 nm light and thermally enhanced molecular reorientation. After preexposure to ultraviolet light. Regardless of the spacer length. After cross-linking. These are soft liquid crystalline azobenzene containing copolymers of acrylate with methacrylate monomers bearing oligo(ethylene oxide) chains. thin films of the liquid crystalline polymers show highly sensitive photoinduced material transfer to generate the surface relief structures. therefore. This results in a drastic improvement of the shape stability. The copolymers display a smectic liquid crystal phase at room temperature. the trans-to-cis photoisomerization readily proceeds without any modification of the surface morphology and can. 101 Zettsu and Seki reported 102 preparation of a group of azobenzene containing polymers that can be used in photoinduced surface relief formations. a high order of in-plane reorientation parallel to cis of linearly polarized 633 nm light can be accomplished. be applied to the photoswitchable alignment of nematic liquid crystals. The typical exposure dose required for full polymer migration is as low as 50 mJ cm -2 O N O x O O O 1-x nR O 10 N 5 CH3 The inscribed surface relief structures can be rapidly and fully erased either by irradiation with incoherent nonpolarized ultraviolet light or by heating close to the clear point of the soft liquid crystalline polymers. 103 . It is also possible to chemically crosslink the polymers with mixed vapors of hydrogen chloride and formaldehyde after surface relief inscription. maintaining the structure at high temperatures up to 250 °C.

to increase the efficiency of stimulated emission processes. Nevertheless. like poly(vinyl fluoride). Information is recorded and erased by exciting the photonic crystal with ~ 360 nm UV light or ~ 480 nm visible light. depending on the spacings of the colloidal particle array. The arrays subsequently self-assemble due to longrange electrostatic repulsions between particles. The less favorable free energy of mixing of cis-azobenzene cross-linked species causes the hydrogel to shrink and blue-shift the photonic crystal diffraction. poly(vinyl . and to localize light. 106 5. robust semisolid photonic crystal materials were formed by polymerizing a hydrogel network around the self-assembled crystalline colloidal arrays. when irradiated with light. they are fairly good insulators. monodisperse colloidal particles into crystalline colloidal arrays. Original chemical approach to fabricating large face-centered-cubic photonic band gap crystals was based on self-assembly of highly charged. a number of common polymers show measurable increase in conductivity. or nearinfrared light. Photoresponsive Polymers 289 5. Ultraviolet light excitation forms cisazobenzene cross-links while visible excitation forms trans-azobenzene crosslinks. The information recorded is read out by measuring the photonic crystal diffraction wavelength. visible. When polymeric materials. thereby altering the arrays of the photonic crystal plane spacings and diffraction wavelengths. 105 O O S N O N N O N S This new photonic crystal material can be made environmentally responsive so thermal or chemical environmental alterations as a result of a material volume changes. More recently.4. Photoconducting Polymers Unless polymers contain long sequences of double bonds.104 These crystalline colloidal arrays are complex fluids that consist of colloidal particles give Bragg diffraction pattern in ultraviolet. Photonic Crystals There is interest in photonic band gap crystals. 105 It is claimed 106 that these photonic crystals can be useful in novel recordable and erasable memories and/or display devices. due to their potential ability to increase light wave guiding efficiency.3. 103.5. particularly in the dark.

The addition of an equivalent amount of an electron acceptor. This polymer absorbs ultraviolet light in the 360-nm region and forms an exciton that ionizes in the electric field. furthermore. all practical photoconductive charge-transporting polymers used commercially are p-type. This associated electron-positive hole pair can migrate through the solid polymeric material. or poly(N-vinyl carbazole) are exposed to light they develop charged species.4. 107 singlet-triplet interaction. Kang and coworkers 111 also explored steady-state and pulsed photoalso trans-polyphenylacetylene films doped with inorganic and organic electron acceptors.6-dicyano-p-benzoquinone. like 2. To date.7-trinitrofluorenone shifts the absorption of this polymer into the visible region by virtue of formation of charge transfer states. laser printers. suggested that the exiton can visit one thousand monomer units during its lifetime. the photosensitivity can be increased and even extended into the visible region of the spectrum. poly(vinyl alcohol). such as poly(2-vinyl carbazole) or poly(vinyl pyrene) have high photoconductive efficiencies. 109 This is a distance of about 200 Å . n-type (electron-transporting) or bipolar (capable of transporting both holes and electrons). The material becomes conductive at 550-nm. These materials may take up a helical conformation with successive aromatic side chains arranged parallel to each other in a stack. Related polymers are presently utilized in photocopiers. Also. it is believed that the primary mechanism for poly(vinylcarbazole) charge carrier generation is due to excitation of the carbazole rings to the first excited singlet state. Since discovery in 1957 that poly(N-vinyl carbazole) has photoconductive properties. 109 Kepler carried out fluorescence quenching studies and concluded that the migration of the exiton is the most probable energy transfer mechanism of poly(vinyl carbazole).3-dichloro-5. an electron and a positively charged hole. by itself is not a conductive species. 108 singletphoton interaction. Photoconductive polymers can be p-type (hole-transporting). When poly(N-vinyl carbazole) is doped with photosensitizers or compounds that form charge-transfer complexes. The excited state. and electrophotographic printing plates. Upon dissociation of this pair into charged species. 109 He. The species can migrate under an electric field and thus conduct electricity.290 Light-Associated Reactions of Synthetic Polymers acetate). 107 triplet-photon interaction. particularly iodine and 2. there has been increasing interest in the synthesis and study of this and other polymeric materials with similar properties that allow various photonic applications. 109 and two-photon interaction. To achieve this additional energy is required and can be a result of singlet-senglet interaction. They concluded that charge transport occurs by a band like mechanism that is . the electron becomes a conductive state. In such an arrangement the transfer of electrons is facilitated. Poly(vinyl carbazole) and other vinyl derivatives of polynuclear aromatic polymers .

The photoeffect is evaluated in terms of the effective gain. One way that can be accomplished is by excitronsurface interaction. G. 111 Guillet 112 states that photoconductivity is equal to the current density J divided by the applied field strength .1. e is the electric charge. Photoconductivity and mobility of the charge carrying species can be determined from a relationship 112: = d2/Vt where d is the thickness of the film. Photoconductive Polymers Based on Carbazole As stated above. compared with the number of photons absorbed at the same time 112: G = Jp / eI0(1 . 112 = J/ = n e n + pe p where e is the charge on the electron. and A is the area of the sample that is being illuminated.4. Bauser and Klopffer explain this as a result of interaction of singlet excitons with trapped holes. 113 Regensburger published an absorption spectrum. the primary mechanism for charge-carrier generation in poly(vinyl carbazole) appears to be due to the excitation of the carbazole rings to their excited singlet states.T)A where Jp is the photocurrent. the conductivity is believed to be the result of an associated electron-positive hole pair migrating through the solid polymeric material. 5. 115 . This is related to the number of negative-charge carriers (usually electrons) per unit volume. respectively. I0 is the number of incident photons per cm2 s 1. is the number or positive charge carriers (or positive holes) per unit. 112 While the singlet excited state is not a conductive species. It represents the number of generated carriers reaching the external circuit per unit time. and n and p are the mobilities of the negative and positive carriers. fluorescence spectrum and photocurrent spectrum for a 7. V is the applied voltage and t is the carrier drift time. T is the optical trasmittance of the film. and p. Dissociation of the electron pair produces a separate electron and a positive hole in such a way that the electron ends up in the conducting state. 114 The shape of the response of the photoconductor to the wavelength of the light flash is very close to the shape of the absorption spectra. where J is amperture/unit electrode area.6 films of poly(Nvinyl carbazole).5. Photoresponsive Polymers 291 modulated by shallow electron traps in the undoped polymer and by trapping the charge-transfer complex in the doped polymer. 112 This requires acquisition of more energy.

000) was formed by dehalogenating polycondensation of 3.4-dimethylvaleronitrile) to polymerize N-vinyl carbazole in a heterogeneous solution in a mixture of methyl and t-butyl alcohols. The author emphasized that this method provides ultrahigh-molecular-weight polymer and conversions greater than 80%.2-. The higher polymer molecular weight typically enhances film mechanical properties. charge-transfer complexes. and poly[2-(methacroyloxy)ethyl-4. 116 Harhold and Rathe 127 reported that they have prepared poly(9methylcarbazole-3. although transparency decreases at high conversions.9-methylcarbazole with chromiun (II) acetate. using boron trifluoride or ethylalumionum dichloride as the catalysts. 2. 118 Charge transfer complexes also form from poly(vinyl carbazole). The polymer (Mn = 10. In film form. and electroluminescent devices.dipenylvinylene). 117 Photoconductive polymers and copolymers were also synthesized by Haque and coworkers 118 from 2-(9-carbazolyl)-1-propenyl vinyl ether: CH2 N (CH2)2 O CH CH2 The polymers and copolymers form by a cationic polymerization mechanism. that acts as the acceptor 145: . It's dark conductivity increases by doping it with arsenic pentafluoride.7-trinitro-9-oxo-2fluorene-carboxylate].5. CH2 CH n N The optical transparency of poly(vinyl carbazole) films produced by this room temperature process appears to be quite high. this material is useful for photoconductors. This polymer was found to be also highly photoconductive.2'-azobis(2.292 Light-Associated Reactions of Synthetic Polymers Lyoo used a low-temperature initiator.6-diyl-1. 116 The polymer that formed has the Mn molecular weights >3 x 106. that acts as the donor.6-bis( -dichlorobenzyl)10.

Photoresponsive Polymers CH3 CH2 O C C O CH2 CH2 O n O C NO2 NO2 NO2 293 O The required mole ratio of components in the complex is 1:1. They also concluded that phosphorescent states of poly(vinyl carbazole)-dimethylterephthalate are similar.0 molar ratio of trinitrofluorene to carbazole chromophores is higher than in the corresponding trinitrofluorene and ethyltrinitrofluorene doped homopolymer of poly(2-carbazolylethyl acrylate).05 to 1. In 1985 Mitra 55 prepared polymeric triphenylmethane dyes based on condensation polymers such as polyesters and polyurethanes: O O N CH2 CH2 C O C m O O Cl N CH2 CH2 CH2 O CH2 O C C O n C CH3 N CH3 N CH3 CH3 . Quantum efficiency of the hole propagation of the copolymer with the 0. implying a significant charge-transfer character in the former.5. 145 Charge transfer complexation occurs in a similar manner in poly(2carbazolylethyl acrylate) molecularly doped with 2.7-trinitrofluorene.119 Kim and Webber studied delayed emission spectra of poly(vinyl carbazole) that was doped with dimethylterephthalate and pyrene. 120 On the basis of their results they concluded that at room temperature dimethylterephthalate does not completely quench the triplet excitation state of poly (vinyl carbazole).4.

did not turn out to be photoconductive. Polyacetylene derivatives exhibit unique characteristics such as semi conductivity. such as 2-N-carozolylethyl acrylate . 122 CH C CH C n N N CH3 CH3 C CH3 CH3 C CH3 CH3 CH3 CH3 C CH3 CH3 C CH3 CH3 It was found 122 that the current conducted by this polymer during irradiation is 40 to 50 time higher than it is in the dark On the other hand. however. high gas permeability. the electron mobility of the di-t-butylcarbazolepolyacetylene (shown above) is lower than in poly(vinyl carbazole).122 Siloxanes with pendant carbazole groups were synthesized by Strohriegl 73 by the following technique: (CH2)x N CH CH2 CH3 Si O H CH3 Si O (CH2)x +2 N The material. This was attributed to the bulkiness of the butyl groups.294 Light-Associated Reactions of Synthetic Polymers These dyes were then shown to sensitize photoconductivity of poly(N-vinyl carbazole). 121 Attempts were made. helix inversion. and nonlinear optical properties. therefore. Copolyacrylates with pendant donor and acceptor chromophores. to incorporate carbazole into polyacetylene in hope of attaining enhance properties. The photoconductivity of copolymers was also investigated.

The product is soluble in organic solvents. Photoresponsive Polymers 295 73 4.5. Another number of radicals apparently forms during illumination but disappears in the dark. Photoconductivity in the visible is obtained by charge transfer complexation. These copolymers: CH2 CH C CH2 CH C n O m O (CH2)x N (CH2)x O C NO2 NO2 NO2 can be prepared by free-radical copolymerization of the appropriate monomers. The polymer possesses carbazole .5.6-diformyl-carbazole and 4-14-bis(-aminoethyl)aminophenylazo]nitrobenzene yields a new polyazomethine.3-hydroxymethyl carbazolyl acrylate with acryloyl-3'-hyroxypropyl3. 1.5-dinitrobenzoate: n O O O O O NO2 CH3 N NO2 m O Illumination of the copolymer samples induces a certain degree of ionization accompanied by proton transfer. carbazole-azo polymer. 119 It was reported 123 that a polymer formed by condensation of N-(3isopentyl)-3. Similar work was done earlier by Natansohn.7-trinitrofluorenone-2-ethyl acrylate do exhibit photogeneration properties. There is a permanent increase in the quantity of radicals generated by light. 119 who copolymerized Nmethyl.

2. 5. It shows high photoconductivity and nonlinear optical properties. and 9-poly[(butoxycarbonylinethyl urethane)-diacetylenes] that result from changes from rod (red or blue) to coil (yellow) conformations of thepolymer backbone. 125 This was shown by Ryba and Petranek to be a result of the spiran ring opening up 125: CH3 CH3 UV light visible light N R NO2 N R O CH3 CH3 NO2 When the irradiation is interrupted and the membrane is irradiated with visible light. 126 These species undergo rapid back electron transfer. the dialkyl aniline donates one of the unpaired electrons in a typical photoreduction reaction to the carbonyl group. solvatochromic. The reaction is reversible and the photoconduction is by a mechanism of the ion radical returning to the ground state. Photoexcitations of the solutions of these polymers in the rod state result in a large transient . because the ring closes back to the spiran structure. to Kapton polyimide film. In other words. 4-. 125 The addition of electron donors. Photoconductive Polymers that Are Not Based on Carbazole When spiropyran is incorporated into plasticized poly(vinyl chloride) membranes and placed between two identical NaCl solutions and irradiated with ultraviolet light for long periods the potential decreases.4. 6-. Hoofman et al.296 Light-Associated Reactions of Synthetic Polymers moieties and azo type nonlinear optical chromophores in the backbone. O N O N O O O n results in an enhancement of photocurrent by as much as five orders of magnitude. 126 Freulich explains the mechanism of enhancement as a result of radiation absorption by the chargetransfer complex formed between the added electron donor and the imide portion of the polymer backbone. like dialkyl aniline. and photoconductive properties of 3-. Excitations are followed by rapid and complete electron transfer from the donor to pyromelitimide to yield the radical anion of the polymer and the radical cation of the donor ... compared with the virgin material. 127 studied the thermochromic. the potential returns to its original value.

while only very small conductivity signals are observed in the coil state. The zwitterionic merocyanine form of crowned spirobenzopyran moiety brings about a significant change in the metal-ion binding ability. 128 reported that they prepared a soluble rigid-rod organometallic polymer containing electron-donating and electron-withdrawing trans-[-Pt-(tibutylphosphine)2-acetylene-R-acetylene-]n (where R = bithiazolediyl) groups. 129 reported applying organic photochromic compounds to photochemical switching of metal-ion complexation and ionic conduction by combining photochromism with metal-ion binding property of crown ether derivatives. They synthesized vinyl polymers. This polyacetylene is luminescent with a singlet emission peak at 539 nm and photoconducting. The electron-donating and electron-withdrawing properties of the thiazole ring confer solubility to the polymer. The thermochromic shift that occurs in going from the rod state at room temperature to the coil state at 65 °C is accompanied by a decrease in the photoconductivity.5. The large conductivity signal in the rod state is attributed to the formation of mobile charge carriers possibly via interchain charge transfer within aggregates. The -conjugation of the ligands extends into and through the metal core and the absorption peaks show a significant red-shift of 17-26 nm compared to the bithienyl counterparts due to the presence of the electron-withdrawing imine nitrogen atoms. This prompted the authors to apply the compound to photo- . Photoresponsive Polymers 297 photoconductivity. Wong et al. 128 Kimura et al. The polymer was formed by cuprous iodide-catalyzed dehydrohalogenation reaction. of the polymer is 215° and it shows relatively good thermal stability. The glass transition temp. incorporating a crown spirobenzopyran moiety at the side chain: O O 1-x O OCH3 N O N O O NO2 CH3 CH3 The crown spiropyran in the electrically neutral form can bind an alkali metal ion with the crown ether moiety. At the same time the spirobenzopyran portion isomerizes to the corresponding merocyanine form photochemically... The decay of the photoconductivity is nonexponential and extends to microseconds.

They observed that the ion-conductivity was increased by ultraviolet light and decreased by visible light. 129 Chan and coworkers 130 prepared polystyrenes and poly(methyl methacrylate)s that contain metal complex cores: O M O n n H H O M = O OC OC Re CO Cl H O H O 2PF6 or M = N Ru N When the polymers are doped with a hole transporting triphenylamine. The photogeneration efficiency is given as the . This theory assumes that some fraction of absorbed photons produce bound thermalized electron-hole pairs that either recombine or dissociate under the combined effects of the Coulombic attraction and the electric field. 150 Chan and coworkers 130 observed an electric field dependent charge separation process in these polymers. It is described well by the Onsager's theory of charge germinate recombination. This suggests that the metal complexes serve as photosensitizers instead of charge carriers. an enhancement in photoconductivity in the visible region is observed.298 Light-Associated Reactions of Synthetic Polymers responsive ion-conductive materials.

Photoresponsive Polymers 299 product of the quantum yield of thermalized pair formation and the pair dissociation probability: where Ig is a recursive formula given by where I0(x) = 1 .. r0 is the initial thermalization separation between the bound charges. charge transfer or any strong interactions between the conjugated polymer pairs Transient absorption spectra of a blend of thin films in the 420-730 nm region were obtained at various time delays following photoexcitation at 532 nm.132 reported exciplex formation and photoelectron transfer between several n-type {electron accepting) -conjugated rigid-rod polymers and donor triarylamine molecules. Dramatically enhanced photoinduced bleaching in the 430-480 nm region was observed. Jenekhe et al.exp(-x). is the primary yield of thermalized bound pairs.5. Jenekhe and de Paor propose that they observed enhanced photobleaching in the blends and that it is a consequence of photoinduced electron transfer. and E is the applied electric field strength. r is the relative permeability. 132 The electron transfer was illustrated as follows: N S O N N S N O N N n UV light n . In particular they reported an investigation of an n-type conjugated polymer poly(benzimido azobenzophe132 No evidence was observed by them of a ground state nanthroline ladder).

Polyimides like Kapton owe their resistance to degradation at least in part to charge transfer character. Materials like 2-(2-hydroxyphenyl)benzoxazole and 2-(2-hydroxyphenyl)benzothiazole contain intramolecular hydrogen bonds and are known to undergo excited state charge transfer reactions and intramolecular proton transfer upon excitation. concentration quenching.. and polythiophene is expected to create excitons. however. it was concluded that the exciton is a single chain. extent of conjugation. Proton or Electron Transfer in the Excited State In 1966 Conwll and Mizes 131 observed that exposure to light frequency beyond the absorption edge in polymers such as poly(p-phenylene vinylene).5. and competition with excimer formation on intramolecular proton transfer as well as on the electro-luminescent device potential of polymeric materials. They reported. This generated considerable interest in the role of various types of charge transfer complex states in the photostabilization of polyimides The photoinduced electron transfer processes of -conjugated polymers are currently of wide interest in view of their importance to the fundamental understanding of the electronic structure and properties of the materials and applications such as photodiodes. electrophotographic photoreceptors. and molecular electronic devices. 133 explored the effects of molecular size. photovoltaic cells. which contain intramolecular hydrogen bonds are known to undergo excited state(charge transfer) intramolecular proton transfer upon photoexcitation. 5. whose structure: . some of which decay radiactively. Jenckhe at al. such as 2-(2-hydroxyphenyl)benzoxazole and 2-(2hydroxyphenyl)-benzothiazole.300 Light-Associated Reactions of Synthetic Polymers N S S N n + N N N n O O N Molecular materials. that the results of their studies with model compounds and several polymers. Based on the similarity of the emission from thin films and oligomers of poly(p-phenylene vinylene).

Therefore. Photoresponsive Polymers H N O F3C N O N O CF3 N O n H O n O 301 suggest that incorporation of such compounds into the backbones of stiff-chain conjugated polymers does not ensure the occurrence of intamolecular proton transfer upon photoexcitation. 134 have considered a polymeric system with semirigid prototype polyquinoline groups that contains intramolecular H bonds between the enol and imine groups. Chang et al. the different absorbing and emitting species result in a large Stokes shift. etc. To address these limitations.5. In most cases. which reverts to the normal form (N) via reverse proton transfer.. the phenomenon has been studied mainly in the solution systems for small organic molecules like pyridine derivatives. however.. The polymer was illustrated as follows: . 134 noted from the literature that the excited-state intramolecular proton transfer is a form of phototautomerization occurring in the excited states of the molecules possessing cyclic intramolecular or solventbridged hydrogen bonds. the electronic excitation of a normal form (N) in the ground state yields a proton-transferred excited-state tautomer (T*) of the much lower energy. Chang et al. This T* relaxes radiatively or nonradiatively to the metastable ground state T. Since this process is fast enough to accompany the short-lived first excited singlet state. 134 pointed out that until now.. 133 Chang et al. phototautomeric fluorescence is rather weak for practical applications at ambient temperature due to more effective internal conversion or broken hydrogen bond by torsional motion.

Ru(bpy)++.302 Light-Associated Reactions of Synthetic Polymers OCH3 OCH3 O n N O X N Where the substituent X on the polymer is an OH group with an intramolecular H bond. the polymer in solution shows dual blue and red fluorescent bands.6.2'bipyridine)ruthenium(II). Nishijima and coworkers were able to generate hydrogen by visible light irradiation with the aid of ruthenium complexes and colloidal platinum stabilized by viologen bearing polymers in aqueous media. The authors claim that a semiempirical molecular orbital calculation of this emission supports the phenomenon of excited-state intramolecular proton transfer. 124 The polymer was prepared as follows: n polymer with + N Br N C4H9 1% viologen groups CH2N(C2H5)3Cl Hydrogen generation requires a photosensitizer.vinyldeoxy - . In the system. an electron donor. water donates the protons and electrons are supplied by ethylenediamine tetraacetic acid disodium salt. Earlier. 124 The viologen groups transport the electrons to the multi-electron redox catalyst (2. 5. fully reversible method for ligation of deoxyoligonucleotides was reported by Saito and co-authors. an electron mediator and a multi-electron redox catalyst. Reversible -Sheet Transitions A convenient. This yields a polymer with 1% viologen groups. 135 5. To obtain the polymer the reaction mixture must be refluxed in methanol for 20 hours.

5. Photoresponsive Polymers

303

uridine at the 5'-end of the DNA strand and a thymine residue at the 3'-end were used to form a cis-syn [2+2] adduct between the vinyl group and the 2,3-double bond by simple irradiation at 366 nm. This adduct formation is completely reversible by irradiation at 302 nm to restore the original compounds
NH2 N O N N O NH O O N N N NH2 O NH O

The authors demonstrated this coupling principle by simultaneous ligation of several single-stranded deoxyoligonucleotides on a DNA template to produce a longer DNA. The process is then quantitatively reversed to give the original oligonucleotides.

5.7. Polymers that Shed Small Molecules, Ions, or Free-Radicals Upon Irradiation
Into this category of materials belong polymers that shed molecules, ionic species, or free-radicals when irradiated with light of the appropriate wave length. One such material is poly[p-(formyloxy)styrene]. It can be prepared from poly(p-hydroxy styrene). The polymer was reported to decarbonylate smoothly in ultraviolet light 136:

n UV light

n

O O C H OH

The reaction can take place in solid state or in solution. It was reported that the material can be used in photolithographic processes and that it produces sharp images. 136 Such images can be developed positively or negatively. Crivello and coworkers 137 prepared aromatic polyimides bearing sulfide linkages in the main chain by condensing sulfur containing dianhydride with aromatic diamines. They also condensed sulfur containing aromatic diamines with dianhydrides. Phenylation with diphenyliodonium salts converts

304

Light-Associated Reactions of Synthetic Polymers

the diarylsulfide groups into triarylsulfonium salts. The resultant photosensitive polyamides undergo main chain cleavage during photolysis with ultraviolet light. These polymers are offered as positive high temperature photoresists. 137 The decomposition upon UV light illumination can be illustrated as follows:
O N O S O O O N O n

AsF6

UV light O N O O S O N O n

O

+

+ H AsF6

The details of the decomposition mechanism of sulfonium salts upon irradiation with ultra-violet light are described in Chapter 2. The illustration above is a simplified version. Preparations of multifunctional photopolymers with both pendant phenacyl ester and vinyl ether groups were reported. 138 These materials were synthesized by one-pot method for the reaction of poly(methacrylic acid) with 2chloroethyl vinyl ether, This was followed by the reaction with phenacyl bromides using l,8-diazobicyclo-[5.4.6]-undecene-7. It was found that the pendant phenacyl ester groups cleave upon photoirradiation to give pendant carboxylate groups. The produced carboxylate groups react with pendant vinyl ether groups to form acetal linkages. 138

5.8. Color Changes
Two distinct triplet excimetric emissions were observed in the solid films of poly[N-(vinyloxy)-carbonyl)-carbazole].139 Phosphorescence spectra of this polymer and its monomers in solutions are essentially the same as those observed for poly(N-vinylcarbazole). The fluorescene spectrum, however, shows a significant shift to the blue. 139

5. Photoresponsive Polymers

305

Copolymers of vinyl viologens, such as N-vinylbenzyl-N'-alkyl and benzyl and N-( -methacroyloxy)propyl-N'-propyl-4,4'-bipyridinium dihalides and polar aprotic comonomers, such as N- vinyl-2-pyrrolydone or N.N'dimethylacrylamide exhibit a strong color formation upon irradiation. 140 One such copolymer can be illustrated as follows:
CH2 CH CH2 CH N O

CH2 N X

X

N

CH2

where, x - Br, BF4(SO4)1/2. The photocolor developments of these aprotic copolymers in the film state are completely reversible and faster than in corresponding copolymers with protic comonomers, such as acrylamide. A characteristic absorption spectra of the copolymer is attributable to single radical cations. The mechanism of reversible color development was shown to be as follows 140:
light N N O2 viologen ion pair in copolymer (colorless) radical cation-anion pair (highly colored) N N

X

X

Photochromic compounds based on l,2-bis(3-thienyl)-cyclopentene derivatives undergo reversible photocyclizations between their colorless ringopen and colored ring-closed forms when irradiated with light of appropriate wavelengths 141:

The photoreaction of the polymer was illustrated as follows 142: . They also demonstrated erasable fluorescence photoimaging on a spin coated film.2-bis(3thienyl)cyclopentene derivatives using ring-opening metathesis polymerization techniques. The strong fluorescent of the polymer in a neat polymeric film shows that it can be photoswitched through highly efficient bistable photochromisms.306 X X X X Light-Associated Reactions of Synthetic Polymers X X X UV light visible light R S S R R S S R X X X X X where X = F or H This was utilized to form several novel homopolymers with l. 141 The color forming cyclization reaction in the polymers can be illustrated as follow: Ph O n H Ph O n H O N O UV light O N O O O S visible llight O O X X X X X S X S X S X X X X R X R X = H R = Cl colorless colored Lim. An and Park 166 synthesized polymers with similar photochromic groups for use in erasable optical memory and fast optical switching.

The photoresponsive groups can be illustrated as follows: . and coworkers.10.11. 99 Light-associated reversible changes of these polyrotaxanes were observed. 144 reported grafting photoresponsive groups to copolymer films. Photoresponsive Polymers F F F F F F UV light F F 307 F F F F S S R n visible light (>350 nm) S S R n CN R= NC 5. Photoresponsive Shape Changes Landlein. 99 Thus. Langer. 5. 167 The polymer was illustrated as follows 143: O C C H H C O (CH2)9 O H C C H O C O n When this polymer as well as its precursor are blended with poly(vinyl alcohol) and poly(m-phenylene-isophthalamide) and formed into membranes. Photoresponsive Gas Barrier Films By incorporating photolabile groups into the polymeric backbone Eisner and Ritter reported that they were able to form photoresponsive membranes. the permeation of gases through the membranes can be controlled by ultraviolet light irradiation. light irradiation with ultraviolet light or heat causes a rearrangement to a mixture of polyrotaxane together with a catenane. Photoisomerizable Rotaxanes Okada and Herada reported formation of photoresponsive polyethylene glycol rotaxanes with anthracene derivatives stopper groups and cyclodextrin cyclic components. 143 5.5.9.

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This photorefractive effect. This provides important advantages in their applications in the fields of optical data storage and information processing.6 Such polymers must have the ability to convert electrical signals into optical output.3 Under the illumination of nonuniform light formed by the interference of two coherent laser beams. These effects include the generation of second harmonics. Since the phenomenon became understood. Photorefractive materials exhibit unique features. a persistent but reversible change in the refractive index of an electrooptic material is caused by nonuniform illumination. This generation of the second harmonics doubles the frequency of light while the 316 . therefore.9. it was first reported in 1991 that it is possible to form polymers that exhibit the photorefractive effect . 4 6. in photorefractive materials.Chapter 6 Photorefractive Polymers for Nonlinear Optics Photorefractivity is defined 1as a modulation of the index of refraction in an electrooptic material by internal electric fields produced by optical redistribution of charge carriers. a spatially oscillating space-charge field is formed.1. 1 The refractive index of material is subsequently modulated via an electrooptic effect. being carried out to develop polymeric materials that could replace inorganic ones. such as photosensitivity. however. Presently used inorganic materials are hard to process. To be more specific. such materials found application in integrated optical devices.5 As a result. In other words. Photorefractive Materials Photorefractive materials are unique in their ability to generate large changes in the indices of refraction in response to relatively low power light. This field forms from generation and redistribution of photoinduced charges. 2. in order for the molecules to exhibit second-order optical effects. This generates a space-charge field that modulates the refractive index. Extensive research is. reversibility.8. In other words. the absorption of light is followed by diffusion and drift of the free charges. It is based on the combined effects of photoconductivity and electrooptic property. It was first observed as a detrimental “optical damage” in lithium niobate and in other inorganic crystals used for second harmonic generation. they must function electrooptically when changes in applied voltage result in changes in their refractive index. Such changes are produced by optical redistribution of charge carriers. they must be “noncentrosymmetric” or not centrally symmetrical 7. such as LiNbO3 or BaTiO3. and beam amplification.

chromophores have been linked to high-Tg polymers such as polyimides. because many nonlinear optics chromophores cannot survive the high processing temperatures (ca.3 m) greater than 30 pm/V and the aim now is to develop materials with r values of 50 pm / volt or even higher. Photorefractive Polymers for Nonlinear Optics 317 electro-optical effects enable the electric current to control and modulate light. Long-term stability of dipole orientation is a problem associated with this type of materials. very impressive progress has been made to date. such as polymer films. In summary. due to fast relaxation of chromophore orientation. 15 liquid crystals. 16 and organic glasses. Lithium niobate has an r value of 30 pm / volt. This too is a problem. The quantity of change in a material’s refractive index that is altered by alterations in an applied electric field is expressed as the electrooptic coefficient r. to be industrially useful. 18 To be of practical use the developed materials must also exhibit reasonable thermal stability (greater than 95% retention of optical o nonlinearity for 1000 hours at 100 C). 19 This chapter tries to illustrate what has been achieved so far. 17 Device-quality materials must possess: 1) large optical nonlinearity. Unfortunately. high optical damage thresholds. Several polymers are already known that possess coefficients (at 1. Provide nonlinear optical properties or changes in the index of refraction of the material in response to changes in an applied electrical field (Exhibit an electrooptic effect). the electric field can alter the index of refraction and thereby change the light propagating through polymeric materials. To realize a stable dipole alignment. the photorefractive polymers are required to do the following: 1. They should also lend themselves to device fabrication without considerable difficulty and maintain sufficiently large and stable nonlinear optics susceptibilities. 3) low optical loss. the device-quality nonlinear optics polymeric materials must retain high optical quality in thin films. to lock the dipole orientation into rigid matrix after poling. 3. Within a relatively short time. 2. Some of these exhibit large bulk nonlinearity in composite systems. In addition. however. 2) high temporal stability of the dipole orientation. . many polymeric materials were developed that do exhibit the photorefractive effects. 10-14 These materials consist of polymers with charge transport agents and photosensitizing dyes. Although it is very difficult to solve all the problems. The first requirement was addressed by a number of research groups and various high chromophores have been developed. To put this in other words. This in turn modulates the phase of light. Transport the charges through the material. the bulk nonlinearity of composite samples tend to decays rapidly.6. and 4) good processibility. 220-250 oC) and the harsh acidic environment of polyamic acid during imidization. Trap the charges. and exhibit low optical propagation loss. It is also known that the photorefractive effect can also be observed in many organic materials.

a result of the electric field induced alignment of the chromophores. The methods that are used in preparation of the polymeric materials with nonlinear optical properties can be as follows. of the material. the electrons must de-localize in response to applied electric fields. This locks in the asymmetry. therefore. Also. A strong electric field is applied while the polymer is heated at. therefore. There are some essential differences between photorefractive polymers and inorganic crystals. The above equation is called the polarization equation. beyond the (1) namely. It was pointed out 23 that the performance of photorefractive polymer composites is too large to be explained by the simple electrooptic photorefractive effect alone.and third-order optical effects. This is done. The other terms. Respond to light by generating electrons and positively charged vacancies. In the organic materials the quantum efficiency for generation of mobile charge. or preferably below. because the chromophores must be aligned in such a way that the material has no center of symmetry. In this equation the (1) term describes linear optics of such phenomena as light reflection and refraction. While the electric field is still applied. The active molecules become mobile and the dipoles are forced to line up. and (3) assembling nonlinear optics chromophores into LangmuirBrodgett layers.. 8 Also. there must be large differences in the dipole moments between the ground state and the excited states. The statistical center of symmetry in polymers is removed via dipolar alignment by application of an external electric field (called poling). (2) covalent attachment of such chromophores25 to amorphous and liquid-crystalline polymers. or glass transition temperature. the mobility is highly field-dependent. is highly field dependent due to Onsager germinate recombination. This has been widely observed in many molecularly doped polymers. 21 It can vary as log E. The electrooptic response in these materials is. This results in spatial asymmetry. (2) and (3) describe the second. . In order for the materials to exhibit second-order effects. 21 High fields are. generally required for facile charge generation. Tg . as already stated above.. for the second-order effects to be large. . the films are then cooled.318 Light-Associated Reactions of Synthetic Polymers 4. 22 This means that higher fields are required to increase the speed of charge transport. Nonlinear optics effects are generally described by a polarization equation for the optical response (P) of a material to an optical electric field (E)20: P= (1) E + (2) E2 + (3) E3 + . respectively. 24 They include (1) doping or simply dissolving in the polymeric matrix chromophores. A theoretical model was offered 10 where both the birefringence and electrooptic coefficient are periodically modulated by the space-charge field due to the orientational mobility of the nonlinear chromophores at ambient temperatures.

(2) will not increase linearly with chromophore loading N. The function of the conjugate bridge is to allow electronic communication between the donor and the acceptor.31 It was shown. Dalton et al. Due to strong interactions among the electric dipoles. that chromophores tend to have high dipole moments. and Shu33 as: .30. Photorefractive Polymers for Nonlinear Optics 319 which are second order nonlinear. therefore. More precisely. that large molecular nonlinearities can be achieved by using extended polyene bridge systems.6. Examples of the electron donors can be amino or methoxy groups and of the acceptors can be nitro or cyano groups. a bridge. The resultant asymmetric distributions of charges markedly affect the interactions of the chromophores with light. Such interaction favor centro-symmetrical ordering of the chromophores in the polymer matrix. The donor-acceptor charge transfer groups are connected with and separated by a -electron segment (consisting typically of polyene. electrostatic interactions occur. 27. 26 The stability of the poled structures. Thus. This maximum is approximately 15 wt % for dipole moments and decreases at higher chromophore concentrations. As a result. This means that the poled nonlinear optics chromophores that possess large dipole moments will tend to relax back to the randomly oriented state..28 studied the influence of the shape of the chromophore on their dipolar interaction. Marder. Several approaches to diminish the dipolar interactions were investigated. polymers with very high Tg and thermal stability have been used with a fair amount of success. and above a critical loading density.2.32 (where is the dipole moment and is the molecular first hyper-polarizability). or heteroaromatic moieties). the term was defined by Jen. Chromophores for Nonlinear Optics A typical nonlinear optics material consists of an electron-accepting group. To maintain this rigidity. where dendrons effectively decrease the interactions among the chromophores due to steric hindrance.29 6. This has also yielded fruitful results.32 For instance. Applications of external electric fields cause the electric charges in the molecules to separate. To obtain large nonlinearities the quantity of chromophores in the system must also be large. chromophores that are active in nonlinear optics are conjugated molecules that contain electron-donating group on one end and electron accepting groups at the other end. and an electron-donating group. however. azo. but it will show a maximum at relatively low loading levels. The conclusion that was reached was that a spherical shape inhibits dipolar interactions. the poled structures are in a metastable state. Another approach was to use chromophore-functionalized dendrimers. one compound . Another approach is to crosslink the polymeric matrix.907 m and a low absorption maximum of 562 nm in chloroform. The problem is. a derivative of isoxazolone exhibits value of 3156 x 10-48 esu at 1. strongly depends on the rigidity of the overall material.

Some examples of chromophores that were incorporated into side chains and main chains of polymers are donor/acceptor substituted stilbenes and azobenzenes. e is the index of the charge-transfer excited state. 34 On the other hand. the unsubstituted polyene segments of the above mentioned chromophore make that compound thermally.320 Light-Associated Reactions of Synthetic Polymers ( ee - gg)( 2 ge / E 2ge) where g is the index of the ground state. and chemically unstable. and is the dipole matrix element between the two states. 33 Unfortunately.37 Another example are the two compounds shown below: CN N CN CN H2N NO2 In some of the early preparations polymers and copolymers of poly(nvinylcarbazole) were used as the polymeric materials 38: n N The polymers were combined (or doped) with such diverse chromophores as (diethylamino)benzaldehyde diphenylhydrazone: . it was shown that thermal stability of many chromophores can be significantly improved by using aromatic amino functional groups in place of aliphatic amino functional groups as the electron donors. photochemically.36 The same is true when a simple polyene bridge is replaced with a thiophene moiety. 35.

3-fluoro-4-N. It is a plasticized guest-host polymer with a low glass transition temperature. and a sensitizer. This material was sensitized for charge generation with 2. a nonlinear optical chromophore. The carbazole units act as hole-transport agents. 2.N-diethylamino-p-nitrostyrene.4. This enables the holes to move to the dark regions of the grating by diffusion or drift under the influence of an applied external field. 5-dimethyl-4-(p-nitrophenyl) azoanisole. is below room temperature. Because.7-trinitro-9-fluorenone. 41 This material was reported to combine close to 100% diffraction efficiency in a 105 m thick film with sub-second response time and high resolution. If a periodic light-intensity pattern is incident to the material.7-trinitro-9-fluorenone (2% by weight). thus reducing the dielectric strength of the material. 2. the polar dye in the nonpolar matrix tends to crystallize slowly and undergoes space separation separation.6. charges are generated in the bright regions due to the optical excitation of the charge-transfer complexes. one material was prepared from photoconducting poly(N-vinyl carbazole) that was doped with a blue-shifting optically nonlinear chromophore.3. The Tg. 42 . however. the space charge field is produced by inhomogeneous charge distribution that modulates the refractive index through the electro-optic effect.39 A material was reported recently that is claimed to be very efficient.5 dimethyl-4-(p-nitrophenylazo)anisole: CH3 N CH3O N NO2 CH3 For instance. Photorefractive Polymers for Nonlinear Optics 321 H CH3CH2 N CH3CH2 C N N or 2. the index modulation amplitude is enhanced further by birefringence. 40 The material is prepared from a photoconducting poly(9-vinylcarbazole). The sensitizer forms charge-transfer complexes with the carbazole moieties. In most photorefractive materials. a plasticizer. the material has a T below room gtemperature. 9-ethylcarbazole. Unfortunately.

4-(4'-nitropnenyl)azo-1. 43 The sytheses were carried out by a Knoevenagel polycondensation of divinylcarbazoles with bis(cyanoacetate)s using 4-(N. Improvements in values of the order of 3-10.4'vinylbenzyl)-oxy]benzene: R R O O N N NO2 is claimed to exhibit very good phase stability and a nearly complete diffraction at 633 nm. 44 The acceptor groups included thiobarbituric acids. are among those that contain isoxazole and tetracyanoindane acceptors. 42 Also. polymers that contain carbazole moieties in the backbone with two acceptor groups as multifunctional chromophores were synthesized. and a cyanosulfone.3-bis[(3'. relative to the values observed for commonly used stilbenes and azobenzene chromophores were readily realized. The photorefractive optical gain of these polymers was demonstrated to be high.N'-dimethyl)pyridine as a base. In 1996.322 Light-Associated Reactions of Synthetic Polymers Another chromophore. sulfoximines.or . A polymeric material of this type can be illustrated as follows: . cyanovinyls. More than one hundred such chromophores were incorporated into processable polymer lattices and evaluated for stability in the polymers under conditions of corona poling (explained above) and optical illumination (at 1. isoxazolones. 43 Second-order nonlinear optical properties of the polymers were confirmed by second harmonic generation. They appear to exhibit the good stability at condition of corona poling and optical irradiation (in the presence of atmospheric oxygen). This led to a conclusion 44 that promising chromophore-containing polymeric materials that can be poled to yield electrooptic coefficients greater that 30 pm/V.3 m). work that focused upon the exploration of alkyl and aryl amine and ketene dithioacetal donor groups together with a variety of electron acceptor groups was reported. tetracyanoindanes.

6.9 m) CN . Additionally. These nonlinear optics chromophores are intended for incorporation into polyimides.96 dB/cm with no loss attributable to intrinsic absorption of the chromophore. polyureas.45 Among them are some promising chromophores that were reported by Jen and coworkers33. Photorefractive Polymers for Nonlinear Optics NC CN 323 O S O n NC CN Table 6. polyurethanes. gives examples of some nonlinear chromophores.6 m) N CN S CN 6200 (1. photochemically. 46 These were formed by incorporating isophorone moieties into chemical structure. new thermally.47 Table 6. was reported to yield up to 30 pm/V at an optical loss of 0. such as: O O N N Ph The above shown chromophore. Some Examples of Chromophores for Nonlinear Optics a NLO Chromophores N N N NO2 (x 10 -48esu) 800 (1. and chemically stable chromophores were reported recently.1. and polyamides.1.

1.324 Table 6. (Continued) NLO Chromophores Light-Associated Reactions of Synthetic Polymers (x 10 -48esu) NC CN N S 6144(1.9 m) NC CN 580 N NO2 N S CN 3450 CN S N O N S O N 5380 N NO2 a 580 from various literature sources Another recent study reports 46 a preparation of two thermally stable chromophores that have the following structure: .

6. optically nonlinear material was doped with a chargetransporting agent. 49 reported that they developed a series of dendrized chromophores and fluorinated chromophore-containing dendrimers that possess nanostructures and electro-optic activities.2-phenelenediamine. and molecular architecture. was accomplished by reacting bisphenol A diglycidyl ether with 4-nitro-1. shape. Subsequent dramatic improvement in performance was achieved in a similar polymer by using nitroaminostylbene as the charge transport agent48. You and coworkers. for instance. This. It is also possible to have the nonlinear optics groups perform charge-generating or trapping functions.10 N N OH O CH3 O OH CH3 NO2 CH3 The crosslinked. a chromophore. they claim to have achieved dramatically enhanced poling efficiency in these materials. Photorefractive Polymers for Nonlinear Optics H2N NH2 H2N 325 NH2 N N N S CN NO2 CN The trapping sites may be provided by additional doping materials. They incorporated these chromophores that contain fluorinated dendrons onto a hydroxystyrene photoresist polymer to form . (dimethylamino) benzaldehyde diphenylhydrazone. By controlling their size.

um) was demonstrated. The poling-induced polar order decays quite rapidly upon heating due to low glasstransition temperature (Tg) of the polystyrene backbone. do not possess the thermal stability that is needed for practical applications. A large electrooptic coefficient (97 pm/V at 1.326 Light-Associated Reactions of Synthetic Polymers side-chain dendrized nonlinear optics polymers. These materials.3 . 49 synthesized a high-Tg aromatic polyimide with pendant dendronized nonlinear optics chromophore with a cardo-bisphenol linkage to a rigid aromatic polyimide backbone: F3C O N O O N O CF3 n RO OR where R = O R O O O O R O 3 N O CN CN NC O where R = O F F F . You and coworkers. however. To overcome this.

Photorefractive Polymers for Nonlinear Optics 327 The authors claim to have successfully applied the site isolation principle to a rigid 3-F cardo-type polyimide with very high Tg.3. Since the NLO chromophore is labile in many reaction conditions. the high Tg approach required high poling temperatures.50 describe the synthesis of several new photorefractive polymers. An optical gain coefficient of 158 cm ^ at a field of 50 V/^m and a diffraction efficiency of 68% at a field of 46 V/^m for polymer PI were obtained.1. 6.3 m) More than 90% of this value is claimed to be retained at 85 oC for more than 650 hours. which are composed of a new type of nonlinear optical chromophore attached to conjugated polymer.3. The resulting polymers exhibit high PR performances. which are among the best values for fully functionalized PR polymers to date. Other approaches to preserve chromophore alignment in poled polymers involve restricting freedom of movement of the chromophores by various crosslinking schemes as well as by using liquid crystalline materials. This.. At the same time high poling efficiency is also claimed to yield very large electrooptic coefficient (71pm/V at 1. One concept is to synthesize polymeric materials with high Tg . Many nonlinear optics chromophores just cannot survive the high processing temperatures (ca. 220-250 oC) or the harsh acidic environment of polyamic acid (in preparation of polyimides) during imidization. 6. 51 Also. as stated earlier.50 Polymer lattice hardening under mild conditions is much desired for processing chromophores into useful device-quality materials. In trying to overcome the draw-back various approaches were tried. such as aromatic polyimides and polyamides. A slow decay of the optical nonlinearity results. the Stille coupling reaction was used to prepare these polymers.51 o . however. is very difficult to do permanently. Crosslinked Polymeric Materials The crosslinking process in some systems must be carried out at 200 C. Polymeric Materials for Nonlinear Optics Poling. These temperatures are extremely demanding for organic molecules. poly(p-phenylene-thiophene). like 225 to 250 oC and for integrated optic applications. is applied to lock in asymmetry. particularly for chromophores with extended conjugation. poling temperatures above 350 oC might be necessary due to the high temperatures that are required during the fabrication of the devices. Marder et al. With time and subsequent heating the orientations of the polymers tend to become disordered.6.

3. 52 suggested that a new poling process is required to increase rotational freedom of nonlinear optics chromophores..2.328 Light-Associated Reactions of Synthetic Polymers 6. The process can be illustrated as follows 52 : O N O O + O N 6. to achieve and maintain polar order in the resulting poled material. Polyurethanes are. consequently are less stable at higher temperature. Beecher et al. Polymers Crosslinked by the Diels-Alder Reaction Dolton et al.3. reported that they carried out photocrosslinking of polyurethane polymers with the aid of free-radical photoinitiators. 53 By placing trans-stilbene groups in the chromophore moieties. 52 pointed out that typical crosslinking processes to achieve stability possess additional deficiencies. Moreover. Dolton et al. These are entanglements of the polymers during the lattice-hardening process that significantly increase the difficulty in aligning dipolar chromophores. This polymer is illustrated as follows 53 : . Ideally. It consists of preparing linear polymers first with pendant protected dienophile groups. To overcome this nonlinearitystability trade off. Polyurethanes Formation of urethane crosslinking linkage from terminal hydroxy groups and isocyanates occurs at relatively low temperatures and essentially neutral conditions. Many tried to overcome this by forming crosslinked three dimensional structure.1. 52 This is claimed to provide significant advantages over the conventional nonlinear optics thermosets. the photocrosslinking steps are restricted to the methacryloyl double bonds. therefore. These groups become unprotected under mild conditions and subsequently undergo Diels Alter addition reactions with other polymer molecules containing pendant diene groups..1.1. The result is lower electrooptic activity of these poled thermoset materials. the reaction for subsequent crosslinking should be triggered only by very mild conditions. 250 oC). and proceed without concurrent trans-cis isomerization of the stilbene. this process should be prior to and separate from any crosslinking process. suitable for the above described purposes and received some attention. preferably without further temperature elevation. By taking into account all these requirements a lattice-hardening approach based on a Diels-Alder [4 + 2] cycloaddition reaction was developed. Linear polyurethanes with covalently attached chromophores have lower Tg (ca. 130 oC) than polymers like polyimides (ca. and.

6. Photorefractive Polymers for Nonlinear Optics O N H O (CH2)2 O N O SO2 photoinitiator (CH2)3 O N N UV light (CH2)2 NH 329 crosslinked structure For this reaction an organometallic photoinitiator was used that absorbs at 532 nm. Addition of phenol is necessary to prevent thermal crosslinking. The following scheme was developed for forming polyurethane thermosets 54 : S HOCH2CH2 N HOCH2CH2 NC CN O NCO + OCH2CH2OH CH3 NCO O H N CH3 CN O S N O C OCH2CH2O CN O CH3 C N H O C O H N CH3 . Photocrosslinking of the oriented polymer can be used to produce a patterned material that exhibits a stable second-order nonlinear optics signal that lasts for several weeks at 100 oC .

These bonds prevent relaxation of oriented molecular dipoles. 55 Following preparation procedure was used: CH3 HOCH2CH2 N NCO polyurethane CH2CH2OH NCO B 4 C4H9 The polymer. .8 x 10-7 to 5.0 x 10-7 esu. 55 In a different approach. The Tg = 121 oC. depending upon poling conditions. This high second-order activity is attributed to the strong electrons accepting nature of the pyridinium groups. This is an indication of an enhanced charge separation and greater nonlinearity. This is believed to be due to the hydrogen bridges that form between neighboring polyurethane chains.330 Light-Associated Reactions of Synthetic Polymers Based on the absorption spectrum of the above material there is a strong chargetransfer (CT) band at 626. a polyurethane was formed from a terpolymer of methyl methacrylate that was functionalized with pendant hydroxy groups 51: and then reacted with a diisocyanate. The alignment of the nonlinear chromophore moieties induced by electric poling exhibits temporal stability. The (2) of this polyurethane was reported to be in the range of 1. with an Mn = 12000. One can compare the above with another polyurethane preparation where a structure with a hemicyanine dye is attached as a pendant group. is soluble in dimethylformamide and can be processed into optical quality films by spin casting.6 nm.

. 51 described preparation of new trifunctionalized DisperseRed type chromophore. The films are then heated to higher temperature for crosslinking and “hardening” the lattices and locking in the dipole alignment. polyurethane.6. This system is claimed to offers some prominent advantages in terms of simpler material processing.N(dihydroxyethyl)aminobenzene-ethenyl-3. wider processing window and higher temporal stability of dipole alignment 51.3 pm/V. in common organic solvents. Photorefractive Polymers for Nonlinear Optics 331 x O OCH3 O y OO O z HOCH2CH2 N(CH2CH2OH)2 O N N O S O The technology involves combining the acrylic polymer with the diisocyanate and then spin casting the material into films that are electrically poled at Tg to align the chromophores. 56 Dalton et al. The products exhibit electrooptic coefficients as high as 20 pm per volt and maintain their optical nonlinearity for several thousand hours at high temperature. to be 40. The d33 coefficient of the dielectric polarized films was reported. Disperse-Red Triol compound by reaction of this chromophore with diisocyanate at 80 o C. It resulted in formation of soluble oligomers that were spin cast to form high optical quality films. . 56 This was carried out on (trans)-7-[4-N.06 m) of 14. A synthesis and characterization of an active styrylthiophene monomer and formation of polyurethane with second-order optical nonlinearity was reported by Wang et al.5-dinitrothiophene to form the corresponding prepolymer. Concurrent corona poling and thermosetting of these films resulted in polyurethane networks with electrooptic coefficients (r33 at 1. The prepolymer and polyurethane are claimed to exhibit good thermal stability and good solubility..5 pm/V and good dynamic thermal stability.

somewhat different preparation of a polyurethane was also reported by Dalton et al.332 HO Light-Associated Reactions of Synthetic Polymers OCN O N O HO CH3O NO2 NCO OCH3 OCH3 NH O O O O NH R= N N OCH3 NO2 Another. 51 It is shown as follows: .

1.3. The . Epoxy Crosslinked Polymers Thermal epoxy crosslinking.6. These polymers were studied at different temperatures below the glass transition by the decay of the nonlinear optical susceptibilities of corona-poled films. This was shown on orientational relaxation of the nonlinear optics chromophores of polyamides with the following structure 57: N N CON H NO2 NCO H (CH2) x CON H NO2 OCN H (CH2x ) n where x = 4. three-dimensional network of covalent bonds that restrict the freedom of chromophore motion.10.6. Photorefractive Polymers for Nonlinear Optics HO N CH3 NCO O OH HN O N O O NH 333 N N NCO N N OH NO2 NO2 O O NH 6. using relatively rigid reagents at optimized stoichiometry substantially enhances the orientational stability of the aligned chromophore substituents by forming ether linkages between polymeric chains and reestablishing hydroxy groups for hydrogen bonding. This produces a dense.12. thereby enhancing temporal stability characteristics.8.3.

and a charge transporting agent. which was obtained via an 11step synthesis. with doped systems in that they tend to undergo phase separation. Polyimides and Polyamides It was shown that the thermal stability of conventionally formed polyimide polymers and copolymers (bearing nonlinear optical chromophores) is adequate for numerous device applications. This polyimide retains its nonlinear optical properties even after . Following is a description of some these materials. 6. in the range of organic single crystals). is the small nonlinear optical response (r33) values for many such polyimides.T)/T as the relevant scaling parameter. Below the second order transition temperature there is not enough energy in the system to enable whole segments of the polymeric chains to move. Polymeric Materials with High Second Order Transition Temperature Generally. multifunctional polymers were synthesized that contain all the necessary components. pyromellitic dianhydride. 6. To try and make doping unnecessary. There is a problems. a substituted porphyrin (charge generator). Crosslinked Polyesters Trollsas and coworkers 58 prepared a crosslinked polyester by in situ photocrosslinking of the ferroelectric monomer. one approach is to synthesize polymeric materials with a high Tg .1. This limits the amount of the nonlinear optics chromophore that can be incorporated into the system. above Tg . 58 6. as stated earlier. thermoplastic polymers undergo cooperative localized motions. which means the material may be suitable for use in electro-optic devices.334 Light-Associated Reactions of Synthetic Polymers time dependence of the decay was shown to be well represented by the Kohlrausch-Williams-Watts stretched exponential function: d(t) = d0 exp[-(t/ ) ] The temperature dependence of the decay correlates with the glass transition temperature. The resulting polymer has a large electro-optical coefficient (1535 pm/V.2. 4-amino-4’-nitrostilbene derivative (the nonlinear optics molecule). Tg.1. One photorefractive polyimide 59 was formed by linking thee units. using normalized relaxation law with (Tg . One limitation of this technology.3. however.3.3. In the attempt to lock in asymmetry.4.2. however. This is not true of all of them.

9 n O O NO2 C6H13 C6H13 O B= O N M N N O C6H13 N N N 0. Photorefractive Polymers for Nonlinear Optics 335 heating at 170 oC for extended periods. The function of the conjugating unit is to transfer electrons. they also incorporated a very active acceptor. The considerations was that if these materials are poled at the glassy temperatures (>250 oC). Jen. The optical gain coefficient is approximately 22 cm -1 in zero field. and Rao was to incorporate into typical nonlinear optics materials 60 electron-rich five-membered heteroaromatic groups. like thiophene as part of an all conjugation between the donor and acceptor substituents. then at operating temperatures of 80 to 120 oC the . The absorption coefficient.6. It works in the absence of an external electric field. The polymer consists of two sections A B : O O A= N N N N 0. In addition. a tricyanovinyl group into the thiophene-based moiety 60: N CN CN S 60 CN Drost and coworkers also chose materials for nonlinear optics applications with high Tg. however. is much higher.1 n O C6H13 The approach by Drost.

and the alignment would be preserved.83 m) with the electro-optical signal showing almost no change when the polymer is heated to 90 oC for greater than 1000 hours 60.336 Light-Associated Reactions of Synthetic Polymers dipoles of the chromophores would not randomize. Polyimides with diamino chromophores were prepared with the aid of the Misunobi reaction 61: H H2N N NH2 N N O O O O N N n O O O O O O X X where. 62 The materials for these investigations were . Long term stability was observed at 170 .180 oC. was reported to have an r33 of 16 pm/V (at 0. SO2CH3. one that contains 32 mol% of nonlinear optics chromophore. X = NO2. The optical loss and refractive indices of fluorinated polyimides and copolyimides were investigated. An example of such a polyimide can be represented as follows 60: O O N O N O N R n O CN NC CN O O O where R = O The above polyimide.

4-dicarboxyphenyl)hexafluoro-propane dianhydride.2'-bis(3. pyromellitic dianhydride. aromatic polyimides was developed Chen.2’-bis(trifluoromethyl)-4.4’-diaminobiphenyl.6. and 2. Following synthesis was used in the preparation of the polymers 63 O O N N HO OH O O N O A CH3 O O N n O CH3 O N O N A . et al. generally applicable synthetic approach for polymers with nonlinear optics side-chains. Photorefractive Polymers for Nonlinear Optics 337 prepared from 2. They can be illustrated as follows: F3C C N O CF3 CF3 O O N n O F3C CF3 O N O N n O F3C O A two step.

and the chromophore loading level in these polyimides was controlled efficiently from 0 to 50% by weight. aromatic polyimides with different polymer backbones and different chromophores were synthesized. hydroxy polyimide was reported. These polyimides were reported to have high glass transition temperatures (Tg > 220 oC) and are claimed to be thermally stable.63 m) and long term stability (>500 h at 100 oC) of the dipole alignment were observed.338 Light-Associated Reactions of Synthetic Polymers NC NC CN CN A= CN . They can be illustrated as follows : . O One-pot preparation of a preimidized. N N NO2 . Using this technique. Large electrooptic (E-O) coefficient (r33) value (11 pm/V measured at 0. This avoids the harsh imidization process and the necessity of preparing the chromophore-containing diamine monomers.83 m and 34 pm/V at 0.64 It is followed by a covalent bonding of a chromophore onto the backbone of the polyimide via a mild postMisunobi reaction. Earlier this group also reported preparation of another polyimide by the same technique 64 : F3C N O O N S S N CF3 N O n O O CN CN The advantage of this one-pot preparation method is that the chromophores are attached to the polymer backbone at the last stage using a very mild condensation reaction between the hydroxy substituted polyimide and a hydroxy-substituted chromophore. Burland and coworkers 65 synthesized somewhat different types of polyimides. The method also allows a wide variety of polyimide backbones.

In still another report in the literature.2-hydroxy) phenoxyaniline and 2. Photorefractive Polymers for Nonlinear Optics O O 339 CF3 CF3 N N N O O N O2N N n In this compound the electron donor is the diarylamino group and the acceptor is the nitro group. The resulting polyimides bearing hydroxy groups were found to react easily with the terminal hydroxy group of the chromophore via the Mitsunobi reaction. 67 . Yu and coworkers66 prepared a similar polyimide that bears phenylene diamine and a diazobenzene-type nonlinear optical chromophore: O N O F3C CF3 N O O N O2N N N N N O x n This high glass transition temperature polymer exhibits large electrooptic coefficients. (Tg > 185°C).35 pm /V. excellent solubilities and process abilities even though the extent of chromophore grafting is up to 95 mol %. It was claimed that the resulting polyimides possess high glass transition temps.6.4'(hexafluoroisopropylidene)diphthalic anhydride with 4-(4-amino. They are connected by an azobenzene bridge. r33 ~ 14 .2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. the syntheses and characterizations of two aromatic polyimides with nonlinear optical chromophore side chains were reported through a two-step synthetic route103 These two polymers were prepared by polycondensation of 4. The second harmonic measurements indicate long-term stability of the dipole orientation (> 800h at 100 oC) . In the above polymer the chromophore is present in every repeat unit and accounts for more that 50 % of the polymer’s weight. respectively.

has a glasstransition temperature (Tg) of 170 °C and its electro-optical response is 33 pm/V. The third-order optical nonlinearity of this polymer is dependent on the chain length and the molecular structure.642 x 10 -13 esu and response time of 24 ps. of the samples orientation are as high as 240° and 224° respectively.5-bis(tributyltin)thiophene to give the polymer 69: F3C N O R C2H5 where R = COO (CH2)2 N S O CF3 N n O R O O S O N N O The polymer. It is claimed that this product of microwave radiation polymerization compares favorably with a product of conventional thermal polymerization. This highly functionalized monomer was subjected to a Pd-catalyzed coupling reaction with 2. . 69 Polycondensation and imidization of m. The half-decay temperatures.m'-diaminobenzophenone and pyromellitic dianhydride under microwave radiation was also carried out. Simultaneous polymerization and poling was carried in situ. 70 The product polyimide was obtained in a two-step process. because it exhibits third-order nonlinear optical coefficient of 1. The relaxation starts rapidly over 195°. Zhu and coworkers 68 reported preparing of two high Tg (250° and 258°) polyimides embedded with triphenyl imidazole chromophores. shown above is soluble in organic solvents. The second harmonic generation measurements technology yielded moderate d33 values of 15 pm/V and 16 pm/V. They preformed the imide structure with an aryl dihalide monomer and incorporated highly efficient chromophore groups before polymerization. The signals of these poled polymer films were reported to be without any decay at < 150°. Yu and coworkers 69 describe a technique to retain stability and maximize the electrooptic response.340 Light-Associated Reactions of Synthetic Polymers Also.

6. Photorefractive Polymers for Nonlinear Optics 6.3.2.2. Polycarbonates

341

Polycarbonates are also high melting rigid polymers. They were, therefore, also looked at for potential use in nonlinear optics. To achieve high molecular weights, some attempts were made to prepare them via ring opening polymerization. This, however, led to intractable materials. 66 The cyclic structure can be shown as follows:
NO2

N

O

O O O

O m O n O

A copolymer, was, therefore, formed in the investigations 66:

NO2

N

O

O O O m O O n

342

Light-Associated Reactions of Synthetic Polymers

The above shown copolymer, after poling, had an electrooptic coefficient of 55 pm per volt at about 1.3 m. The chromophore, not attached covalently to the polymer, in this case is based on a heterocyclic acceptor that contains two electron withdrawing groups, dicyanomethilidine and sulfone. The donor is a din-butylamino moiety. This chromophore can be illustrated as follows.

(CH3CH2CH2CH2)2N 2 O S O

CN CN

This chromophore was dispersed in a polycarbonate matrix and the composite film poled at 80 oC. The thermal stability of this material, however, does not exceed 150 oC. 6.3.2.3. Highly Aromatic Polyquinolines Chen et al. 71 prepared polyquinolines with both aliphatic and aromatic in-chain structures to provide sites far the side-chain nonlinear optics chromophores. The aromatic ones are also be high melting, rigid molecules. They can be illustrated as follow:

O N O CN NC N CN O n N

6. Photorefractive Polymers for Nonlinear Optics

343

N

O

N O N (CH2) m

n

CN NC CN

These polymers were processed into optical-quality thin films for potential device fabrication. The authors claim good solubility for several of these materials in common organic solvents with molecular weights as high as 41,000. These materials are reported to be especially advantageous for use in nonlinear optics applications due to combination of film forming ability, good thermal stability, and high glass transition temperature. It is also claimed that when chromophore dipoles are aligned by contact or corona poling, useful levels of second order nonlinearity are induced that appear stable at temperatures necessary for the fabrication of optical devices. 71 6.3.2.4. Polynaphthalenes Polymers containing binaphthalene units can adopt a helical configuration. Due to the twisted configuration of the binaphthalene moiety, the polymers that form through rigid groups with triphenylamine derivatives are helices. It is the rigidity of the system that gives rise to rigid, rod like, helical structures. All bonds that form the helix have the same configuration (either S or R). As a consequence, if both R and S monomers are incorporated in the same backbone, no helical configuration can be formed. The rigidity of the backbone can greatly diminish unwanted dipolar interactions between the chromophores, allowing a very high chromophore density.72 In addition, when the polymers are chiral, they can increase the nonlinear optical response. 72 Samyn et al.,72 reported preparation of chiral chromophorefunctionalized polybinaphthalenes for nonlinear optics. These polymers were

The chromophores were attached to the binaphthalene units via alkyl spacers: OR OC6H12 RO S a H12 C6O S b n where R is . In this way. more clearly. The polymers were prepared by direct polymerization. The reaction conditions allow use of a great variety of chromophores with different structures. The same group reported 72 preparation of eight other chiral. in the nonlinear optical properties. The authors report that the typical tree-like macromolecular architecture of these molecules gives rise to a unique behavior in the glass transition temperature as well as in nonlinear optical properties. linear increase as a function of chromophore concentration. The typical tree-like macromolecular architecture of the polymers is reflected in the behavior of the glass transition temperature and. The nonlinear optical response shows a continuous increase in function depending on the chromophore content. using Stille coupling between a bis(trimethyltin) compound and dibromo-substituted binaphthalene monomers. This group of polymers can be illustrated as follows 72: .72 By attaching chromophores as side chains to the rigid non bendable backbone a treelike structure with flexible branches forms. They reported that use of diiodo-functionalized instead of dibromo-functionalized chromophores results in a significant increase of molecular weight. using Stille coupling reaction between a chiral bis(trimethyltin) binaphthalene derivative and diiodofunctionalized chromophores. the nonlinear optical properties can be increased in a way that is not possible with other chromophore-functionalized polymer materials. The nonlinear optical response shows a continuous. chromophore-functionalized donor-embedded polybinaphthalenes.344 Light-Associated Reactions of Synthetic Polymers formed by direct polymerization. O N x S O N O x is hexyl. indicating that the dipolar interactions between the chromophores are eliminated.

3%. Photorefractive Polymers for Nonlinear Optics 345 O OC6H13 H13 C6O N OC6H13 OC6H13 N A where A ca be: NC CN O S O S O N . starts with preparation of two fluorinated poly(arylene ether)s. Both of the two polymers are thermally stable and readily soluble in common organic solvents. O N N O 6. 73 The polymers were formed by Knoevenagel condensation reactions between perfluorophenyl-containing poly(arylene ether) and cyano acetylated chromophores. The glass .2. respectively.5. containing perfluorophenyl moieties in the main chains and second-order nonlinear optical chromophores in the side chains.3. and their weight percentages were both 42.6. Fluorinated Poly(arylene ethers) Another approach. The molar percentages of the pendant chromophores were estimated to be 162% (1) and 138% (2) for the two polymers. .

respectively. in section B only one R group is substituted and the other one is an aldehyde. 73 The polymer consists of three sections.groups. F section A F F F O CH2 R O x F F F F R where R = NC COO N N N NO2 the second copolymer is very similar. In section A both R groups are substituted. The in-situ second harmonic generation measurement revealed the resonant nonlinear optics coefficient (dss) values of 60 (1)and 31 (2) pm/V for the poled films. If rigid moieties are . and many have very low Tg-s. Actually it is the opposite.346 Light-Associated Reactions of Synthetic Polymers transition temperatures (Tg's) of the two polymers were determined to be 186 (1) and 192 °C (2). except that the R groups are: CN OOC F N N N F F F F 6. Polysiloxanes The polysiloxanes are not noted for high grass transition temperatures. respectively. while in section C both R groups are aldehyde.4.

The Red 17 structure. 4-(aminoN. These materials are formed by reactions of an organic polyfunctional alkoxy silane derived from Red 17 dye with tetramethoxysilane in the sol-gel formation. the selective reflection band characteristic of cholesteric mesophases shifts to lower wavelength: NO2 CH3 CH3 CH3 N R O NO2 N R spyropyran CH3 Si O O CH3 Si O CH3 Si (CH2)2 N O NO2 CH3 O "merocyanine" blue CH3 CH3 The photochromic reaction leading to the blue merocyanine formation results in a narrowing of the reflection bandwidth. 74 At higher compositions they are amorphous. they can maintain an orderly arrangement. however. With increased spiropyran content. Photorefractive Polymers for Nonlinear Optics 347 introduced into the polymeric structures.N-diethanol)-2-methyl-4'-nitroazobenzene was reacted with 3(isocyanatopropyl)-triethoxysilane via urethane linkages to introduce the alkoxysilyl reacting groups: . Sanchez and coworkers 74 obtained very high second order nonlinear optical properties from materials derived from sol-gels and based on organicinorganic hybrid structures. As such. It was reported that siloxanes containing up to 20 % spiropyran groups are liquid crystalline.6. they can form liquid crystals.

which were subsequently aged 3 days.52 pm/V at 1064 nm of Nd:YAG laser. Transparent coatings were then spin coated onto glass substrates and dried to prepare films for optical property measurements. The twodimensional structure self-assembles when UV light generates polydiacetylene comb polymers.4. The monolayers of this amphiphilic polymer were then repeatedly deposited onto hydrophobic substrates during every upstroke cycle of the vertical dipping method to form Z-type monolayers. The maximum diffraction efficiency ( max) of 71% was obtained at the electric field of 70 V/ m.7-trinitro-9-fluorenone was used as a photoconducting medium and l-[4-(2-nitrovinyl)phenylpiperidine was added as an optically nonlinear chromophore. asymmetric polydiacetylene can be used to form stable monolayers at the air-water interface of a Langmuir trough. carrying the nonlinear optics chromophore. 78 that a diacetylene monomer with a rigid backbone and capable of forming hydrogen bonds was polymerized in such a way as to form two-dimensional super-molecular assembly. was co-hydrolyzed with tetramethoxysilane in a tetrahydrofuran and water medium acidified with HCI to form sols. The material forms blue solid thin films which generate third-order nonlinear optical signals and exhibit photochemical stability to 1064 nm radiation from a . formation of photorefractive silicone composite with good performance was reported.77 demonstrated that a soluble.5.348 Light-Associated Reactions of Synthetic Polymers (H5C2O)3SiCH2CH2CH2 O2N N N N CH2CH2OCONH H3C (H5C2O)3SiCH2CH2CH2 CH2CH2OCONH This structure. 75 On the other hand. The second order nonlinear coefficient (d 33) was estimated to be 1. 76 A carbazole-substituted polysiloxane that was sensitized by 2. and hydrogen bonds are established within molecular layers. it was reported recently. The second harmonic generation increases in these films with the number of layers. It was claimed that thermally precuring the samples considerably improves their nonlinear optics response and thermal stability. Polyacetylenes Cheong and coworkers. and there are indications of a high degree of orientation anisotropy of the backbone. Chromophore orientation of these films by the standard corona poling technique resulted in second harmonic generation responses as high as 150 pm/V. The photorefractive property of polymer was determined by diffraction efficiency using a 100 m-thick film. In addition. 76 6.

It was observed. Thin films of the polymers exhibit good optical quality. 79 synthesized of a soluble polymer from diacetylene with push-pull azobenzene and pyrimidine rings attached. The two-dimensional structure is still maintained. first in THF and then as a solid state condensation. that the results do not conform in a consistent manner to both the theory of third-order effects and to a previously suggested connection between intramolecular conjugation and optical absorption of polydiacetylenes. Polymers with Carbazole Structures in the Backbone Zhang and coworkers 80 prepared carbazole group containing polymers by the Knoevenagle reaction.06 X 10-30 esu. The explanation that was offered is that possibly intermolecular interactions in these highly ordered structures play a role in defining optical properties. .6. The resulting polydiacetylene with push-pull azobenzene chromophores as side chain and a pyrimidine ring covalently bonded to the diacetylene conjugated system was found to have nonlinear refractive index of 1. 6. They can be obtained from their chloroform solutions by spin-coating.01 X 10 -11 esu and y is 1. After electric poling. X(3) is 1. The polymer was formed from an asymmetric polydiacetylene having a pyrimidine ring and an azobenzene chromophore directly linked to the two ends of a diacetylene moiety. The macro and microscopic susceptibilities X(3 ) and y for the functionalized polydiacetylene.18 x 10 -11 esu. This is reversible. Third-harmonic generation signals retain much of their original intensity through the thermochromic transitions. Heating the polymer to 62 oC changes the color to bright red. The reaction was carried out in two stages. 77 This thermochromic process is accompanied by endothermic and exothermic signatures detected by differential scanning calorimetry. 78 The acetylene groups containing monomer was illustrated as follows: O O O O O OH Wang et al. This yielded high molecular weight polymers. The material was polymerized thermally or under light illumination. Photorefractive Polymers for Nonlinear Optics 349 Q-switched Nd:YAG laser. however.6.

showing the ferroelectric C* phase at concentrations up to 60% by weight of B . and are appropriately substituted to afford a system where the DR1 unit is essentially forced by the two liquid crystal cores to orient normal to the liquid crystal director. The ferroelectric liquid crystal mixtures show a good linear relationship between the maximum observed ferroelectric polarization and concentration of B.350 Light-Associated Reactions of Synthetic Polymers the films are reported to show reasonable second-order nonlinear optical responses 80: H O H O (CH2)6 CN CN N C7H15 n O 6. Furthermore. however. They reported instead preparation. Polarized light spectroscopy showed that the DR1 unit makes an angle of about 60" with the liquid crystal director. the second-order nonlinear optical susceptibility (x(2)) of the ferroelectric liquid crystals are usually low and their thermal stability is limited. provided adequate second order susceptibility X(2) can be obtained. the dopants were only soluble up to about 30% by weight in a standard ferroelectric liquid crystal host. Walba et al. Unfortunately. very interesting approaches to utilization of liquid crystals. While this strategy did indeed afford the desired supermolecular stereochemistry. Furthermore. Both materials possess a broad monotropic smectic A* phase. it was not clear whether the side-by-side dimer structure was compatible with smectic mesogenicity. Combined with their excellent processibility on silicon integrated circuits. compound B is shown to mix in all proportions with a standard C phase host. Several. showing a narrow enantiotropic A* phase. While crystallization from this phase occurs eventually. both structures can be kept in the A* phase at room temperature for days. structures A and B. these liquid crystals provide an attractive potential approach to synthesis of materials for second order nonlinear optics. and most . in good agreement with the expected super-molecular structure. Liquid Crystal Polymers Chiral smectic ferroelectric liquid crystals are liquids that possess spontaneous polar order. were carried out. The polyunsaturated analog B possesses improved mesogenicity. structure and properties of two similar side-by side dimers that possess good smectic liquid crystallinity. 81 tried to create a "side-by-side" type dimer structure where two conventional liquid crystal core structures that are covalently connected by an azo link.7.

81 is based on two monomers. R is decyl in A and 9. The nonlinear optics-chromophores aligned in the direction of the polarization. where only one is nonlinear optics-active81. 81The possibility to modify the monomer system are strongly limited due to the demands of ferroelectricity and possibility to crosslinking.12-octadecadienyl in B.4 pm/V). The thermal and mechanical stability of nonlinear optics materials were improved 82 when a polymer was synthesized with ferroelectric liquid crystalline side-chain and then further improved by Keller et al 83 when they formed a ferroelectric liquid crystalline main-chain polymer. This ferroelectric mixture can then be aligned and photocrosslinked into a pyroelectric polymer. 81 The new chiral monomer displays a large spontaneous polarization (175 nC/cm 2) . promising one single monomer system was recently developed. However.3 pm/V in the chiral smectic C (SC*) phase. Walba et al. perpendicular to the long axis of the molecules were later successfully varied.6 0.81 The molecular structure of this polymer was later modified in order to increase the nonlinear optics activity. The acrylate monomer mixture displayed a ferroelectric SC* phase which could be photocrosslinked into a pyroelectric polymer. demonstrating that compound B "fits the C* binding site" in the desired manner. 81 This can be illustrated as follows: NO2 O O OR O O O OR N O where.6. shown below. developed by Walba et al. The idea was therefore to synthesize a crosslinkable monomer or a crosslinkable monomer mixture that possesses a chiral smectic C (SC*) mesomorphism over a wide temperature range. The system.81 synthesized a low molar mass ferroelectric liquid crystal specially designed for second-order nonlinear optics that showed a second harmonic coefficient (d22) of 0. The thermal and mechanical stability and the long-term properties of nonlinear optics-materials are known to be improved by crosslinking. Photorefractive Polymers for Nonlinear Optics 351 importantly the expected sign of the polarization.. The crosslinked material displays a clear second harmonic signal (d-coefficient = 0.

A cyano-biphenyl-based chromophore was selected as an nonlinear optics mesogenic moiety and an oligomethylene space was used to decouple the chromophores from the main chain and to enhance the possiblity of self organization into anisotropic mesophase 92: n N (CH2)n O CN O O These polymers were also reported to demonstrate good second-order nonlinear optical properties. The choice of maleimide was based on its high dipole moment at right angle to the backbone and its cyclic structure imparting great stiffness to the chains. You et al. Kajzar and coworkers 1 reported forming side chain liquid crystalline polymers with high Tg containing maleimide units along the backbone. C16 H33 C16 H33 C16 H33 S C16 H33 C12 H24 N R n C16 H33 N R S C12 H24 x C16 H33 S y . yielding a high Tg. A Stille coupling reaction was used to prepare these materials. And the photocrosslinked pyroelectric polymer shows a considerably enhanced second-order nonlinear optical activity. 49 describes the synthesis and physical study of several new photorefractive polymers that consist of a nonlinear optical chromophore attached to conjugated poly(p-phenylene-thiophene)s backbones.352 Light-Associated Reactions of Synthetic Polymers in the chiral smectic C phase. The modifications of the molecular structure was possible through the use of the enantioselective biocatalyst Candida antarctica lipase B.

49 Barmatov and coworkers 84 took an approach of forming photooptically active polymers by using hydrogen bonding between functionalized liquid crystalline copolymers and low-molecular-mass dopants. none separating mixtures. Photorefractive Polymers for Nonlinear Optics CN NC where: R = O C4H9 C4H9 CN 353 The resulting polymers exhibit high photorefractive performances. Induction of a nematic mesophase is observed in the case of a smectic polymer matrix doped with low molecular weight photochromic dyes. 6. The photochromic dopants used by them contain azobenzene components: x O (CH2)4 O O O (CH2)4 O O y O N O N N O N O N N N R COOH C N The formation of hydrogen bonds between the carboxylic acid groups of the functionalized liquid crystal copolymers and the pyridine portion of the dopants leads to stable.8. An optical gain coefficient of 158 cm -1 at a field of 50 V/ m and a diffraction efficiency of 68% at a field of 46 V/ m for polymer were obtained. Acrylic Polymers Syntheses and characterization of three fully functionalized photorefractive polymethacrylates containing different chromophores were reported85 Carbazole and nonlinear optics-functionalized methacrylate .6. In mixtures containing up to 30 % of the dopants no separation was observed.

It decreases with decreasing alkyl chain spacer because of restriction of the thermal conformational change by the polymer backbone. 47. The resultant acrylic monomers were then copolymerized with methyl methacrylate and butyl acrylate to yield photorefractive acylic copolymers that can be illustrated as follows 87: m O O O O n N X NO2 These polymers are very soluble in organic solvents. The molecules contain 4-12 carbon alkyl chain spacers between the polymer backbone and the pendant sallicylidene aniline units. when doped with 1 wt % 2. The rate of thermal decay reactions depended on the alkyl chain length of sallicylidene aniline units. of 48. and 52° C. 86 reported synthesis and photochromic behavior of methyl methacrylate copolymers that contain anil groups..7-trinitro-9-fluorenylidene)malononitrile. and the rate was five to seven times slower than those of monomers blended in with poly(methyl methacrylate). The photochromic behavior was investigated in the solid state. The color thermal decay reactions increased with increasing temperature.354 Light-Associated Reactions of Synthetic Polymers monomers in a 1:1 ratio were polymerized with 20 mol % of dodecyl methacrylate to obtain photorefractive polymers. These groups are pendant 4(methacryloyloxyalkyl)-N-(4-methoxysalicylidene)-aniline units. These polymers. The glass transition temperature. respectively. The resulting polymers had glass transition temps. 85 Hirai et al. They fabricate into optically clear polymer films. showed good photorefractive properties. is 150 °C for . A net two-beam coupling gain and a diffraction efficiency of 60% were observed. Chromophores with indole and nitrobenzene push pull groups were reacted with methacroyl chloride and acryloyl chloride. Photochromism was observed at 445 nm in five copolymer films under UV irradiation. The difference in the thermal decay reaction is small when the carbon number of the alkyl spacers was greater than 10.08 mol azo groups.4. and contains more than 0. at 58 V/ m.

by nucleophilic substitution reaction. Some mesomorphic structural order was exhibited by a polymer with 33 mol % chromophoric units. Polymers containing 6-17 mol % pf chromophore segments yielded amorphous and optically clear thin films.(N-methyl-N-hydroxyethylamino)phenylazo]-phenyl-6nitrobenzoxazole chromophores were reported. Then a postazo coupling of p-ethylsulfonylbenzenediazonium fluoroborate or p-octylsulfonylbenzenediazonium fluoroborate was carried out with the aniline or indole ring.. Large nonlinear optical coefficients (d33 as high as 49 pm/V) and photoconductive sensitivity (on the order of 10-9 S-cm -1/W-cm -1) were observed for both copolymers. 89 reported a new post functional approach to preparation of second-order nonlinear optical polyphosphazenes containing a sulfonyl-based chromophores. The polymers exhibit good solubility in common organic solvents and are thermally stable. by second harmonic generation measurements. Values ranging from 40 to 60 pm/V were measured with increasing chromophore molar contents. respectively.88 Methacrylate polymers containing different molar contents of these nonlinear optical active molecular segments were synthesized. Photorefractive Polymers for Nonlinear Optics 355 the methyl methacrylate copolymer and 8 °C for the butyl acrylate copolymer. The poled films of both exhibit a resonant d33 value of 27 and 18 pm/V. This yielded sulfonyl-based chromophorefunctionalized polyphosphazenes. one containing aniline and the other containing indole groups as side chains were obtained from poly(dichlorophosphazene). Two polyphosphazenes.6. The sulfonyl groups act as acceptors. The syntheses and nonlinear optical properties of methacrylate polymers based on 2-[4. while at about 393 nm in the other one. Polyphosphazenes Qin et al.88 6. These polyphosphazenes can be illustrated as follows 90: P O N m P O N n P N o OC2H5 (CH2)2 (CH2)2 N N N SO2C2H5 .9. The maximum absorption in one appeared at about 440 nm.

The nonlinear optics materials have T g . al.10. 91 found that molecules containing two 2.356 Light-Associated Reactions of Synthetic Polymers P O (CH2)2 N N n P N m O P N o OC2H5 SO2C2H5 N N N (CH2)2 6.6-diacetamido-4-pyridone groups and a nonlinear optical chromophore will self-assemble with diimides or bis(uracil) structures. O CF3 NH O N C6H13 CF3 C6H13 NH O HN NH O R O NH N N (CH2)2 N N NO2 NH O R 2 The "lock" and "key" structure in these super-molecular assemblies is provided by three hydrogen bonds per repeat unit. to yield polymer-like hydrogen-bonded assemblies. Miscellaneous Materials Yu et.

The cut-off wavelength ( co) of these polymers is shorter than the visible region. et al. Kimura. On the other hand. is 2. Twieg and coworkers. which opens to give tetracyanobutadiene derivative: C6H13 NC NC n CN CN . 93 reported preparation of poly(norbornene) copolymers functionalized with nonlinear optical chromophore side groups. Photorefractive Polymers for Nonlinear Optics 357 values in the 72-100 °C range and are stable up to 120 °C. The copolymer can be illustrated as follows: m C6H13 94 nO NO2 O (CH2)2 N Katz et al. catalyst in the polymerization of norbornene. The second-order nonlinear optical coefficient. A copolymer of hexylnorbornene and a norbornenefunctionalized Disperse Red I chromophore was scaled up and studied in detail. Use was made of ( 6-toluene)Ni(C6F5)2. Presumably.2-9. utilized tetracyanoethylene to form polymers with tetracyanoderivatives that are donor-acceptor molecules in a long -conjugated system.V -1. co ca. i. this reaction is initiated by charge transfer followed by closure via a 1. Initial studies indicate that electric field poling is effective but that relaxation of polar order in the poly(norbornene) is faster than in a comparable methacrylate copolymer. This [2+2] cycloaddition is followed by electrocyclic ringopening to give tetracyanobutadiene. 92 synthesized polymers bearing oligo-aromatic esters as side chains to form second-order nonlinear optical active polymers on the basis of architecture..6. These polymer films exhibit good transparency in the visible region. at which point the hydrogen bonds break and the structure is lost. 55 Tetracyanoethylene was reacted quantitatively with electron-rich acetylenic polymers to form polymeric materials containing repeating nonlinear optics chromophores. d33.4-dipolar intermediate to a cyclobutene.e.8 pm. nitriles and amines other than trisubstituted amines strongly inhibit the reaction. which are much shorter than the typical second order nonlinear optics polymer containing chromophores like azobenzene. 330-370 nm. The nickel complex used to polymerize the norbornene monomers is tolerant to many functional groups found in nonlinear optical chromophores.

Liphardt et al. tetrahydrofuran. Also. The materials are a mixture of the electrooptic polymer based on bisphenol A and 4. etc. .358 Light-Associated Reactions of Synthetic Polymers NC C6H13 CN n NC CN The polymer is a film former and forms by this reaction in virtually quantitative yields.4’-nitroaminostilbene with 29 % by weight of benzaldehyde diphenylhydrazone. it produces the necessary bulk linear electrooptic response. 95 describe photorefractive polymers with performance competitive with available crystals. The transport agent transfers the charge generated at the dye molecules to other parts of the material. toluene. like acetone. The films can be cast from common organic solvents. a hole transporting agent: OH O N O n A C2H5 H N C N N +C H NO2 2 5 The stilbene dye substituent plays two roles in these polymers: It is a source of charges and. when aligned in a static electric field.

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