Preparation and Properties of High Performance

Epoxy–Silsesquioxane Hybrid Resins Prepared Using

a Maleimide–Alkoxysilane Compound as a Modifier
YING-LING LIU,1 GUNG-PEI CHANG,1 CHUAN-SHAO WU,2 YIE-SHUN CHIU3
1
Department of Chemical Engineering, Chung Yuan Christian University, Chungli, Taoyuan 320, Taiwan
2
Department of Textile Science, Nan Ya Institute of Technology, Chungli, Taoyuan 320, Taiwan
3
Department of Chemistry, Chung Yuan Christian University, Chungli, Taoyuan 320, Taiwan

Received 6 June 2005; accepted 31 July 2005

DOI: 10.1002/pola.21057
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: An alkoxysilane compound possessing maleimide moiety (MSM) was pre-

pared from N-(4-hydroxyphenyl)maleimide and 3-glycidoxypropyltrimethoxysilane
and was used as a modifier of epoxy resins. In situ curing epoxy resins with MSM
resulted in epoxy resins with good homogeneity. Just 5–10 wt % of MSM is sufficient
to yield high glass transition temperature (165 8C), good thermal stability above
360 8C, and high flame retardancy (LOI ¼ 30) to bisphenol-A-based epoxy resins.
V
C 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5787–5798, 2005

Keywords: epoxy resin; flame retardancy; maleimide

INTRODUCTION the problems of relatively poor thermal stability,

Epoxy resins are one of the most important ther-
mosetting materials that are used as insulators in
printed circuit boards and electronic or electrical
industries. Recently, new challenges involving
developments of advanced package techniques,
halogen-free issues, and lead-free processes are
met by epoxy resins. Halogen-free epoxy resins
exhibiting good flame retardancy and excellent
thermal stability above 300 8C are highly expected
to meet the criteria for future applications.1
Halogen-free flame retardant epoxy resins have
been widely studied with a focus on phosphorus-
containing compounds.2–13 Nowadays, one trend
in the developments of epoxy resins is by the
replacement of the phosphorylated epoxy resins
with phosphorus-free formulations,14–17 to avoid
Correspondence to: Y.-L. Liu (E-mail: ylliu@cycu.edu.tw)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 5787–5798 (2005)
V
C 2005 Wiley Periodicals, Inc.
hydrolysis character, and undefined toxicity, which
generate from phosphorus compounds. Another
trend is to increase the flame retardant efficiency
of the epoxy resins by developing synergistic sys-
tems of flame retardants.8,10–11,18,19 Moreover, en-
hancement of thermal stability of epoxy resins is
also attractive, as high processing temperatures
are employed in the advanced packing techniques
and lead-free processes.1 Major approaches are
formation of epoxy–silica nanocomposites18–25 and
modification of epoxy resins with nitrogen-con-
taining heterocyclic compounds having imide and
triazine groups.12,14,26–28
On the basis of the aforementioned concepts,
the target of this work was to develop halogen-free
and phosphorus-free characteristics, synergistic
effect of flame retardancy, and good thermal
stability in epoxy resins, with a ‘‘one-pot’’ modifi-
cation. An alkoxysilane compound possessing
maleimide moiety (MSM) was prepared from N-(4-
hydroxyphenyl)maleimide (HPM) and 3-glycidoxy-
5787
5788 LIU ET AL.
propyltrimethoxysilane (GPTMS) and was used
as a modifier to epoxy resins. While adding MSM
in epoxy formulations, polymerization of malei-
mide groups under epoxy curing process would
increase the crosslinking densities and glass tran-
sition temperatures of the cured epoxy resins.24
The nitrogen-containing heterocyclic maleimide
groups could also increase the thermal stability
of epoxy resins. Nanostructured silica formed
from sol–gel reactions of alkoxysilane groups of
MSM provides another contribution to enhance
the thermal stability of epoxy resins. In addition,
superior flame retardant property is expected
from the MSM-modified epoxy resins (MSMERs),
as a silicon–nitrogen synergistic effect of flame
retardancy enhancement was performed by means
of the action of silica and maleimide networks.8,12
Moreover, MSM could be used as an additive-type
modifier and functioned as a reactive-type flame
retardant, so as to exhibit both the advantages of
additive- and reactive-type flame retardants.29
EXPERIMENTAL
Materials
HPM was prepared in the laboratory.14 Diglycidyl-
ether of bisphenol A (BE188, epoxy equivalent
weight ¼ 188 g/mol) was obtained from Chang
Chun Plastics, Taiwan. p-Toluenesulfonic acid
(p-TSA), tetrahydrofuran (THF), 4,40 -diaminodi-
phenylmethane (DDM), and GPTMS were pur-
chased from Aldrich Chemical and were used as
received.
Instruments
Infrared spectra (FTIR) were recorded with a
PerkinElmer Spectrum One FTIR. Liquid samples
were measured with KBr windows. The cured res-
ins were measured with a PerkinElmer Spectrum
One FTIR equipped with an attenuated total
reflectance (ATR) accessory. 1H NMR spectra were
recorded with a Brüker MSL-300 (300 MHz) NMR
spectrometer, using CDCl3 as a solvent. Solid-
state NMR analysis was performed with a Brüker
DSX400WB (400 MHz) NMR spectrometer. The
morphology of the fracture surface of the cured
hybrid resins was observed with a scanning elec-
tron microscope (SEM, Hitachi S-3000 N Hi-SEM,
Japan). Energy dispersive X-ray (EDX) measure-
ments were conducted with a Horiba ES-320 EDX
micro analyzer. Differential scanning calorimetry
(DSC) thermograms were recorded with a Ther-
mal Analysis DSC-Q10 differential scanning calo-
rimetry. The testing condition was from 30 to
300 8C, at a heating rate of 10 8C/min, under a
nitrogen gas flow of 40 mL/min. Thermogravimet-
ric analysis (TGA) was performed with a Thermal
Analysis TGA-2050 thermogravimetric analyzer,
at a heating rate of 10 8C/min, under nitrogen
atmosphere or air. The gas flow rate was 100 mL/
min. Dynamic mechanical analysis (DMA) was
performed with a PerkinElmer dynamic mechani-
cal analyzer DMA 7e, at a frequency of 1 Hz and a
heating rate of 3 8C/min. Limited oxygen index
(LOI) values were measured with a Stanton Red-
craft flame meter. The percentage in the O2–N2
mixture, deemed sufficient to sustain the flame,
was taken as the value of LOI.
Synthesis of Maleimide–Silane Hybrid
Monomer (MSM)
HPM (3.46 g, 25 mmol) and GPTMS (7.08 g, 30 mmol)
were dissolved in 40-mL N,N-dimethylsulfoxide
(DMSO) and the solution was charged into a
round-bottom flask. After adding 0.02 g of triphe-
nylphosphine as a reaction promoter, the mixture
was allowed to react at 150 8C for 5 h. After cooling
to room temperature, the reaction mixture was
poured into excess toluene and the precipitant
was collected by filtration. The solid product was
washed with toluene and then dried at 50 8C
under vacuum for 24 h to give the final product.
Yield: 60%. FTIR (KBr, cm
1): 3385 (

OH),
3065 (C

H in phenyl group), 2940 (aliphatic
C

H), 1778 (C¼ ¼O asymmetrical stretching),
1705 (C¼ ¼O symmetrical stretching), (1150 C

N


C in maleimide ring), 1094 (Si

O

C). 1H NMR
(CDCl3, ppm): 0.79 (Si

CH2

), 1.80 (SiCH2


CH2

), 2.13 (Si

OCH3), 3.45–3.72 (

OCH2

),
6.79 (

CH¼ ¼CH

of maleimide ring), and 6.87–
7.17 (aromatic protons).
Preparation of MSM-Modified Epoxy Resins
MSMERs were prepared by the reported
method.11 For the preparation of MSMER-10 (10
wt % of MSM in the resin composition), MSM (1.1
g) was dissolved in 10-mL THF by adding 0.12 g of
distilled water and 0.01 g of p-TSA. The mixture
was stirred at room temperature for 1 h to yield
solution A. Solution B was prepared by dissolving
8.0 g of BE188 and 2.0 g of DDM in 15 mL of THF.
Solution A and B were then mixed together and
stirred at room temperature for 1 h. The solvent
 PREPARATION AND PROPERTIES OF EPOXY–SILSESQUIOXANE HYBRID RESINS 5789

Figure 1. Preparation of maleimide-containing trimethoxysilane compound MSM.

was removed under vacuum, and the residual was
then heated at 30 8C (1 h), 120 8C (1 h), 150 8C (1 h),
200 8C (1 h), and 230 8C (2 h) to yield cured resins.
RESULTS AND DISCUSSION
Preparation of Hybrid Monomer MSM
One-end functionalized trialkoxysilanes are use-
ful coupling agents for improvement of organic–
inorganic interfacial compatibility. These com-
pounds are also utilized as ceramic precursors for
preparation of polymer–silica hybrid materials
and nanocomposites.30 The organo-functional
groups of silane compounds react with organic
polymers to provide interfacial linkages between
ceramic and polymeric domains. On the other
hand, one-end functional alkoxysilane compounds
are also used as additives and property-improving
agents for polymers.11,31 On the basis of this
concept, an alkoxysilane compound with a malei-
mide functional group was prepared in this work,
and then the prepared maleimide–silane hybrid
compound (MSM) was used as a modifier of epoxy
resins. Figure 1 shows the preparation scheme of
MSM, which was obtained through the addition
reaction between oxirane and phenol groups by
using triphenylphosphine as a reaction promoter.
Occurrence of this reaction was demonstrated
using FTIR measurements (Fig. 2). The absorp-
tion peaks of oxirane ring (910 cm
1) and
Ph

O

H (3482 cm
1) vanished after the reac-
tion. Appearance of the broad peak at 3385 cm
1

Figure 2. FTIR spectra of cured MSMERs. [Color figure can be viewed in the
online issue, which is available at www.interscience.wiley.com.].
5790 LIU ET AL.

Table 1. Preparation Compositions and Characterization Data of MSMER Resins

Thermal Stability

In Nitrogen In Air

Modifier Char Yield Char Yield

Amount at 800 8C at 800 8C
Sample (wt %) Tg (8C) Td (8C) (%) Td (8C) (%) LOI

MSMER-0 0 136 345 18.4 339 0 22

MSMER-5 5 162 347 22.9 364 1.8 28
MSMER-10 10 165 349 28 361 2.2 30
MSMER-20 20 169 350 33.1 355 3.4 32
MSMER-30 30 168 343 35.3 351 3.9 30
CMSM Pure MSM 211 366 55.5 362 14.3 40

in the FTIR spectrum of the reaction product indi-
cated the formation of secondary alcohol after the
reaction. Other characteristic absorption peaks
for MSM were observed at 2943 and 2874 (ali-
phatic C

H), 1775 (C¼ ¼O asymmetrical stretch-
ing), 1714 (C¼¼O symmetrical stretching), 1397
(C

N), 1150 (C

N

C in maleimide ring), and
1094 (Si

O

C) cm
1. 1H NMR analysis results
of MSM further support its chemical structure,
with the characteristic absorption peaks at 0.79
(Si

CH2

), 1.80 (SiCH2

CH2

), 2.13 (Si


OCH3), 3.45–3.72 (

OCH2

), 6.79 (

CH
¼¼CH

of maleimide ring), and 6.87–7.17 (aro-
matic protons) ppm.
Preparation and Characterization of MSMERs
MSM could be considered as a crosslinkable mono-
mer. The crosslinking reaction of MSM took place
by means of self-addition reaction of maleimide
groups and gel-reaction of hydrolyzed silanol
groups. These reactions could be performed under
the curing conditions of epoxy resin. Solely, curing
of MSM resulted in a MSM cured resin (CMSM),
which is hard, smooth, and transparent. CMSM
exhibits superior properties, such as high glass
transition temperature of 211 8C, good thermal
stability above 360 8C, high char yield of 55%
(heating in nitrogen at 800 8C), and high LOI
value of 40. Thus, using MSM as an additive modi-
fier for commercial bisphenol-A type epoxy resins
is attractive. Preparation of MSMERs was then
done by blending MSM sol solution and BE188/
DDM solution together. The mixture was ther-
mally cured under certain conditions. Here MSM
was used as an ‘‘additive-type’’ modifier, and func-
tioned as a ‘‘reactive-type’’ agent.29 MSMER sam-
ples containing 5–30 wt % of MSM were prepared
(Table 1). MSMER is expected to possess silses-
quioxane network (from sol–gel reactions of alkox-
ysilane groups), heterocyclic imide structure (from
maleimide curing reaction), maleimide network,
and epoxy network (from BE188/DDM matrix) in
its cured structure. In addition, as shown later,
Michael addition reaction between the amine
groups of DDM and maleimide groups of MSM
might also occur,32 to form covalent linkages be-
tween the maleimide and epoxy networks. There-
fore, the structures in MSMER could be a totally
linked network, rather than an interpenetrating
network structure.
The cured resins were characterized using
FTIR. Figure 2 showed the FTIR spectra of
CMSM, MSMER-5, and MSMER-20. The occur-
rence of sol–gel reactions of methoxysilane groups
demonstrated the disappearance of the absorption
peaks from

Si

OCH3 at 2943 and 2874 cm
1
and the appearance of absorption peaks from
Si

O

Si at 1000–1100 cm
1 (broad).33 The exis-
tence of the absorption peak at 919 cm
1 from
Si-OH indicated the performance of the sol reac-
tion and the incompletion of the gel reaction.33
Similar results were also observed with solid-state
29
Si NMR analysis, as discussed later. For
MSMERs, the disappearance of absorption peaks
of

NH2 (3200–3500 cm
1) and oxirane ring (910
cm
1) demonstrated the occurrence of amine–
epoxy curing reaction. The absorption peaks of


C¼ ¼O and

Si

O

groups at 1711 and 1000–
1100 cm
1, respectively, were observed with
MSMERs to indicate the incorporation of MSM
structure into the resins. The existence of these
two absorption peaks indicated that the cured
samples possess MSM The performance of the gel
 PREPARATION AND PROPERTIES OF EPOXY–SILSESQUIOXANE HYBRID RESINS 5791

29
Figure 3. Solid-state Si NMR spectra of (a) MSMER-10 and (b) MSMER-20.

reaction of the silanol groups and formation of sil- observed and assigned to the corresponding ab-
sesquioxane structure in the MSMERs were char- sorption of nonhydroxy-substituted silsesquiox-
acterized by solid-state 29Si NMR (Fig. 3). Two ane (T3) and monohydroxy-substituted silses-
major peaks at about
64 ppm and
59 ppm were quioxane (T2), respectively.34 A shoulder at about
5792 LIU ET AL.

47 ppm was observed with the NMR curves indi-
cating the existence of some dihydroxy-substi-
tuted silsesquioxane (T1) in the cured resins. The
peak-integration area of T1 absorption peak was
relatively small to indicate the high conversion of
the gel reaction of the silanol groups. It was note-
worthy that MSMER-20 showed a higher content
of T3 structure than did MSMER-10. Therefore,
high alkoxysilane loadings promote the formation
of silsesquioxane network in MSMERs.
All the prepared MSMER samples were trans-
parent, indicating that no macrophase separation
occurs during curing and in the resins obtained.
However, opacity was observed with MSMER-40,
to a certain extent, to indicate that the amount of
MSM added to the epoxy resins is limited because
of the compatibility between MSM and epoxy
domains. The morphology of the hybrid resins was
observed with an SEM. Figure 4 shows typical
SEM micrographs of the cross section surface of
MSMER-20. No inorganic particles were observed
in the smooth surface of MSMER-20. On the other
hand, the silsesquioxane structures were observed
with tightly packed granules of 50 nm in diameter.
The structures indicated that the organic epoxy
domain and the inorganic silsesquioxane domain
were mixed on the molecular scale to form epoxy–
silsesquioxane nanocomposites. Formation of co-
valent linkages between epoxy and silsesquioxane
domains with DDM bridges should contribute to
the homogeneity. The distribution of MSM in the
cured epoxy resins was further examined with
SEM–EDS silicon mapping. The results are also
shown in Figure 4. Certain amounts of silicon
(shown as the bright dots), corresponding to the
silsesquioxane structure, were observed to be
homogeneously distributed in the measured win-
dow. This distribution of silicon elements gave fur-
ther evidence for the homogeneity of the MSMER
samples.
Thermal Analysis and Flame Retardancy
The glass transition temperatures of the prepared
epoxy resins were read from DSC measurements,
at a heating rate of 10 8C/min under nitrogen
(Fig. 5). Figure 6 shows the plot of the glass transi-
tion temperatures of MSMERs vs. the MSM con-
tents in the resins. Significant improvement of
the glass transition temperatures was observed
with MSMERs. A small amount of MSM, 5 wt %,
leveled up the glass transition temperature of
epoxy resins from 136 to 162 8C. Increase of the
MSM contents further increased the glass transi-
tion temperatures of MSMERs. However, the
amplitude of increase was not so obvious. Such
high Tgs lead these modified epoxy resins to be
qualified for application in high Tg printed circuit
boards and other advanced materials in microelec-
tronics. Both silsesquioxane network from silanol
gel reaction and maleimide network from malei-
mide crosslinking reaction contribute to the high
Tgs of MSMER samples. In general, alkoxysilane-
modified polymers with low alkoxysilane contents
showed decreased Tgs owing to plasticizing
effect.18,35 However, MSMERs do not encounter
such a drawback because of the incorporation of
another crosslinkable maleimide group. Moreover,
the Tg of CMSM is as high as 211 8C. Therefore,
CMSM might be considered as another class of
high performance thermosetting materials. Ther-
mal stability and thermal degradation behavior of
the epoxy resins were examined using TGA, and
the results are shown in Figure 7. Generally, addi-
tion of a flame retardant to epoxy resins usually
brings down their thermal stability.36 However,
all the MSMERs exhibited improved thermal
stability, and the amplitudes of improvement
increased with increasing the MSM amounts. In
addition, the thermal degradation patterns of
MSMERs are similar to that of pristine BE188-
based resin. In nitrogen, a one-stage weight loss
was observed. Another weight loss at a high tem-
perature region appeared for samples heated in
air, and this weight loss originated from the ther-
mally oxidative reactions.36 The activation energy
of the degradation reaction was calculated from
TGA thermograms,37 and the results were shown
in Figure 8. Increase of activation energy was
observed for MSMER samples, to indicate that
addition of MSM increased the energy barrier of
thermal degradation reactions. The increase of
activation energy was much significant for sam-
ples heated in air, especially for modified epoxy
resins containing high MSM contents. Both the
results from TGA thermograms and activation
energies of degradation reactions indicated that
using MSM as a modifier resulted in high perform-
ance epoxy resins possessing superior thermally
antioxidative stability.
Flame retardant property of the modified resins
was first evaluated with char yields38 (Table 1).
Adding MSM into BE188-based epoxy resin mark-
edly increased their char yields when heated in
nitrogen. High amounts of char yields correspond
to small amounts of flammable volatiles evolving
from resin degradation and reduced flammability
of the resins.38 High LOI values of 28–32 observed
 PREPARATION AND PROPERTIES OF EPOXY–SILSESQUIOXANE HYBRID RESINS 5793

Figure 4. Morphology of cross section surface of MSMER-20. (a) SEM micrograph

and (b) EDS–Si mapping micrograph.

for MSMERs demonstrated their superior flame values with the silicon and nitrogen contents of
retardancy (Table 1). Figure 9 showed the rela- MSMERs resins. Both char yields and LOI values
tionships of char yields in nitrogen and LOI increased with increasing the SiþN contents of
5794 LIU ET AL.

Figure 5. DSC thermograms of cured MSMERs.

the resins. Two conclusions could be drawn from
the plots. One is that the silicon–nitrogen syner-
gism on flame retardancy is observed, and the
other is that the flame retardation is performed
through a condensed-phase mechanism in the
MSMERs. Furthermore, considering processing
convenience and product cost, decreasing the
amounts of flame retardant used in the epoxy for-
mula would be desired. MSM exhibited its supe-
rior performance under this basis, as just 5 wt %
MSM is sufficient to pull the flame retardancy of
BE188-based epoxy resin above the criteria of
practical products.
Mechanical Property of MSMERs
Figure 10 showed the DMA thermograms of
MSMER-0, MSMER-10, and MSMER-20. The
appearance of tan d peaks in Figure 10 indicated
that a secondary phase transition occurred in

Figure 6. Plot of the glass transition temperatures of MSMER resins vs. their
MSM contents.
 PREPARATION AND PROPERTIES OF EPOXY–SILSESQUIOXANE HYBRID RESINS 5795

Figure 7. TGA thermograms of MSMERs.

these temperature regions. Accompanied with a
rapid decrease of storage modulus, this transition
is assigned to be the transition from glassy to rub-
bery states, i.e. the glass transition. The tempera-
tures at tan d peaks were the glass transition
temperatures of the tested samples. The glass
transition temperatures of MSMER-20 and
MSMER-10 read from tan d curves are 188 and
178 8C, respectively, both are 15–20 8C above the
values read from DSC measurements and are
higher than the glass transition temperature of
MSMER-0 (141 8C). In addition, the high storage
modulus and high glass transition temperature of
MSMER-20 indicated its high crosslinking den-
sity in network. MSMER-20 also showed rela-
tively small values of tan d peak and small area
5796 LIU ET AL.

Figure 8. The plots of activation energies of degradation reactions vs. degradation

conversions in air.

under tan d curve, indicating its reduced energy
dissipation in deformation.
CONCLUSIONS
An alkoxysilane compound possessing MSM was
prepared from HPM and GPTMS. MSM could be
used as an additive to the conventional epoxy
resin formulations, and the modified epoxy compo-
sitions could be processed under unaltered condi-
tions. Spectral analysis and SEM observation
indicated that epoxy–silsesquioxane hybrid struc-
tures in molecular level were formed in the cured
MSMERs. Curing reaction of maleimide groups
and sol–gel reactions of trimethoxysilane groups
of MSM brought highly crosslinking structures to
the epoxy resins to increase their glass transition

Figure 9. The relationships of the silicon þ nitrogen contents of MSMERs with

char yield in nitrogen and LOI values of the resins. [Color figure can be viewed in
the online issue, which is available at www.interscience.wiley.com.].
 PREPARATION AND PROPERTIES OF EPOXY–SILSESQUIOXANE HYBRID RESINS 5797

Figure 10. Plots of storage modulus and tan d vs. temperatures obtained from
DMA measurements on MSMER-0, MSMER-10, and MSMER-20. [Color figure can
be viewed in the online issue, which is available at www.interscience.wiley.com.].

temperatures, thermal stability, and mechanical
properties. Silsesquioxane and maleimide groups
from MSM also performed a silicon–nitrogen syn-
ergism of flame retardation on epoxy resins. Other
advantages of using MSM in epoxy modification
included low cost of raw materials, easy prepara-
tion and purification processes, and small amount
of usage, further increasing its potential of appli-
cations in commerce.
Financial support for this work from the National Sci-
ence Council, Taiwan is highly appreciated.
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