Structure and Properties of Poly(methyl methacrylate)

Particles Prepared by a Modified Microemulsion

Polymerization

WAN JIANG,1 WULI YANG,1 XIANBIAO ZENG,2 SHOUKUAN FU1

1
Department of Macromolecular Science and Key Laboratory of Molecular Engineering of Polymers (Ministry of
Education), Fudan University, Shanghai, 200433, People’s Republic of China

2
Chemistry and Chemical Industry College, Hunan Normal University, Changsha, 410081, People’s Republic of China

Received 27 January 2003; accepted 13 June 2003

ABSTRACT: Nanoscale poly(methyl methacrylate) (PMMA) particles were prepared by

modified microemulsion polymerization. Different from particles made by traditional
microemulsion polymerization, the particles prepared by modified microemulsion po-
lymerization were multichain systems. PMMA samples, whether prepared by the
traditional procedure or the modified procedure, had glass-transition temperatures
(Tg’s) greater than 120 °C and were rich in syndiotactic content (55– 61% rr). After the
samples were dissolved in CHCl3, there were decreases in the Tg values for the
polymers prepared by the traditional procedure and those prepared by the modified
process. However, a more evident Tg decrease was observed in the former than in the
latter; still, for both, Tg was greater than 120 °C. Polarizing optical microscopy and
wide-angle X-ray diffraction indicated that some ordered regions formed in the particles
prepared by modified microemulsion polymerization. The addition of a chain-transfer
agent resulted in a decrease in both the syndiotacticity and Tg through decreasing
polymer molecular weight. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42:
733–741, 2004
Keywords: modified microemulsion polymerization; poly(methyl methacrylate);
nanoparticles; syndiotactic; glass-transition temperature (Tg)

INTRODUCTION groups5– 8 have tried to overcome these draw-

Microemulsion polymerization has widely been
studied since the first reports by Stoffer and Bone
in the early 1980s,1,2 and this procedure is effec-
tive in producing polymer latices of 10 –100 nm.3,4
However, two major drawbacks limit its broad
application: (1) low monomer/surfactant weight
ratios, usually less than 1, and (2) low polymer
contents, usually less than 10 wt %. A number of
Correspondence to: S. Fu (E-mail: skfu@srcap.stc.sh.cn)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 42, 733–741 (2004)
© 2003 Wiley Periodicals, Inc.
backs to make microemulsion polymerization
more practical. Recently, our laboratory devel-
oped a modified microemulsion polymerization to
prepare a high-solid-content nanosize polymer la-
tex, in which the monomer was gradually added
into the polymerizing microemulsion system
without disturbing its stability.9,10
A microsphere prepared by traditional micro-
emulsion polymerization generally contains only
a single-chain polymer or a polymer with few
chains and shows some novel characteristics in its
conformation and thermal behaviors. Qian et al.11
found that a single-chain polystyrene (PS) glass

733
734 JIANG ET AL.
prepared by microemulsion polymerization had a
higher conformational temperature than ordinary
multichain PS according to Fourier transform in-
frared (FTIR) and displayed an exotherm peak
near the glass-transition temperature (Tg) during
the first differential scanning calorimetry (DSC)
scan. The results were interpreted in terms of the
existence of nematic localized cohesion entangle-
ments in PS glass. Wu et al.12 reported that the
density of particles of PS with few chains (0.95
g/cm3) was 9.5% lower than the densities of tra-
ditional PS latex and bulk PS (1.05 g/cm3). Our
group13 found that particles of PS with few chains
showed two exotherm peaks near 107 and 157 °C
during the first DSC scan, and in the subsequent
scan, both exotherm peaks disappeared and, only
one glass transition similar to that of ordinary PS
was kept. The second exotherm peak was ascribed
to the relatively compact conformation of PS
chains and the slightly ordered regions that con-
sequently formed inside the particles of PS with
few chains during the heating process. Our
group14 also reported that the DSC curve of a
poly(methyl methacrylate) (PMMA) microsphere
prepared by traditional microemulsion polymer-
ization had one higher Tg (135 °C) in the first scan
and that Tg’s of the second and the third scans
were still higher (125 °C) than that of ordinary
PMMA (105 °C). Recently, Pilcher and Ford15 dis-
covered that PMMA with few chains had higher
Tg’s (125–126 °C) and 58 – 61% rr triads at 60 °C
(polymerization temperature) and 63– 65% rr tri-
ads at 35 °C.
With modified microemulsion polymerization,
relatively concentrated polymeric microemul-
sions (polymer content ⫽ 10 –30 wt %) were
achieved, with particle diameters of 20 – 40 nm
maintained.9 For PMMA prepared by modified
microemulsion polymerization, we found that a
higher Tg existed in the first scan and also in the
second scan. Here we report some characteristics
of PMMA nanoparticles from the modified sys-
tem, such as the Tg, tacticity, and particle size,
and discuss the conformation and configuration in
the restricted volume of a nanosize particle.
EXPERIMENTAL
Materials
Monomers were purchased from Shanghai Chemi-
cal Reagent Co. and were distilled under reduced
pressure before polymerization. Sodium dodecyl
sulfate (SDS) was purchased from Shanghai Shen-
gong Bioengineering Corp. and was used as re-
ceived. Ammonium persulfate (APS) was purchased
from Shanghai Aijian Reagent Factory and purified
by recrystallization in water. Cetyltrimethylammo-
nium bromide was purchased from Shanghai
Chemical Reagent and purified with a mixture of
ethanol and acetone (1:1). Nonyl phenol poly(ethe-
noxy ether) NP-9 (EO: 9) and nonyl phenol poly-
(ethenoxy ether) NP-40 (EO: 40) were purchased
from Henkel KGaA and used as received. Ascorbic
acid from Shanghai Xingxing Medicine Developing
Center and a 30% hydrogen peroxide solution from
Shanghai Taopu Chemical Factory were used as
received. N,N,N⬘,N⬘-Tetramethylethylenediamine
(TMEDA), 1-pentanol (n-Pt), methanol, and chloro-
form from Shanghai Chemical Reagent were used
as received. Deionized water was used for all the
polymerization experiments.
Preparation of PMMA Nanoparticles by Modified
Microemulsion Polymerization
The recipes of modified microemulsion polymer-
izations under various conditions are shown in
Table 1. The general procedure of microemulsion
polymerization with SDS/n-Pt as a surfactant and
cosurfactant and APS as an initiator can be de-
scribed as follows. The premicroemulsion, com-
posed of the entire amount of the surfactant, the
auxiliary surfactant, water, and an amount of the
monomer that was slightly higher than its solu-
bility in water, was added into a 100-mL, four-
necked flask equipped with a reflux condenser, an
addition funnel, a thermometer, a nitrogen gas
inlet, nitrogen gas outlet, and a magnetic stirring
bar. The premicroemulsion was heated to 70 ⫾ 2
°C for the APS initiator (30 ⫾ 2 °C for redox
initiators) and was stirred under a nitrogen at-
mosphere. Then, the requisite amount of the ini-
tiator, which was dissolved in a minimum quan-
tity of water, was added. When the polymeriza-
tion started, the rest of the monomers in the
addition funnel were added into the reaction flask
in a starving addition manner.
The polymer particles were precipitated in
methanol, and the mixture was allowed to stand
overnight. The precipitated polymer was vacuum-
filtered, washed successively with methanol and
water, and dried in a vacuum desiccator for 24 h
at 50 °C. No surfactant peaks were detected in the
1
H NMR spectra of the purified samples.
 MODIFIED MICROEMULSION POLYMERIZATION 735

Table 1. Compositions and Particle Sizes of the Samples

Surfactant H2O Dz CV, variable

Sample (g)a Initiator (g) (mL) MMA (g)b (nm) coefficient (%)

A1 SDS/n-Pt APS (0.114) 42 1 ⫹ 5.1 20 31

(0.7/0.1)
A2c SDS/n-Pt APS (0.114) 42 1 18 24
(5.4/0.7)
A3d SDS/n-Pt APS (0.6) 42 1 ⫹ 5.1 20 32
(0.7/0.1) (SH, 0.06)
A4 SDS/n-Pt APS/TMEDA 43 1 ⫹ 5.1 22 35
(0.7/0.1) (0.037/0.02)
A5c SDS/n-Pt APS/TMEDA 185 2.2 21 37
(22/0.62) (0.037/0.02)
A6 SDS/n-Pt H2O2/asorbic acid 43 1 ⫹ 5.1 27 34
(0.7/0.1) (0.06/0.09)
A7c SDS/n-Pt H2O2/asorbic acid 43 1 26 30
(5.4/0.7) (0.06/0.09)
A8d SDS/n-Pt H2O2/asorbic acid 43 1 22 41
(5.4/0.7) (0.06/0.09)
(SH, 0.01)
C CTAB (1.5) H2O2/asorbic acid 42 1 ⫹ 5.1 17 36
(0.06/0.09)
N1 NP-9/NP-40 APS (0.114) 38 1 ⫹ 5.1 22 34
(4.5/0.5)
N2 NP-9/NP-40 H2O2/asorbic acid 38 1 ⫹ 5.1 19 10
(4.5/0.5) (0.06/0.09)
N3 NP-9/NP-40 APS/TMEDA 38 1 ⫹ 5.1 18 25
(4.5/0.5) (0.114/0.06)
N4c NP-9/NP-40 APS (0.114) 47 2.1 105 20
(0.72/0.08)
A9e SDS (0.015) APS (0.037) 43 6.1 137 29
a
n-Pt was used as a consurfactant.
b
The first part of the monomer was in the initial microemulsion, and the second part was postadded.
c
The sample was polymerized by traditional microemulsion polymerization.
d
SH was used as the chain-transfer agent to reduce the molecular weight of the polymer.
e
The sample was polymerized by emulsion polymerization.

Characterization of the Nanoparticles spectrometer was used for 1H NMR analysis with
CDCl3 as a solvent. The tacticities of the samples
The particle size and size distribution were mea-
were measured from the integrated ratios of the
sured by dynamic light scattering on a Malvern
syndiotactic (rr), isotactic (mm), and heterotactic
4700 from Malvern Instruments, Ltd. Gel perme-
(mr) triad signals of ␣-methyl protons.16 The sam-
ation chromatography measurements were car-
ple structure was observed with a Leitz polarized
ried out with an HP series 1100 chromatograph
optical microscopy (POM) instrument. Wide-an-
equipped with Zorbax columns and refractive-in-
gle X-ray diffraction (WAXD) was performed with
dex/ultraviolet dual-mode detectors. The elution
a Rigaku D/max-II diffractometer with Cu K␣
rate of tetrahydrofuran (THF) was 1 mL/min, and
radiation, with a scanning speed of 4°/min.
standard PS was used for calibration. The Tg val-
ues of the samples were measured with a Setaram
DSC92 differential scanning calorimeter at a
heating rate of 10 °C/min from 20 to 200 °C fol- RESULTS AND DISCUSSION
lowed by rapid cooling. Stannum (mp ⫽ 353.35 K)
and indium (mp ⫽ 429.78 K) were used to cali- Our modified microemulsion polymerization pro-
brate the instrument. A Bruker Avance 500 NMR cedure includes three steps: (1) the initiation of
736 JIANG ET AL.

Table 2. Molecular Weights, Tg’s, and Tacticities of the Samples

Mw Mn Tg Tg
Sample (⫻105) (⫻105) Mw/Mn (°C) (°C)a rr mr mm

A1 2.4 1.7 1.4 128.0 124.1 0.56 0.35 0.09

A2b 10.0 1.9 5.4 132.1 123.5 0.55 0.37 0.08
A3 0.42 0.15 2.8 115.2 — 0.48 0.39 0.13
A4 2.1 1.2 1.8 127.9 123.5 0.57 0.35 0.08
A5b 9.8 1.7 5.7 131.6 123.8 0.57 0.35 0.08
A6 2.8 0.7 4.0 127.0 124.2 0.56 0.32 0.12
A7b 9.7 2.3 4.3 132.1 124.3 0.56 0.37 0.07
A8 0.13 0.09 1.4 110.7 — 0.47 0.37 0.16
C 7.6 5.3 1.4 132.1 130.2 0.61 0.33 0.06
N1 2.5 0.7 3.6 125.9 123.4 0.55 0.37 0.08
N2 5.4 1.6 3.3 129.8 126.7 0.57 0.36 0.07
N3 5.7 2.4 2.4 129.3 126.4 0.59 0.35 0.06
N4c 2.1 0.9 2.3 115.4 112.7 0.51 0.41 0.08
A9c 1.8 1.0 1.8 110.0 109.5 0.50 0.42 0.08
ICId 1.5 0.8 1.9 105.5 — 0.48 0.42 0.10
a
After the sample was dissolved in CHCl3 and precipitated with methanol.
b
The sample was polymerized by traditional microemulsion polymerization.
c
The sample was polymerized by emulsion polymerization.
d
The PMMA sample was provided by ICI Co.

polymerization in a traditional microemulsion
system, (2) the slow and continuous addition of
most of the monomer (during this stage, it is
important to avoid a buildup of unreacted mono-
mer droplets), and (3) the postaddition reac-
tion.9,10 With this procedure, PMMA microlatices
with nanosize particles were prepared, as shown
in Table 1. For their counterparts, some PMMA
nanoparticles made by traditional microemulsion
polymerization and emulsion polymerization,
data are also provided. All the particles prepared
by modified microemulsion polymerization or tra-
ditional microemulsion polymerization were
17–27 nm. In comparison, the modified procedure
needed less surfactant to stabilize the particles.
With the microemulsion polymerization, polymer
particles of a generally constant nanosize could be
prepared when the amount of the surfactant or
the surfactant/monomer ratio changed over a
rather wide range.
In Table 2, it can be seen that PMMA made by
traditional microemulsion polymerization had a
higher weight-average molecular weight (Mw
⬃ 106) and a wider molecular weight distribution
than PMMA by modified microemulsion polymer-
ization. For example, A2 and A1 had similar par-
ticle sizes, but Mw of A2 was 106, and that of A1
was 2.4 ⫻ 105; the molecular weight polydisper-
sities [weight-average molecular weight/number-
average molecular weight (Mw/Mn)] were 5.4 and
1.4, respectively. On the basis of the data in Ta-
bles 1 and 2, the number of macromolecule chains
per microsphere (Np) can be estimated as follows:
N p ⫽ Mp/(Mw/NA) ⫽ 共1/6兲␲DW3dp/共Mw/NA) (1)
where dp is the density of PMMA latices (1.18
g/cm3)15 and NA is Avogadro’s constant. With Dz
instead of Dw used as an estimation, Np of A2 was
2, and Np of A1 was 11, according to eq 1. The
results of A5 (2–3 chains) and A4 (17–18 chains)
were similar to those mentioned. It was assumed
that a particle was a system with few chains
when Np was less than 5. The nanoparticles pre-
pared by traditional microemulsion polymeriza-
tion (A2, A5, and A7) were systems with few.13,15
For the modified systems (A1, A4, and A6), the
analysis indicated that they were multichain sys-
tems. In a modified microemulsion polymeriza-
tion, the surfactant/monomer ratio used was
lower than that of the traditional procedure, so
the chances of the radicals entering the pre-exist-
ing polymer particles were enhanced. In addition,
the monomers were added incessantly during the
modified polymerization but not during the tradi-
tional polymerization. Therefore, there were
lower molecular weight and more polymer chains
 MODIFIED MICROEMULSION POLYMERIZATION 737

Figure 1. DSC curves of PMMA particles polymerized by modified microemulsion

polymerization (A4): (1) first scan and (2) second scan.

(⬎10) in the polymer particles prepared by the
modified microemulsion polymerization than in
those prepared by the traditional one.
The representative thermal behaviors of
PMMA particles made by the modified and tradi-
tional procedures are shown in Figures 1 and 2.
The results were similar: the samples displayed
one peak of the superposition of an exothermic
transition and a glass transition at about 130 °C
in the first scan. A subsequent scan after cooling
to the ambient temperature still showed a higher
Tg value (generally ⬎120 °C), and both exotherm
peaks disappeared. Because the particles made
by the traditional and modified procedures were
nanosize, they had larger specific surface areas,
and during the rising temperature procedure, the
loss of surface area resulted in an energy release,
that is, an exotherm (the sintering phenome-
non).13 The PMMA samples prepared by the tra-
ditional and modified microemulsion polymeriza-
tions had Tg’s greater than 120 °C in the second
scan of DSC (the Tg discussed later is also the Tg

Figure 2. DSC curves of PMMA polymerized by traditional microemulsion polymer-

ization (A2): (1) first scan and (2) second scan.
738 JIANG ET AL.
Figure 3. 1H NMR spectrum (400 MHz) of PMMA particles polymerized by modified
microemulsion polymerization (A1).
in the second scan), which is much higher than
the values of 105 °C for commercial PMMA (Table
2).17,18 Tg of the particles from the traditional
procedure was higher than that from the modified
procedure when the particle size was similar (e.g.,
A5 and A4 and A7 and A6).
To explain the high Tg’s, we measured the 1H
NMR spectra of PMMA nanoparticles in CDCl3
solutions and analyzed the tacticity to the triad
level on the basis of the ␣-methyl protons.15,16
Figure 3 presents a representative spectrum of
PMMA particles, in which the syndiotactic (rr),
heterotactic (mr), and isotactic (mm) triad peaks
of ␣-methyl protons are 0.85, 1.02, and 1.20 ppm.
As shown in Figure 3 and Table 2, the polymers
prepared by the modified and traditional micro-
emulsion polymerizations were rich in syndiotac-
tic content (55– 61% rr) in comparison with com-
mercial PMMA (48% rr).17,18 A 13C NMR solid
spectrum of sample A1 (not shown here) also con-
firmed the high syndiotacticity content in the par-
ticles prepared by modified microemulsion poly-
merization. Because a random coil of PMMA with
a molecular weight of 106 has an unperturbed
root-mean-square end-to-end distance of 55 nm in
bulk,19 all the particles made by the modified and
traditional procedures were toward the low end of
the nanoscale (⬍30 nm), and the polymer chains
were in a restricted space. Especially near the
surface of a particle, the path of its random walk
had to turn back into the particle. The restricted
volume affected the conformation and tacticity of
the polymer chains,20 and the polymer chain
needed to have more gauche conformations than
its unperturbed state to reduce its high potential
energy in a small particle. Therefore, the end
propagation of high-molecular-weight chains was
also restricted during polymerization, and the
tacticity of the polymer could be altered, too. Be-
cause the energy of the racemic dyads was lower
than that of the meso dyads, it could result in a
configuration rich in syndiotactic content. For
comparison, the tacticity of samples from emul-
sion polymerization (N4 and A9) were also
checked. A9 was 137 nm, and the syndiotactic
content decreased to 50%, similar to commercial
PMMA. The results indicated that the small par-
ticle size of PMMA with a high molecular weight
could result in higher syndiotactic contents and
higher Tg’s.
Furthermore, the purified particles prepared
by traditional microemulsion polymerization and
modified microemulsion polymerization were dis-
solved in CHCl3 and precipitated with methanol

Figure 4. FTIR spectra of PMMA polymerized by (a)
traditional microemulsion polymerization (A2) and (b)
modified microemulsion polymerization (A1).
again. After that, as shown in Table 2, the sam-
ples exhibited slight differences in DSC. There
were decreases in the Tg values for the polymers
by both the traditional and modified microemul-
sion polymerizations, but the decrease for the
former was more obvious than that for the latter;
still, both were greater than 120 °C. This suggests
that the rich syndiotacticity in the polymer defi-
nitely had an effect on the Tg value of the samples
by the modified microemulsion polymerization
and by the traditional microemulsion polymeriza-
tion as well. For the higher molecular weight
samples, the polymer chain from the traditional
procedure had a more compacted state than that
from the modified procedure, and the decrease in
the Tg value was greater than that from the mod-
ified procedure after dissolution. The infrared ab-
sorption bands in the 1300 –1000-cm⫺1 range of
PMMA are known to be conformation-restriction-
sensitive.21 Moreover, the absorption peaks ␯1
(1240 cm⫺1) and ␯2 (1270 cm⫺1) have been used in
the literature to calculate the ratio of local back-
bone and side-chain conformational energies; the
bigger the ratio (␯1/␯2) is, the higher the local
backbone conformational energy is.22 In Figure 4,
it can be seen that the ␯1/␯2 ratio for samples
polymerized by traditional microemulsion poly-
merization was a little higher than that of sam-
MODIFIED MICROEMULSION POLYMERIZATION 739
ples polymerized by modified microemulsion po-
lymerization. This suggests that the former had a
slightly higher local backbone conformational en-
ergy than the latter. Therefore, when the confor-
mational energy was released after the samples
were treated with a solvent (CHCl3), Tg of the
former decreased close to that of the latter.
In addition, we added a chain-transfer agent
[dodecanethiol (SH)] to reduce the molecular
weight with the aim of seeing if there was still a
high Tg during DSC scanning. From Table 2, for
samples A3 and A8, it can be seen that both the
syndiotacticity and Tg decreased a lot, near to the
values of commercial PMMA. This could be attrib-
uted to the addition of the chain-transfer agent,
which resulted in a decrease in the molecular
weight of the nanoparticles of the same size as
that of the sample in which SH was not added.
When the molecular weight decreased, the num-
ber of polymer chains increased, and the unper-
turbed root-mean-square end-to-end distance de-
creased less than the nanoparticle size; then, the
conformation and configuration restriction of the
polymer chain during propagation decreased, and
the influence on the tacticity of PMMA also de-
creased.
A PMMA particle of A1 was also observed with
POM, as shown in Figure 5. A light area can
clearly be seen in the photograph. The light area
represents some kind of ordered region. WAXD
observations are shown in Figure 6. There were at
least three diffraction peaks in the S-PMMA film
at 2␪ ⫽ 10.9, 13.2, and 17.4°.23 The PMMA sam-
ples polymerized by modified microemulsion po-
lymerization did not show clear peaks where the
S-PMMA film did, but they showed two peaks at
Figure 5. Polarizing optical microscopy photograph
of PMMA (A1).
740 JIANG ET AL.
Figure 6. XRD curves of PMMA: (1) N1, (2) C, (3) A1, and (4) ICI.
21 and 23°. These peaks indicated that there were
some ordered regions in the particles made by
modified microemulsion polymerization. The com-
mercial PMMA had no diffraction peaks. The
WAXD signal agreed with the syndiotactic con-
tent of the particle; that is, the richer a sample
was in syndiotactic content (C ⬎ A1 ⬎ N1), the
more definite and resolved the X-ray diffraction
peaks were (C ⬎ A1 ⬎ N1).
CONCLUSIONS
Nanoscale PMMA particles (17–27 nm) were pre-
pared by a modified microemulsion polymeriza-
tion in which relatively concentrated polymeric
microemulsions (polymer content ⫽ 10 –30 wt %)
were achieved with a low amount of surfactant
(1–2 wt %). The nanoparticles prepared by tradi-
tional microemulsion polymerization were sys-
tems with few chains, whereas those prepared by
the modified microemulsion polymerization were
multichain systems. The samples by both proce-
dures displayed one exotherm peak at about 130
°C in the first DSC scan and showed one higher Tg
(generally ⬎120 °C) in a subsequent scan after
cooling to the ambient temperature, as well as no
exotherms. All the PMMA samples prepared by
the traditional and modified procedures were rich
in syndiotactic content (55– 61% rr). After they
dissolved in CHCl3, there were decreases in the
Tg value for the polymers made by the traditional
procedure and the modified process, but the de-
crease for the former was greater than that for
the latter, yet for both, Tg was greater than 120
°C. The addition of a chain-transfer agent re-
sulted in a decrease in both the syndiotacticity
and Tg through decreasing polymer molecular
weight. Polarizing optical microscopy and WAXD
indicated that some ordered regions formed in the
particles prepared by modified microemulsion po-
lymerization.
The authors thank the Major State Basic Research
Development Program (G1999064802) and the Na-
tional Natural Science Foundation of China (20244002)
for their financial support.
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