A Flame-Retardant Phosphate and Cyclotriphosphazene-

Containing Epoxy Resin: Synthesis and Properties

Y. W. CHEN-YANG, H. F. LEE, C. Y. YUAN

Department of Chemistry, Chung Yuan Christian University, Chung-Li, Taiwan 320, R.O.C.

Received 20 November 1999; accepted 27 December 1999

ABSTRACT: A novel flame-retardant epoxy resin, (4-diethoxyphosphoryloxyphenoxy)(4-

glycidoxyphenoxy)cyclotriphosphazene (PPCTP), was prepared by the reaction of epi-
chlorohydrin with (4-diethoxyphosphoryloxyphenoxy)(4-hydroxyphenoxy)cyclotriphos-
phazene and was characterized by Fourier transform infrared, 31P NMR, and 1H NMR
analyses. The epoxy resin was further cured with diamine curing agents, 4,4⬘-diami-
nodiphenylmethane (DDM), 4,4⬘-diaminodiphenylsulfone (DDS), dicyanodiamide
(DICY), and 3,4⬘-oxydianiline (ODA), to obtain the corresponding epoxy polymers. The
curing reactions of the PPCTP resin with the diamines were studied by differential
scanning calorimetry. The reactivities of the four curing agents toward PPCTP were in
the following order: DDM ⬎ ODA ⬎ DICY ⬎ DDS. In addition, the thermal properties
of the cured epoxy polymers were studied by thermogravimetric analysis, and the flame
retardancies were estimated by measurement of the limiting oxygen index (LOI).
Compared to a corresponding Epon 828-based epoxy polymer, the PPCTP-based epoxy
polymers showed lower weight-loss temperatures, higher char yields, and higher LOI
values, indicating that the epoxy resin prepared could be useful as a flame retardant.
© 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 972–981, 2000
Keywords: flame retardant; phosphate; cyclotriphosphazene; epoxy resin

INTRODUCTION strated high efficiency as flame retardants for

Epoxy resins are widely used as structural adhe-
sives, coatings, and advanced composite matrices
in the aerospace and electronic industries because
of their high tensile strength and modulus, low
shrinkage on cure, high adhesion to many sub-
strates, excellent chemical and corrosion resis-
tance, and good dimensional stability.1–3 The
flammability of epoxy resins, however, is a major
hazard in their applications. Therefore, many
flame retardants have been developed to improve
their flame retardancy.4 – 8 Among them, organo-
phosphorous compounds, generating negligible
amounts of toxic gas and smoke, have demon-
Correspondence to: Y. W. Chen-Yang (E-mail: yuiwhi@
mbox.cycu.edu.tw)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 38, 972–981 (2000)
© 2000 John Wiley & Sons, Inc.
972
epoxy polymers.
A traditional technique for preparing flame-
retardant epoxy polymers is to blend phosphorus-
containing additives with epoxy resins. The addi-
tive approach may be simple, but the reactive
approach, incorporating phosphorus-containing
chemical units directly into a polymer backbone,
is considered more effective. The main advantage
of using the reactive-type flame retardants is the
ability to bestow permanent flame retardancy
and, simultaneously, to maintain the original
physical and mechanical properties of the epoxy
polymer in a better way. Therefore, the study of
incorporating phosphorus-containing groups onto
the polymer backbone has attracted much atten-
tion recently.9 –18
Organocyclotriphosphazene materials, with
phosphorus and nitrogen atoms in a ring, are
known to exhibit good thermal stability and flame

retardancy. The presence of phosphorus and ni-
trogen atoms in the backbone, as well as the ether
linkages in the form of phenoxy groups intro-
duced into the cyclotriphosphazene as side
groups, have resulted in the development of a new
class of hybrid inorganic– organic phosphazene
polymers, such as polyurethanes,19 polyamides,20
polysulfones,21 maleimide resins,22–25 and epoxy
resins.26 These studies demonstrated that the in-
corporation of a substituted cyclotriphosphazene
ring into the polymer backbone significantly im-
proved heat and fire resistance. In addition,
Sadikov et al.27 reported the existence of a posi-
tive synergism between phosphorus and nitrogen.
Therefore, it is expected that the incorporation of
both phosphate groups and cyclotriphosphazene
rings into the epoxide resin may increase its phos-
phorus content and significantly improve the
flame retardancy of the corresponding cured ep-
oxy polymers.
One way to incorporate the phosphorus-con-
taining moieties into epoxy polymers is to chem-
ically modify either component with a phospho-
rus-containing oxirane or a phosphorus-contain-
ing curing agent. Nevertheless, flame retardation
can be more effective if the oxirane is phosphorus-
containing instead of the curing agent.14 There-
fore, in this study a phosphate- and cyclotriphos-
phazene-containing epoxide resin was prepared
and cured with several commercially available
diamine curing agents to prepare the correspond-
ing epoxy polymers. The curing reactions were
studied by differential scanning calorimetry
(DSC). Also studied were the thermal properties
and the flame-retardant properties of the cured
epoxy polymers.
EXPERIMENTAL
Materials
Hexachlorocyclotriphosphazene (N3P3Cl6) was
provided by the Nippon Fine Chemical Co., Ja-
pan. 4-Methoxyphenol, tetrahydrofuran (THF),
and dichloromethane (CH2Cl2) were purchased
from Merck Chemical Co. The curing agents, 4,4⬘-
diaminodiphenylmethane (DDM), dicyanodiamide
(DICY), and 4,4⬘-diaminodiphenylsulfone (DDS),
were purchased from Aldrich Chemical Co. and
used as received. 3,4⬘-Oxydianiline (ODA) was
purchased from Chriskev Chemical Co. Epon 828
was obtained from Shell Chemical Co., and DER
732, a low molecular weight liquid diglycidyl
FLAME-RETARDANT EPOXY RESIN 973
ether of bisphenol A, was obtained from Dow
Chemical Co. Triethylamine (TEA) was pur-
chased from R.D.H Chemical Co. The THF and
TEA were dried and distilled prior to use.
Synthesis of Hexakis(4-methoxyphenoxy)-
cyclotriphosphazene (1)
A suspension of sodium 4-methoxyphenoxide in
dry THF(250 mL) was prepared from 4-methoxy-
phenol (106.9 g, 0.86 mol) and sodium hydride
(20.7 g, 0.86 mol) under a dry nitrogen atmo-
sphere. A THF solution (100 mL) of N3P3Cl6 (50 g,
0.14 mol) was added dropwise, and the reaction
mixture was maintained at reflux for 24 h with
vigorous stirring. We isolated the product by pre-
cipitating it into methanol and washed it several
times to remove NaCl. The weight of 1 obtained
was 95.6 g (76.2%).
Synthesis of Hexakis(4-hydroxyphenoxy)-
cyclotriphosphazene (2)
A solution of boron tribromide (0.103 mol, 9.757
mL) in CH2Cl2 (50 mL) was added dropwise into a
solution of 15 g (0.0172 mol) of 1 in CH2Cl2 (50
mL). The reaction mixture was stirred at room
temperature for 3 h and then poured into 100 mL
of water. A white solid was collected by filtration,
washed several times with water, and dried to
obtain 13.17 g (97.1%) of 2.
Synthesis of (4-Diethoxyphosphoryloxyphenoxy)
(4-hydroxyphenoxy)cyclotriphosphazene (3)
A solution of 2 (6 g, 7.6 mmol) in 70 mL of dry
THF was prepared in a three-necked flask pro-
vided with a stirrer, reflux condenser, and a ni-
trogen inlet. To this solution, 3.68 mL of distilled
dry TEA (26.6 mmol) was added. The flask was
kept in an ice bath, and a solution of a 3-equiva-
lent ratio of diethylchlorophosphate (3.3 mL, 22.8
mmol) in 30 mL of dry THF was added dropwise
over a period of 30 min. The system then became
thick because of the precipitation of amine hydro-
chloride. After the system had been maintained
at 0 °C for 2 h, it was further reacted at room
temperature for another 48 h. The produced
amine hydrochloride salt was separated by filtra-
tion, and the solvent was removed under distilla-
tion. The residue obtained was then dissolved in
CH2Cl2, washed several times with water, and
dried over magnesium sulfate. Finally, this solu-
tion was vacuum-distilled, and liquid 3 was ob-
974 CHEN-YANG, LEE, AND YUAN
Table I. Curing Cycles of the Epoxy Resins
Curing
Epoxy Resin Temperature
Compositions (°C)
Epon 828/DDM 110
PPCTP/DDM 110
PPCTP/DDS 150
PPCTP/DICY 145
PPCTP/ODA 120
tained and identified as N3P3[OC6H4OP(O)-
(OC2H5)2]2.37(OC6H4OH)3.63 (yield ⬃ 71%).
Synthesis of (4-Diethoxyphosphoryloxyphenoxy)(4-
glycidoxyphenoxy)cyclotriphosphazene (PPCTP) (4)
To a solution of 3 (2 g, 2.0 mmol) in 10 mL of
KOH/ethanol (1 mol/L) solvent in a three-necked
flask provided with a stirrer, reflux condenser,
and a nitrogen inlet, 10 mL of epichlorohydrin
(0.12 mol) was added. The reaction mixture was
stirred for 48 h at room temperature. The precip-
itate was filtered, and the filtrate was shaken
with CH2Cl2 (30 mL), washed with a saturated
solution of NaHCO3, and then washed with dis-
tilled water. The organic layer separated was
dried over magnesium sulfate and evaporated un-
der reduced pressure. This solution was finally
vacuum-distilled, and a light-yellow liquid,
PPCTP (4), was obtained (yield ⬃ 69%).
Preparation of the Polymers
The epoxy polymers were prepared via the ther-
mal curing of PPCTP with various curing agents.
The reactant compositions were mixed homoge-
neously at a 1 : 1 equivalent ratio. The curing
conditions (listed in Table I) determined by the
DSC tracings of the respective epoxy resins were
followed for the preparation of the corresponding
epoxy polymers.
Measurements
DSC and thermogravimetric analysis (TGA) were
obtained with a Seiko SSC-5200 calorimeter and
a Seiko TG/DTA 220 analyzer, respectively. The
DSC measurements were performed at a heating
rate of 10 °C/min under a nitrogen atmosphere.
The temperature readings were calibrated with
an indium standard. The TGA measurements
Curing Postcuring
Time Temperature Time
(min) (°C) (min)
30 160 30
30 150 30
30 200 30
30 190 30
30 170 30
were implemented at a heating rate of 10 °C/min
from 50 to 600 °C in a nitrogen atmosphere at a
flow rate of 200 cm3/min. Fourier transform infra-
red (FTIR) spectra were recorded with a BIO-
RAD FTS7 instrument. For the spectra, 64 scans
at a resolution of 4 cm⫺1 were signal-averaged.
The elemental analysis was carried out for C, H,
and N with a Perkin–Elmer elemental analyzer
with acetanilide as a standard. The 1H, 13C, and
31
P NMR spectra were obtained with a Bruker AC
200 spectrometer. An 85% H3PO4 aqueous solu-
tion assigned to 0 ppm was used as an external
reference for the 31P NMR spectra. As a conven-
tion, the 1H and the 13C NMR spectra were refer-
enced to the signal of tetramethylsilane. The lim-
iting oxygen index (LOI) values were measured
by a modified method as reported in the litera-
ture.28
RESULTS AND DISCUSSION
Synthesis and Characterization
The phosphate- and cyclotriphosphazene-contain-
ing epoxy resin (PPCTP) was considered a cyclo-
triphosphazene substrate containing phosphate
and epoxide functionalities. Therefore, as de-
picted in Scheme 1, the hydroxy-function-contain-
ing cyclotriphosphazene 2 was prepared first by
the reaction of N3P3Cl6 with 4-methoxyphenol to
obtain 1 and then by reduction with an excess of
BBr3.29 Through a partial phosphorylation, 2 was
reacted with diethylchlorophosphate to give 3. Fi-
nally, PPCTP was obtained by the reaction of 3
with epichlorohydrin.
The structures of both cyclotriphosphazenes 1
and 2 were confirmed by FTIR and NMR (1H, 13C,
and 31P) spectroscopy. The corresponding data
are listed in Table II. The only sharp singlets at ␦
⫽ 10.62 ppm and ␦ ⫽ 10.07 ppm in the 31P NMR
 FLAME-RETARDANT EPOXY RESIN 975

in Table III. The content of the epoxide group in 4

Scheme 1.
spectra of the two compounds indicate a complete
and equivalent substitution of the chlorine in the
parent N3P3Cl6.
The different functional groups attached to the
cyclotriphosphazene ring were unambiguously
identified by 1H and 13C NMR spectra. The sin-
glets at ␦ ⫽ 3.72 ppm (1H NMR) and at ␦ ⫽ 55.4
ppm (13C NMR) are the characteristic peaks for
the methoxy group in 1. These peaks disappeared
from the spectrum of 2, supporting the structure.
The results are similar to those reported by
Medici et al.29
The functionalized cyclotriphosphazenes 3 and
4 were also characterized by FTIR and 1H and 31P
NMR spectra. The corresponding data are listed
was determined by titration and confirmed by
elemental analysis.
As shown in the FTIR spectrum of 3 [Fig. 1(a)],
the strong absorptions peaking between 1262 and
1185 cm⫺1 correspond to the PAN stretching in
the backbone; the strong absorptions peaking at
3272 cm⫺1 correspond to the free OOH stretching
of the 4-hydroxyphenoxy(OOC6H4OH) group.
The absorption at 1033 cm⫺1 indicates the forma-
tion of the P(O)OOOCH2O linkage, and the
strong absorptions peaking at 1170 and 953 cm⫺1
(OPOOOPh) reveal the presence of a phosphate
structure.
As was expected, the 1H NMR spectrum of 3
showed a multiplet between 7.01and 6.83 ppm for
the aromatic phenoxy protons (OC6H5) and a mul-
tiplet between 4.24 and 4.09 ppm (OOCH2CH3)
and a triplet between 1.37 and 1.26 ppm
(OOCH2CH3) for the ethoxy group of the phos-
phate.
Because the (4-diethoxyphosphoryloxyphenoxy)-
[OC6H4OP(O)O(OC2H5)2] and 4-hydroxyphenoxy-
(OC6H4OH) groups have similar shielding effects
on the phosphorus atoms attached to the cyclot-
riphosphazene ring, the 31P NMR spectrum of 3
showed an overlap multiplet peak between 9 and
10 ppm that was difficult to resolve, whereas a
singlet peak at ⫺6.26 ppm was assigned to the
phosphorus of the diethyl phosphate group. This
result confirms the occurrence of phosphorylation
and supports the structure expected for 3.
In the FTIR spectrum of 4 [Fig. 1(b)], the
strong absorption peaking at 3272 cm⫺1 of 3 dis-

Table II. Characterization Data for Compounds 1 and 2

Elemental Analysis (%) NMR (ppm)

Compound C H N O 31
P 1
H 13
C IR (cm⫺1)

1
Calcd. 57.7 4.81 4.81 22.00 10.62 3.72 (s, 3H, OCHគ 3) 55.4 គ H3)
(C 1507 (CAC)
Found 57.5 4.84 4.81 22.04 6.8–6.6 (m, 4H, aromatic) 114.2 (aromatic) 1260 (PAN)
121.8 (aromatic) 1180 (PAN)
144.3 (aromatic) 1035 (PhOOOC)
156.6 (aromatic) 972 (POOOPh)
2
Calcd. 54.76 3.80 5.32 24.30 10.07 6.71 (s, aromatic) 116.5 (aromatic) 3321 (OOH)
Found 53.89 3.84 5.34 25.05 122.5 (aromatic) 1505 (CAC)
144.1 (aromatic) 1255 (PAN)
155.2 (aromatic) 1182 (PAN)
960 (POOOPh)
976 CHEN-YANG, LEE, AND YUAN

Table III. Characterization Data for Compounds 3 and 4

Elemental Analysis NMR (ppm)

Compound C H N 31
P 1
H IR (cm⫺1)

3
Calcd. 49.11 4.62 3.78 9–10 4.24–4.09 (m, 2H, OCHគ 2CH3) 3272 (OOH)
Found 48.95 4.70 3.81 ⫺6.26 1.37–1.26 (t, 3H, OCH2CH គ 3) 1262–1185 (PAN,
PAO)
7.01–6.83 (4H, aromatic) 1170 (PAN)
1033 (P(O)OOOCH2)
953 (POOOPh)
1505 (CAC)
4
Calcd. 51.60 5.02 3.20 9–10 2.89–2.62 (2H, 1265–1188 (PAN,
OOH2CHCOCH គ 2) PAO)
Found 51.41 5.13 3.24 ⫺6.26 3.23 (m, OOH2CH គ COCH2) 1500 (CAC)
3.89–3.48 (2H, 1031 (POOOCH2)
OOH គ 2CHCOCH2)
1.41–1.19 (t, 3H, OCH2CH គ 3) 952 (POOOPh, COC)
4.32–4.13 (m, 2H, OCH គ 2CH3)
6.90–6.67 (aromatic)

appeared, indicating that the free OOH was no a peak at ␦ ⫽ 3.89 –3.48 ppm for
longer in 4. The absorption peak around 914 cm⫺1
on the oxirane ring overlaps the strong absorption
peaking at 952 cm⫺1 for POOOPh as expected.
The 1H NMR spectrum of 4 showed a multiplet
at 3.23 ppm for
and a triplet at 1.41–1.19 ppm (OOCH2CH3), a
multiplet at 4.32– 4.13 ppm (OOCH2CH3), and
multiplets at ␦ ⫽ 6.90 – 6.67 ppm for aromatic
protons. The 31P NMR spectrum of 4 showed a
a doublet of multiplets at ␦ ⫽ 2.89–2.62 ppm for multiplet peak located between 9 and 10 ppm for

Figure 1. FTIR spectra of (a) compound 3 and (b) Figure 2. DSC thermograms of the cure of PPCTP,
compound 4. Epon 828, and DER 732 with DDM.
 FLAME-RETARDANT EPOXY RESIN 977

Table IV. The Initial Curing Temperature of

Various Epoxies Cured by the DDM Curing Agent

Epoxy Resin Initial Curing Temperature (°C)

PPCTP 76
DER 331 80
Epon 828 87
DER 732 100

the phosphorus atoms of the cyclotriphosphazene

ring and a singlet at ⫺6.26 ppm for [P(O)(C2H5)2].
These results imply that the oxiranes were suc-
cessfully substituted onto 3 to form 4, as expected.
Because both the phosphate and epoxide
Figure 3. DSC thermograms of the cure of PPCTP
groups were incorporated into the cyclotriphos-
with different curing agents.
phazene substrate by reactions involving the free
OOH groups, the content of the epoxide group
was determined by the number of free OOH reactivity of these four curing agents toward
groups left after the phosphorylation of compound PPCTP resin increases in the order DDS ⬍ DICY
2. The titration method, which is a traditional ⬍ ODA ⬍ DDM, the same order as the nucleophi-
and effective method for the determination of ep- licity of the corresponding amino group. The high-
oxide content,3 was used to determine the average est reactivity of DDM toward PACTP was attrib-
n value (number of epoxide groups per molecule) uted to the comparatively high basicity of its
of 4; a value of 3.63 was obtained. The elemental amine nitrogen because of the electron-donating
analysis data listed in Table III confirm the re- effect of the methylene group.
sult.

Thermal and Flame-Retardant Properties

Reactivity of PPCTP Toward the Curing Agents
The curing reaction of PPCTP with the curing
agent DDM was studied by DSC and compared to
that of Epon 828 and DER 732. The reactivities of
these systems were determined by the starting
temperatures of the exothermic peaks. As shown
in Figure 2 and Table IV, PPCTP is more reactive
toward DDM than the other two commercial ep-
oxy resins. This may be ascribed to the electronic
effect. The polymerization of an epoxy resin with
an amine is considered to occur via a nucleophilic
attack of the amine nitrogen on the methylene
carbon atom of the epoxy group. The electron-
withdrawing cyclotriphosphazene ring in the
PPCTP reduces the electron density of the meth-
ylene carbon atom and makes the reaction be-
tween the oxirane ring and the amine easier.
The reactivities of various curing agents to-
ward PPCTP were also studied via DSC. The DSC
thermograms of PPCTP and the selected curing-
agent compositions are shown in Figure 3. As
summarized in Table V, the exothermal starting
temperature increases in the order DDM ⬍ ODA
⬍ DICY ⬍ DDS, indicating that the chemical
The thermal properties of the cured epoxy poly-
mers were evaluated by TGA under nitrogen. Fig-
ure 4 shows the TGA thermograms of the cured
PPCTP/DDM and Epon 828/DDM polymers. The
Epon 828/DDM polymer exhibited a 5% weight
loss at 338 °C and a rapid weight loss around 387
°C. Unlike the one-stage weight-loss behavior of
the Epon 828/DDM polymer, the PPCTP/DDM
polymer showed a two-stage weight loss. The
first maximum weight-loss temperature (Tmax1)
around 313 °C indicates that the thermal stability
of the PPCTP/DDM polymer was less than that of
the Epon 828/DDM polymer. Nevertheless, the
Table V. The Initial Curing Temperatures of
PPCTP Cured by Various Curing Agents
Curing Agent Initial Curing Temperature (°C)
DDM 76
ODA 82
DICY 130
DDS 135
978 CHEN-YANG, LEE, AND YUAN

Figure 4. TGA thermograms of PPCTP and Epon 828 Figure 5. TGA thermograms of PPCTP cured with
cured with DDM. various curing agents.

temperature in the high-temperature region but

percentage of the weight loss of PPCTP/DDM be-
fore reaching 313 °C was less than 10%. This
weight loss could be ascribed to the decomposition
of the phosphate groups that caused the forma-
tion of the phosphorus-rich residues to inhibit
further decomposition of the polymer. Conse-
quently, the second maximum weight-loss tem-
perature (Tmax2) of the PPCTP/DDM polymer was
higher than the Tmax of the Epon 828/DDM poly-
mer (as listed in Table VI), implying that the
thermal stability of the resin at a high tempera-
ture was improved as the phosphate and the cy-
clotriphosphazene moieties were covalently incor-
porated into the epoxy resins. This phenomenon,
in agreement with other studies,18 played an im-
portant role in improving the flame-retardant
properties of the resins.
The formation of phosphorus-rich char in the
decomposition of cyclotriphosphazene-containing
epoxy resins not only increased the weight-loss
also resulted in a high char yield. An increase in
char formation can usually limit the production of
combustible carbon-containing gases, decrease
the exothermicity due to pyrolysis reactions, and
decrease the thermal conductivity of the surface
of a burning material. Therefore, the flammabil-
ity of the material is reduced.
More TGA thermograms of the PPCTP resin
cured by the various curing agents are shown in
Figure 5. The weight-loss data are summarized in
Table VI. The results show a similar weight-loss
behavior for all the PPCTP epoxy polymers with
the various curing agents. The initial pyrolysis
temperature decreased when the phosphorus-con-
taining PPCTP epoxy was incorporated, and the
first rapid maximum weight-loss temperatures of
the PPCTP-based cured resins were all lower, just
as the char yields at 600 °C were all higher, than
that of the Epon 828-based resin, as discussed
previously.

Table VI. Thermogravimetric and LOI Data of the PPCTP-Containing Epoxy Polymers

Temperatures of Weight Loss from

TGA (°C) (in N2) Char at
Epoxy Resin 600°C Phosphorus
Compositions T 5% Loss T max1 T max2 (%) Content (%) LOI

Epon 828/DDM 338 — 387 16.2 0.00 18.5

PPCTP/DDM 281 313 454 41.2 10.45 32.0
PPCTP/ODA 275 318 466 46.2 10.47 33.0
PPCTP/DDS 321 360 469 53.1 10.85 34.0
PPCTP/DICY 301 333 479 50.0 11.68 36.0

Figure 6. The effect of the phosphorous content on
the LOI value.
The flame-retardant properties of the epoxy
polymers were further examined through mea-
surement of the values of the LOI. As listed in
Table VI, the LOI values of the cured PPCTP-
based epoxy polymers were at least 13.5 higher
than that of the phosphorus-free Epon 828/DDM
epoxy polymer, indicating that the flame retar-
dancy of all the PPCTP-based epoxy polymers
prepared in this study was highly improved. This
was attributed to the high nitrogen and phospho-
rus contents in the polymers, which are believed
to have a synergistic effect during burning. In
addition, the PPCTP/DICY polymer showed a
higher LOI value than the other PPCTP-based
epoxy polymers, indicating a more effective syn-
ergism of phosphorus–nitrogen elements due to
the higher nitrogen content in DICY. The LOI
value increased with an increase in phosphorus
content and char yield at 600 °C as expected and
as shown in Figures 6 and 7.
To learn the possible mechanism of the flame
retardancy of the PPCTP-containing epoxy res-
ins, the cured resins were heated from room tem-
perature to 380 and 600 °C; then, the residues
were analyzed by FTIR and elemental analysis.
After heating, the samples became spumific char,
implying that some volatile compounds evolved
during degradation. However, this phenomenon
was not found in the Epon 828/DDM system.
The FTIR spectra of the PPCTP/DDM sample
before and after heating are presented in Figure
8. In the spectrum labeled a, the absorption that
peaked at 1503 cm⫺1 is assigned to CAC of the
aromatic ring, and the bands between 1100 and
1300 cm⫺1 are assigned to the combination of the
stretching vibrations of the PAN bonds in the
FLAME-RETARDANT EPOXY RESIN 979
Figure 7. The effect of the char yield on the LOI
value.
cyclotriphosphazene ring and that of the PAO
bond in the phosphate group. The spectral region
between 740 and 1100 cm⫺1 corresponds to the
absorption range of the POOOC bonds. The
bands that peaked at 1035 and 950 cm⫺1 repre-
sent POOOC2H5 and POOOPh stretching vi-
brations, respectively. In the spectrum labeled b,
the characteristic absorption bands of the cyclot-
riphosphazene ring, 1185 and 1233 cm⫺1 for the
PAN vibration and 950 cm⫺1 for the POOOPh
vibration, remain at 380 °C. However, the disap-
pearance of the band at 1035 cm⫺1 and the
change of the spectral region between 1100 and
1300 cm⫺1 indicate the cleavage of phosphate
groups in the first thermal degradation as predi-
cated by the TGA thermogram. The cleavage of
ethoxy groups, which may be oxidized to CO2, was
believed to be the cause of the formation of spume
at this stage. However, the spectrum labeled c
indicates that the aromatic rings were completely
decomposed and the residue was mainly phospho-
Figure 8. FTIR spectra of the condensed phase dur-
ing thermal degradation at various temperatures: (a)
25 °C, (b) 380 °C, and (c) 600 °C.
980 CHEN-YANG, LEE, AND YUAN

Table VII. Elemental Analysis Data of PPCTP-Containing Epoxy Polymers at Various Temperatures

O% H% N% P%

30°C 380°C 600°C 30°C 380°C 600°C 30°C 380°C 600°C 30°C 380°C 600°C

EPON 828/DDM 74.71 79.17 75.3 6.92 6.27 3.19 2.81 3.02 3.26 — — —
PPCTP/DDM 56.73 55.75 43.04 5.67 4.65 1.72 3.96 2.92 3.02 10.45 11.58 15.84

rus compounds after the sample was heated at
600 °C, which indicates that most of the phospho-
rus atoms remained in the char.
Table VII shows the changes in the relative
chemical composition of the PPCTP/DDM sam-
ples before and after being heated at 380 and 600
°C. In comparison to the result of the Epon 828/
DDM cured resin, the change of the chemical
composition of the PPCTP/DDM samples show
that there was a decrease in the content of carbon
and nitrogen, whereas the content of phosphorous
significantly increased as the heating tempera-
ture increased. This confirms the accumulation of
phosphorus in the char during decomposition as
found in the FTIR spectra.
The overall result suggests that with phos-
phate and phosphazene moieties in the epoxy-
resin system, the formation of a vapor phase to
dilute the oxygen concentration above the sample
together with the formation of the phosphorus-
rich condensed phase to inhibit further decompo-
sition of the sample during the thermal degrada-
tion, the resulting high char yield, and the en-
hanced flame-retardancy effect was enhanced as
indicated by the high LOI value. This demon-
strates that the phosphate- and cyclotriphospha-
zene-containing epoxy resin prepared in this
study, PPCTP, is useful for formulating a flame-
retardant epoxy-resin/amine-curing-agent sys-
tem and has potential for wide versatility in its
applications.
CONCLUSION
A novel flame-retardant epoxy resin, PPCTP, was
synthesized. Flame-retardant cured epoxy resins
were also prepared via the curing of PPCTP with
several commercial curing agents. Compared
with Epon 828 and DER 732, the higher reactivity
of PPCTP toward diamine curing agents is attrib-
uted to the presence of the electron-withdrawing
cyclotriphosphazene group in the PPCTP. Fur-
thermore, the reactivities of the curing agents
toward PPCTP are in the order DDM ⬎ ODA
⬎ DICY ⬎ DDS. The higher char yields and LOI
values of the PPCTP-based epoxy polymers exhib-
ited their good flame-retardant properties. Such
properties make PPCTP useful as a flame-retar-
dant resin for preparing flame-retardant epoxy-
resin systems.
The authors wish to thank the National Science Coun-
cil, R.O.C. for its financial support and Nippon Fine
Chemical Company, Japan for providing the hexachlo-
rocyclotriphosphazene.
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