Polymer Bulletin 20, 549-556 (1988) Polymer Bulletin

9 Springer-Verlag 1988

Infrared-spectroscopic investigations of molecular order

in liquid crystalline side chain polymers
K.-R, Buerkle 1, W.F.X. Frank 2'*, and B. Stoll 1
1Abteilung Angewandte Physik, Universit~t UIm, Oberer Eselsberg, D-7900 UIm,
Federal Republic of Germany
2Forschungsinstitut der DBP, Am Kavalleriesand3, D-6100 Darmstadt,
Federal Republic of Germany

Summary
Infrared dichroism was used to determine the order parameters of
liquid crystalline side chain polymers. By this the order parameters
of the main chain, of the spacer and of the mesogenic group can be
obtained separately. Therefore spectra of two liquid crystalline
polyaCrylates were recorded with polarized light at different tempe-
ratures. In a poly(acrylate) with 6 CH= groups in the spacer a high
order parameter was found not only for the mesogenic group, but also
for the spacer and the main chain. The orientation of the
poly(acrylate) with a spacer of only 2 CH2 groups is lower due to the
stronger interaction of main chain and mesogenic group.

I. Introduction
Liquid crystalline side chain polymers became more and more in-
teresting during the last years. They show an electro-optical beha-
viour like low molecular weight liquid crystals, combined with
freezing of the molecular motion at the glass transition. Therefore
they are discussed for use in future optical display or storage devi-
ces (1,2).
Macromolecules of this class of substances contain three molecular
units: The mesogenic group, the spacer and the main chain . The meso-
genic group is usually formed by two para-substituted benzene rings;
it can be considered as a rigid rod. The spacer is typically an
alkane chain containing 2 - ii CH2-groups (3,4). Via the spacer, the
mesogenic groups are linked to the main chain. The main chain be an
organic polymer molecule or a SiO chain molecule. In Ic polymers two
substances are chemically linked which have a principally different
phase behaviour. The mesogenic group together with the aliphatic
spacer normally undergoes a liquid crystalline mesophase. This
partially ordered state is present in a temperature range between the
crystalline state and the isotropic phase (melt). The main chain can
be considered as a usual polymer: if there is no crystallisation it
shows only a glass transition. There is no long range order evident
in non crystalline polymers, except when they are oriented by exter-
nal strain. The composed system shows liquid crystalline ordering,
and, at the clearing point Te, a phase transition where it becomes
isotropic. To lower temperatures it passes a glass transition, where
the liquid crystalline order freezes (2).

*To whomoffprintrequestsshouldbe sent

550

Because of the interaction between the main chain and the mesogenic
group via the flexible spacer, an ordering of the main chain below Tc
is possible. On the other hand the ordering of the mesogenic groups
can be influenced by the main chain. While the ordering of the meso-
genic groups is known to be comparable with that of low moleculer
weight liquid crystals, only little is known about the main chain and
the spacer. Former measurements by NMR and IR-dichroism show that the
orientation of these parts of the Ic polymer is very low (3,4~. For
these experiments the liquid crystalline polymers have been oriented
by a magnetic field or mechanical strain, respectively.
This paper reports on studies of molecular order of two liquid
crystalline side chain polymers. Here, the orientation of the molecu-
les is provided by surface effects (see chapt.2). IR spectra showing
characteristic dichroism for several absorption bands are recorded as
a function of temperature.
Order parameters of different parts of the molecules are calculated
from the linear dichroism of characteristic absorption bands. Using
this method no labeling of the molecules is necessary like in NMR.

2. Samples and Preparation

Two polyacrylates and a low molecular weight liquid crystal with a
chemical structure similar to the side groups of the polymers were
studied. The chemical structures of the polymers are the same except
the length of the spacer (see fig.l). The polymers where synthesized
by R. Zentel at the University of Mainz (5). The three substances
show a liquid crystalline mesophase of the nematic type. The
transition temperatures and molecular weights are listed in table i.
According to (5) the abreviations P/H/6/CN, P/H/2/CN and L/7/CN are
used to identify the samples. P and L stand for the polymer and for
the Low molecular weight liquid crystal, respectively; H means the
hydrogen atom at the main chain next to the mesogenic group, the
figure gives the length of the aliphatic side chain and CN denotes
the cyano end group.
In order to measure the IR-dichroism it is necessary to prepare a
thin film of the samples with a well known direction of orientation.
Therefore two KBr-plates where coated with a thin polyimide film and
then rubbed by a rotating wheel of foamed polystyrene. Between these
plates the polymers, heated to the isotropic state, where pressed to
a film of about 10~m in thickness. Annealing this film at a tempera-
ture only a few degrees below the clearing point leeds to a sample
which is homogenous oriented with the mesogenic groups directed
parallel to the direction of rubbing (6). This method is well known
for the orientation of low molecular weight liquid crystals. By this
process the latter are aligned in a relatively short time, whereas
the polymers need many hours of annealing to form a homogenous film
(7).

Table I: Sample M, phase transitions

P/H/6/CN 20000 g 33~ n 133~ i

P/H/2/CN 18000 g 75~ n ll0~ i
L/7/CN 321 k 45~ n 55~ i

CH=
I
c,-coo-(c,.).-o @ coo @ CN
x
Fig. I:
Chemical structure
of the samples
,-cc,.). ~ coo ~ c,
 551

3. D i c h r o i s m a n d O r i e n t a t i o n
M a c r o s c o p i c o r i e n t a t i o n of a s a m p l e leads to d i f f e r e n t a b s o r p t i o n of
IR r a d i a t i o n d e p e n d i n g on the s t a t e of p o l a r i s a t i o n . A transition
m o m e n t a b s o r b s o n l y the e l e c t r i c f i e l d c o m p o n e n t of the i n c i d e n t
r a d i a t i o n w h i c h is p a r a l l e l to its own d i r e c t i o n . In the m i d i n f r a r e d
region, the t r a n s i t i o n m o m e n t is c a u s e d by a molecular vibration,
which, in m a n y cases, is l o c a l i z e d w i t h i n few c h e m i c a l bonds. Thus,
by m e a s u r i n g the d i c h r o i s m of the d i f f e r e n t absorption bands at
special wavelengths i n f o r m a t i o n on the o r d e r i n g of s p e c i a l groups,
e.g. m e s o g e n i c group, s p a c e r and m a i n c h a i n can be o b t a i n e d . Here we
d e s c r i b e how the o r d e r p a r a m e t e r is c a l c u l a t e d f r o m the m e a s u r e d
dichroism.
In the n e m a t i c p h a s e the r o d - l i k e m e s o g e n i c g r o u p s are o r i e n t e d in
one m a i n d i r e c t i o n . There is no p o s i t i o n a l long range order. In
u n i a x i a l l y o r d e r e d systems, the s t a t e of o r d e r is e x p r e s s e d in t e r m s
of the o r d e r p a r a m e t e r :

S = (3<cos20>-I)/2 (i)

8 is the a n g l e b e t w e e n the m o l e c u l a r a x i s of an i n d i v i d u a l m o l e c u l e
and the d i r e c t o r ~ w h i c h is p a r a l l e l to the o p t i c a l axis. T h e n e m a t i c
o r d e r is c o m p l e t e l y d e s c r i b e d by the d i s t r i b u t i o n of 8. S is the
s e c o n d m o m e n t of the L e g e n d r e e x p a n s i o n of this d i s t r i b u t i o n . Di-
c h r o i s m and b i r e f r i n g e n c e m e a s u r e m e n t s give o n l y a v a l u e of S and no
f u r t h e r i n f o r m a t i o n a b o u t the d i s t r i b u t i o n f u n c t i o n .
T h e d i c h r o i s m is m e a s u r e d in t e r m s of the d i c h r o i t i c r a t i o R, i.e.
the r a t i o of the a b s o r b a n c e of r a d i a t i o n w i t h the e l e c t r i c l f i e l d
parallel (A)I) and p e r p e n d i c u l a r (A~) to the o p t i c a l axis, w h i c h is
g i v e n by the d i r e c t i o n of rubbing:

R = AlilA~ (2)

T h i s r a t i o and the order parameter are related by the well known

f o r m u l a (8):

I R - 1
S= (3)
(3cos26-i)/2 R + 2

6 is the a n g l e b e t w e e n the m o l e c u l a r a x i s and the t r a n s i t i o n m o m e n t .

B e c a u s e 6 is not known, in m a n y cases, an o p t i c a l o r d e r p a r a m e t e r is
d e f i n e d w h i c h d e p e n d s o n l y on the m e a s u r e d a b s o r p t i o n values:

R - 1
SopT - (4)
R + 2

In o r d e r to r e g i s t r a t e the d i c h r o i s m of an a b s o r p t i o n b a n d as a
f u n c t i o n of t e m p e r a t u r e it is r e c o m m e n d e d to r e l a t e the m e a s u r e d
v a l u e All or A~, r e s p e c t i v e l y , to the a b s o r p t i o n of u n p o l a r i z e d light,
Ax.o, at the same w a v e l e n g t h . I n t r o d u c i n g

NI) = AjI/AI.o , N~ = A~/Az.o (5a,b)

the o p t i c a l order parameters a r e then c a l c u l a t e d (9) by :

So~T = 1 - N ~ and Sop~ = (NIl+I)/2, (6,7)

respectively.
The i n f l u e n c e of the i n t e r n a l f i e l d is t a k e n into a c c o u n t by a p p l y i n g
an e x p r e s s i o n g i v e n by V u k s (10). This leads to a c o r r e c t i o n f a c t o r
552

for the d i c h r o i t i c r a t i o in eq.6, so that ( n ~ / n z . o ) N ~ m u s t be used

i n s t e a d of N ~ (12).
If the o r d e r p a r a m e t e r is known, the r e f r a c t i v e index can be c a l c u -
l a t e d by:
n~ = n z . o - 1/3 {S ~ n ( T = 0 K ) } (8)

An(T=UK) is the d i f f e r e n c e of the r e f r a c t i v e i n d i c e s n.-n_~ e x t r a -

p o l a t e d to 0 K. This leads to a c o r r e c t i o n of the o r d e r p a r a m e t e r :

1 An(T=0K) -i
So~ = (i - N~) [ 1 N~ I 191
3Sa nz=o

with S6 = (3cos~6 - 1)/2 (i0)

4. E x p e r i m e n t a l
M I R s p e c t r a of the t h r e e s u b s t a n c e s at d i f f e r e n t t e m p e r a t u r e s in the
n e m a t i c and the i s o t r o p i c p h a s e w e r e r e c o r d e d w i t h a P e r k i n - E l m e r PE-
283 s p e c t r o m e t e r . The IR b e a m was p o l a r i z e d by a w i r e grid on an AgCl
s u b s t r a t e ( P e r k i n - E l m e r ) . W i t h the slit p r o g r a m u s e d the r e s o l u t i o n
was b e t t e r than 2 c m -x in the e x a m i n e d w a v e n u m b e r range.
A d d i t i o n a l l y the c h a n g e of t r a n s m i s s i o n w i t h t e m p e r a t u r e was m e a s u r e d
at a f i x e d w a v e n u m b e r . W i t h this m e t h o d the t e m p e r a t u r e d e p e n d a n c e of
the Cs s t e t c h i n g a b s o r p t i o n and its d i c h r o i s m was r e g i s t r a t e d con-
tinuously. These measurements m u s t be c a r r i e d out w i t h v e r y low
h e a t i n g rates (0.i - 0.5 K/min) to k e e p the samples, e s p e c i a l l y the
polymers, in e q u i l i b r i u m . T h e s a m p l e s w e r e h e a t e d w i t h t e m p e r a t u r e
c o n t r o l l e d s i l i c o n oil, f l o w i n g t h r o u g h two ring c h a n n e l s a r o u n d the
KBr plates. A P t - 1 0 0 - r e s i s t was p l a c e d in a hole in one of the KBr
p l a t e s to m e a s u r e the t e m p e r a t u r e of the sample.

5. Results and discussion

As e x p e c t e d , the s p e c t r a r e c o r d e d f r o m the s a m p l e s in the n e m a t i c
p h a s e show a s t r o n g d i c h r o i s m (fig.2). It d e c r e a s e s w i t h t e m p e r a t u r e
a n d f i n a l l y d r o p s to zero at the t r a n s i t i o n t e m p e r a t u r e nematic-
i s o t r o p i c . D e p e n d i n g on the a n g l e 6 b e t w e e n the m o l e c u l a r axis of the
mesogenic group and the t r a n s i t i o n moment, some b a n d s are m o r e
i n t e n s e w h e n the e l e c t r i c f i e l d is p a r a l l e l to the o p t i c a l axis of
the sample, some o t h e r b a n d s show the o p p o s i t e b e h a v i o u r .
In the f i g . 3 - 5 t h r e e w a v e n u m b e r r e g i o n s a r e s h o w n as e x a m p l e s for an-
i s o t r o p i c a b s o r p t i o n of the s u b s t a n c e s u n d e r study. T h e s e s p e c t r a

P/H/6/CN

Fig. 2: T e m p e r a t u r e d e p e n d a n c e of the s p e c t r a of P/H/6/CN

W a v e n u m b e r range 2350 cm -x - 400 cm-i
T e m p e r a t u r e r a n g e 50~ - 135~
 553

Table 2: Band assignments

Wavenumber Vibration 6

2235 cm -x C~N-stretching e 0o
1420 cm -x CH2-bending
1410 cm -~ CH~-bending
1020 c m -x C-C-stretching
880 cm -~ #-H-bending (AT) ~ 90 ~
690 c m -x # - H - b e n d i n g (BI) ~ 90 ~
540 c m -~ C~N-bending ~ 90 ~

w e r e r e c o r d e d at a c e r t a i n t e m p e r a t u r e w i t h i n the n e m a t i c r a n g e to
h a v e a h i g h d e g r e e of o r d e r . In t a b l e 2 t h e a s s i g n m e n t s of a f e w
b a n d s a r e given, w h i c h a r e s e l e c t e d for f u r t h e r c o n s i d e r a t i o n s . Bands
that appear in the s p e c t r a of t h e p o l y m e r s b u t not in the m o n o m e r
L/7/CN w h e r e a s s i g n e d to v i b r a t i o n s of the s p a c e r or t h o s e of the
m a i n chain. T h e a s s i g n m e n t to the s p a c e r m u s t be t a k e n into a c c o u n t
b e c a u s e of the o x y g e n a t o m s at b o t h s i d e s of t h e spacer. T h i s p o s s i -
b l y leads to a f r e q u e n c y s h i f t of the CH2 v i b r a t i o n s c o m p a r e d w i t h
L / 7 / C N . T h e b a n d s a s s i g n e d to the s p a c e r a n d t h e m a i n c h a i n can a l s o
be o b s e r v e d in the s p e c t r u m of p o l y ( b u t y l a c r y l a t e ) (II) w h i c h r e p r e -
s e n t s t h e p o l y m e r i c s a m p l e s w i t h o u t the m e s o g e n i c groups.
The optical order parameters SopT of the b a n d s a s s i g n e d in t a b l e 2
are shown in fig.6 and 7. They were calculated from the band
i n t e n s i t i e s u s i n g eq.4. T h e o r d e r p a r a m e t e r s e v a l u a t e d by t h i s m e t h o d
a r e c a l c u l a t e d f r o m the t r a n s m i s s i o n p e a k i n t e n s i t i e s a n d a r e w i t h i n
an e r r o r r a n g e of 10 50 %. T h i s is c a u s e d by the u n c e r t a i n i t y of
t h e b a s e lines d u e to b a n d o v e r l a p p i n g . T h e r e f o r e no i n t e r n a l f i e l d
correction is n e c e s s a r y . To get the m o l e c u l a r o r d e r p a r a m e t e r s f r o m
S o ~ T t h e v a l u e s of t h e a n g l e 6 in e q . 3 m u s t be known.
As an e x a m p l e we look at two v i b r a t i o n s of t h e m e s o g e n i c group: the
CN-stretching vibration at 2235 c m -x w i t h 6 ~ 0 ~ , a n d the o u t - o f -
plane bending vibration of the h y d r o g e n a t o m s of the b e n z e n e ring
(880 c m -x, 6 = 90~ The calculated values SopT a r e d e p i c t e d in

ITICN

Alt~ Aj.A.
PIHI21CN

All

i i i
1480 1440 1400 1360 1320 1040 1020 1000 900 B00 700 600 500
. ~i r - ~ I cm -1 ~/r -1

Fig 3-5: Three wavenumber s e c t i o n s of the s p e c t r a recorded

at a t e m p e r a t u r e of the n e m a t i c r a n g e
554

1.5

A 2236 cm "1
SOPT [] 1420 cm -1
0 1410 cm -1
9 1020 cm -1

1.0
I. 1010 cm -1 P/H/6/CN
9 880 cm -1
9 ~390 cm -I
r 640 cm -I

0.5

!
0.0
0 o
Fig 6:
Optical order 0 9
parameters cal-
culated from
several absorp- -0.5 1 I I ... I I

tion bands of 320 340, 360 380 400

P/H/6/CN ," T/K

1.5

2235 c m -1
SOPT [] 1420 c m -1
0 1410 c m -1

T
9 1020 c m -1

1.0
I. 1010 crn-* PIHI21CN
9 880 cm -I
9 690 c m -1
O 640 r -1

0.5

O O
O O O
0.0

Fig 7:
Optical order
parameters cal-
S~e~
culated from
several absorp- -0.5 I .... i i i I
tion bands of 320 340 360 380 400
P/H/2/CN
T/K
fig.6. Taking into account the corresponding values for 6 leads to
identical values for S describing the orientation of the whole meso-
genic group. The temperature behaviour of So~T in fig.6 agrees with
that of low molecular weight liquid crystals like L/7/CN.
 555

F i g . 6 s h o w s that the b a n d s a s s i g n e d to v i b r a t i o n s of the s p a c e r or

t h o s e of the m a i n c h a i n of P / H / 6 / C N show the same b e h a v i o u r as one of
the two b a n d s m e n t i o n e d above. If a n g l e s of ~ ~ 0 ~ for the b a n d s w i t h
p o s i t i v o p t i c a l o r d e r p a r a m e t e r s are a s s u m e d , a n d 6 ~ 90 ~ for the
o t h e r s , it can be seen that the o r d e r p a r a m e t e r s of the spacer, the
m a i n c h a i n and the m e s o g e n i c g r o u p are the same. O t h e r a n g l e s w o u l d
lead to o r d e r p a r a m e t e r s that are h i g h e r or n e g a t i v e and are t h e r e -
fore not p o s s i b l e .
In P / H / 2 / C N the 1420 m -I band leads to very small v a l u e s of SopT
(fig.7). O b v i o u s l y p a r t s of the s p a c e r or the m a i n c h a i n are d i s -
o r d e r e d . B e c a u s e this is a C H - v i b r a t i o n it c a n ' t be a s s i g n e d p r e -
c i s e l y to a s p e c i a l C H - g r o u p of the m o l e c u l e . T h e r e f o r e no m o r e de-
t a i l e d c o n c l u s i o n s c a n be d r a w n f r o m the d i c h r o i s m of this band.

The CN s t r e t c h i n g v i b r a t i o n a l band.
T h e o r d e r p a r a m e t e r of the m e s o g e n i c g r o u p c a n be d e t e r m i n e d v e r y
exactly with the isolated absorption b a n d of the C s
v i b r a t i o n . T h e t r a n s i t i o n m o m e n t of this v i b r a t i o n is k n o w n to be
p a r a l l e l to the C N - g r o u p . T h i s axis and the axis t h r o u g h the c e n t e r s
of g r a v i t y of the two b e n z e n e rings include an a n g l e of a few
d e g r e e s . This m e a n s that the o p t i c a l o r d e r p a r a m e t e r is lower than
the m o l e c u l a r order parameter by a f a c t o r Sa (eq i0). This was
n e g l e c t e d in the c o n s i d e r a t i o n s up to now. The f a c t o r is the same for
the two p o l y m e r s and the low m o l e c u l e r w e i g h t l i q u i d c r y s t a l L/7/CN.
T h e r e f o r e we can c o m p a r e m o l e c u l a r ordering by c o m p a r i n g o p t i c a l
order parameters.
We m e a s u r e d the t r a n s m i s s i o n at the c e n t e r of this b a n d w h i l e h e a t i n g
the s a m p l e s v e r y s l o w l y t h r o u g h the w h o l e n e m a t i c r a n g e u p to the
i s o t r o p i c state. We used IR r a d i a t i o n p o l a r i z e d p a r a l l e l and p e r p e n -
d i c u l a r to the o p t i c a l axis of the l i q u i d c r y s t a l . W i t h eq.6 and 7,
r e s p e c t i v e l y , both lead to i d e n t i c a l v a l u e s of the o r d e r p a r a m e t e r .
H o w e v e r , u s i n g the A_~ v a l u e s the e r r o r t o l e r a n c e s of S are the b e t t e r
ones. T h e i s o t r o p i c a b s o r p t i o n was c a l c u l a t e d f r o m the t r a n s m i s s i o n
in the i s o t r o p i c phase. T h e i n f l u e n c e of the i n t e r n a l f i e l d was
c o r r e c t e d u s i n g eq.9 . The v a l u e s of the r e f r a c t i v e i n d i c e s in eq.9
w e r e m e a s u r e d w i t h an o p t i c a l m i c r o s c o p e (12), or t a k e n f r o m (13)
(see t a b l e 3). The v a l u e n ~ . o of P/H/2/CN was a s s u m e d to be the same

T a b l e 3: P/H/6/CN P/H/2/CN L/7/CN

Refractive
indices nl.o 1.57 (13) - 1.546 (13)
An(T=0K) 0.19 (12) 0.39 (12) 0.41 (12)

0.8

l
8
0.6

0.4

0.2

Fig 8:
optical order 0.0
p a r a m e t e r s cal- L/7/CN P/H/2/CN
culated from
-0.2 I I I I ~ I
the CN s t r e t c h i n g 320 340 360 380 400 420
absorption bands
(continously measured) ,, T / K
556

as of P/H/6/CN. For the correction 6 was taken 0 ~ .

The temperature dependence of So~T is shown in fig.8 for the three
substances.
For a more detailed comparision of the curves we used an empirical
equation for the temperature dependance of SopT (14):

SopT = SSa = So (I-T/T~z) = (ii)

Using a logarithmic regression procedure So and the exponent e can be

calculated from the measured So,T values (see table 4). Since S is
known to become I at 0 K for low molecular weight liquid crystals,
the obtained value of So must be the same as S,. With S~ = 0.84
(L/7/CN) the angle 6 is calculated to be 19 ~ . If there is an
additional disorder due to interaction of the mesogenic group and the
main chain, So will be smaller then S~, this must be the reason why
So is only 0.77 (see table 4) for P/H/2/CN.

Table 4: P/H/6/CN P/H/2/CN L/7/CN

Results of linear re-
gression procedure So 0.86 0.77 0.84
0.24 0.23 0.20

Conclusions
The results of this study show that in Ic side chain polymers the
order of the mesogenic groups can be transformed to the main chain.
On the other hand the arrangement of the mesogenic groups is influen-
ced by the main chain, if there is a strong interaction between these
parts given by a short spacer.

Agknowledgements
The authors are obliged to Dr. R. Zentel of the University of Mainz
for sample preparation and to the Deutsche Forschungsgemeinschaft for
financial support.

References
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Accepted October 6, 1988 C