Synthesis and Properties of Phosphorus-Containing Epoxy

Resins by Novel Method

CHUN SHAN WANG, CHING HSUAN LIN

Department of Chemical Engineering, National Cheng Kung University, Tainan, Taiwan 701, Republic of China

Received 1 February 1999; accepted 8 June 1999

ABSTRACT: Novel phosphorus-containing epoxy resins (1–3% phosphorus content) were

synthesized by the reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide
(DOPO) and the diglycidyl ether of bisphenol A and then cured with 4,49-diaminodi-
phenyl sulfone or phenol novolac. Differential scanning calorimetry, high performance
liquid chromatography, and epoxide equivalent weight titration were used to trace the
reaction between the DOPO and the epoxy. The thermal stability and flame retardancy
were checked by thermal gravimetric analysis, the limiting oxygen index, and the
UL-94 vertical test. The glass transitions were measured by dynamic mechanical
analysis. The relation between these properties (thermal stability, flame retardancy,
and glass transition) and the DOPO contents (phosphorus content) were discussed.
© 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3903–3909, 1999
Keywords: advanced epoxy; phosphorus; DOPO; flame retardancy; limiting oxygen
index; UL-94

INTRODUCTION dide, tetrabutyl phosphonium bromide, triphenyl

Because epoxy resins have excellent heat, mois-
ture, and chemical resistance, superior electrical
and mechanical properties, and good adhesion to
many substrates, they are widely used in the
fields of coatings, adhesives, casting, potting,
composites, laminates, and encapsulation of semi-
conductor devices. Among the epoxy resins, ad-
vanced epoxy resins containing halogen atoms are
particularly useful in circuit boards or other elec-
trical laminate applications and encapsulation
applications and other applications where flame
retardant properties are desired. The advanced
epoxy resins are mostly derived from diglycidyl
ether of bisphenol A (DGEBA) and tetrabromo
bisphenol A (TBBA) with suitable catalysts. The
catalysts used for the advancement reaction in-
clude ethyl triphenyl phosphonium acetate-acetic
acid complex, ethyl triphenyl phosphonium io-
Correspondence to: C. S. Wang
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 37, 3903–3909 (1999)
© 1999 John Wiley & Sons, Inc. CCC 0887-624X/99/213903-07
phosphine, and so on. However, bromine-contain-
ing polymers release hydrogen bromide during
combustion, which causes corrosion and toxicity.
Organic phosphorus compounds typically gener-
ate less toxic gas and smoke than halogen-con-
taining compounds. Some phosphorus-containing
advanced epoxy resins were recently reported
that exhibited good flame retardancy.1– 4
In this article we provide a novel method to
create phosphorus-containing epoxy resins for
printed circuit board applications by an addition
reaction between an active hydrogen and an ep-
oxy group. Thus, 9,10-dihydro-9-oxa-10-phospha-
phenanthrene 10-oxide (DOPO, with an active
hydrogen in its structure) was used to react with
DGEBA; then the resulting resins were cured
with 4,49-diaminodiphenyl sulfone (DDS) and
phenol novolac (PN). The properties of the cured
resins were evaluated by differential scanning
calorimetry (DSC), thermal gravimetric analysis
(TGA), dynamic mechanical analysis (DMA), the
limiting oxygen index (LOI), and the UL-94 ver-
3903
3904 WANG AND LIN

tical test and these data were compared with that

of the neat DGEBA system.

EXPERIMENTAL

Materials
DGEBA with an epoxide equivalent weight
(EEW) of 187 g/eq was kindly supplied by Nan Ya
Plastics (Republic of China). Its trade name is
L-128E. PN with an OH equivalent weight of 105
g/eq was kindly supplied by Chang Chun Petro-
chemical (Republic of China). Triphenyl phos-
phine (Ph3P) and DDS were purchased from Ac-
ros. DOPO was purchased from TCI.

Characterization Scheme 1. Structures of phosphorus-containing ep-

DSC scans were obtained from samples of about 8
mg in a nitrogen atmosphere at various heating
rates (5–20°C/min) using a Perkin–Elmer DSC 7.
TGA was performed with a Perkin–Elmer TGA 7
at a heating rate of 20°C/min under nitrogen or
air from 60 to 800°C. DMA was carried out with a
Perkin–Elmer DMA 7e. The storage modulus G9
and tan d were determined as the sample was
subjected to a temperature scan mode at a pro-
grammed heating rate of 10°C/min from ambient
to 220°C at a frequency of 1 Hz and an amplitude
of 6 m. A sample with a 15-mm length, 10-mm
width, and an approximate 1.5-mm thickness was
used. The test method was performed in three-
point bending mode with a tension ratio at 110%.
The EEW of the epoxy resin and advanced epoxy
resin were determined by the HClO4/potentiomet-
ric titration method. High performance liquid
chromatography (HPLC) was performed with a
Shimadzu instrument with a RP-18 column. The
LOI was determined with an Atlas Limiting Ox-
ygen Index Chamber according to the standard
procedure (ASTM D-2863-77) with a test speci-
men bar of 7–15 cm in length, 6.5 6 0.5 mm in
width, and 3.0 6 0.5 mm in thickness. The UL-94
vertical test was performed according to the test-
ing procedure of FMVSS 302/ZSO 3975 with a
test specimen bar of 127-mm length, 12.7-mm
width, and about 1.27-mm thickness.
Synthesis of Phosphorus-Containing Epoxy Resins
The DGEBA was reacted with the DOPO at 160°C
for 300 min (Scheme 1). A typical example for IIP3
[phosphorus content is 3% (w/w)] is shown below.
oxy resins.
To a four-neck round-bottom flask equipped
with a heating mantle, stirrer, thermocouple, and
temperature controller were added 700 g of
DGEBA and 185 g of DOPO. The reaction mixture
was gradually heated to 160°C and maintained at
that temperature for 300 min. A phosphorus-con-
taining epoxy with an EEW of 308 g/eq was ob-
tained (306 g/eq theoretically).
The IIP1 and IIP2 [phosphorus content of 1 and
2% (w/w), respectively] were synthesized in the
same manner. Their EEWs were 215 and 252
g/eq, respectively (216 and 252 g/eq theoretically,
respectively).
Curing Procedure for Advanced Epoxy Resins
The phosphorus-containing epoxy resins (IIP1–
IIP3) and DGEBA were separately cured with
DDS or PN. The reactant compositions were
mixed in a 1 : 1 equivalent ratio. The mixture was
heated on a hot plate at about 150°C with contin-
uous stirring until a homogeneous solution was
obtained. The DDS curing systems did not require
a curing accelerator, but for the PN curing system
0.2 wt % of Ph3P was added as an accelerator and
stirred by hand until a homogeneous solution was
obtained. The mixtures were cured at 160°C for
1 h and 180°C for 4 h. After that the samples were
allowed to cool slowly to room temperature to
prevent cracking.

Figure 1. DSC thermograms of (a) neat DGEBA
(heating rate 20°C/min), (b) 30 phr of DOPO in DGEBA
(heating rate 5°C/min), (c) 30 phr of DOPO in DGEBA
(heating rate 10°C/min), and (d) 30 phr of DOPO in
DGEBA (heating rate 20°C/min).
RESULTS AND DISCUSSION
Synthesis of IIP1–IIP3
DSC Analysis
DSC traces of 30 phr of DOPO in DGEBA at
various heating rates and neat DGEBA are
shown in Figure 1. The melting of DOPO (mp
5 118°C) was not observed clearly in the DSC
scans, perhaps because the DOPO was already
dissolved in the DGEBA. An exotherm was ob-
served at about 180°C (5°C/min scan rate) and the
exothermic peak increased with the heating rate
while no exotherm was observed for neat DGEBA
below 280°C. A Japanese patent5 reported that
DOPO reacted with ethylene oxide to form an
addition product. The reaction is shown as fol-
lows:
Thus, the first exothermic peak may be attrib-
uted to the reaction between the DOPO and the
PHOSPHORUS CONTAINING EPOXY RESINS 3905
epoxy group. Another exothermic peak at about
260°C may be attributed to the etherification re-
action between the formed OH group and the
epoxy. The etherification reaction is shown as fol-
lows:
HPLC Trace
Although the reaction between DOPO and
DGEBA was observed during the DSC scan, the
time required to complete the reaction is still
unknown. Thus, HPLC was used to trace the re-
action. The HPLC traces showed that little reac-
tion occurred between DOPO and DGEBA below
120°C, even after 120°C for 8 h. When the reac-
tion temperature was elevated to 160°C, the re-
action occurred gradually and was completed in
300 min. Thus, DOPO-DGEBA adducts were syn-
thesized at 160°C for 5 h. To prevent degradation
at higher temperatures the higher reaction tem-
peratures were not tried.
EEW Titration
The EEW was analyzed during the reaction to
trace the reaction. For the IIP2 system the EEW
at 0% conversion is 217 g/eq and the EEW at
100% conversion is 252 g/eq theoretically. The
plot of the EEW versus the reaction time is shown
in Figure 2. The EEW increases with time and
reaches a theoretical value at 300 min, implying
the reaction is near completion after 300 min.
This result is consistent with the results of the
HPLC trace.
Thermal Properties of Cured Epoxy Resins
TGA Analysis
TGA traces of cured phosphorus-containing epoxy
resins provided additional information in regard
to their thermal stability and thermal degrada-
tion behavior. TGA thermograms and the first
derivative of the IIP/DDS series and IIP/PN se-
ries under air are shown in Figures 3 and 4,
respectively. The onset degradation temperature
(T d onset) decreased with phosphorus content;
3906 WANG AND LIN
Figure 2. The relation between EEW and reaction
time for the IIP2 system.
however, char yields increased with phosphorus
content. From the first derivative shown in Figure
3, the order of the first step decomposition tem-
perature was DGEBA/DDS . IIP1/DDS . IIP2/
DDS . IIP3/DDS; however, the order of the sec-
ond step decomposition temperature was
DGEBA/DDS , IIP1/DDS , IIP2/DDS , IIP3/
DDS. This behavior may be attributed to the de-
composition of the phosphorus group at earlier
stages in air, which formed a protection layer on
the polymer chains. Thus, as the phosphorus con-
tent increased, the first decomposition tempera-
Figure 3. TGA thermograms and first derivative of
the IIP/DDS series under air: (a) DGEBA/DDS, (b) IIP1/
DDS, (c) IIP2/DDS, and (d) IIP3/DDS.
Figure 4. TGA thermograms and first derivative of
IIP/PN series under air: (a) DGEBA/PN, (b) IIP1/PN, (c)
IIP2/PN, and (d) IIP3/PN.
ture decreased and the second decomposition
temperature increased. Although the first step
decomposition temperature decreased with in-
creasing content of DOPO, when compared with
other phosphorus-containing polymers,6,7 the de-
composition temperatures of these phosphorus
containing epoxies were extremely high.
Yokoyama et al.8 –12 reported that polymers with
a high aromatic content could possess fire retar-
dancy and thermal stability. The high T d in the
resulting epoxy resins may be attributed to the
high aromatic content of the DOPO. It may also
be attributed to the cyclic OAPOO chain being
more thermally stable than the open OAPOO
chain,6,7,13,14 which means that an introduction of
doubly stranded units into the backbone may en-
hance their thermal stability.8 –12 Char yields of
IIP/DDS series epoxy resins were higher than
that of DGEBA/DDS under air. At 700°C a 0%
char yield was found in DGEBA/DDS; however,
5–20 and 15–20% char yields were found in IIP/
DDS and IIP/PN series, respectively. Van Krev-
elen15 proposed that the char residue on pyrolysis
is linearly proportional to the oxygen index of
halogen-free polymers. Increasing the char for-
mation limits the production of combustible
gases, decreases the exothermicity of the pyroly-
sis reaction, decreases the thermal conductivity of
the burning materials, and consequently limits
the flammability of the materials. The results
shown in Figures 3 and 4 indicate that the flame
retardancy of IIP/DDS and IIP/PN series was el-
evated via the phosphorus group. Furthermore,
the residual char increased with phosphorus con-
 PHOSPHORUS CONTAINING EPOXY RESINS 3907

Table I. TGA Analysis of Cured Epoxy Resins

Char Yield at
T d 5% (°C) 700°C

Sample ID N2 Air N2 Air

DGEBA/DDS 405 379 15.1 0

IIP1/DDS 388 375 15.93 4
IIP2/DDS 386 363 17.64 11.3
IIP3/DDS 375 356 20 18.7
DGEBA/PN 423 417 19.1 0
IIP1/PN 396 386 22.5 15.9
IIP2/PN 371 383 25 19.5
IIP3/PN 366 364 26.9 20.7

tent indicating the flame retardancy is increased Figure 5. Dynamic mechanical analyses of IIP/DDS
with phosphorus content. This is consistent with series: (a) DGEBA/DDS, (b) IIP1/DDS, (c) IIP2/DDS,
and (d) IIP3/DDS.
the LOI measurement and UL-94 vertical test
discussed below. Similar TGA results were ob-
served in nitrogen and their results are shown in
Table I. the modulus at room temperature was not a func-
tion of the phosphorus content. These results in-
DMA Analysis dicated that the incorporation of DOPO into the
epoxy did not reduce the rigidity of the resulting
More detailed information may be obtained from
epoxies. This may be attributed to the high rigid-
measurements of the DM behavior of the samples
ity of DOPO, which compensates somewhat for
as a function of temperature. Figure 5 shows the
the loss in crosslink density. At high temperature
DMA of the IIP/DDS series. The order of their
the order of the modulus and height of the loss
glass transition temperatures (T g ) was DGEBA/
tangent suggests that the “crosslink density ef-
DDS . IIP1/DDS . IIP2/DDS . IIP3/DDS and the
fect” is more important than the “rigidity effect.”
height of the loss tangent was DGEBA/DDS
Similar results were shown in the IIP/PN system
, IIP1/DDS , IIP2/DDS , IIP3/DDS. At room
and the values are listed in Table II.
temperature the storage modulus was almost the
same for each sample, while at high temperature
LOI and UL-94 Measurement
the order of the modulus was DGEBA/DDS
. IIP1/DDS . IIP2/DDS . IIP3/DDS. As shown in The LOI value can be used as an indicator to
Scheme 1, the DOPO reacted with the epoxy evaluate the flame retardancy of polymers. The
group, thus reducing its functionality and conse- LOI is defined as the minimum fraction of oxygen
quently reducing its crosslink density. However, in an oxygen–nitrogen mixture that is just suffi-

Table II. DMA Analysis of Cured Epoxy Resins

T g (°C) Height of Modulus at 50°C, Modulus after T g

Sample ID (DMA) Loss Tangent 3108 Pa 3108 Pa

DGEBA/DDS 190 0.555 18.8 0.49

IIP1/DDS 188 0.653 19.2 0.24
IIP2/DDS 155 0.932 20.4 0.08
IIP3/DDS 124 1.483 18.1 0.02
DGEBA/PN 151 0.367 16.4 0.23
IIP1/PN 134 0.731 18.48 0.05
IIP2/PN 129 0.91 21.3 0.03
IIP3/PN 117 1.20 17.78 0.02
3908 WANG AND LIN
Table III. UL-94 Test and LOI Measurement of Cured Epoxy Resins
UL-94 Test Burning Timea
Sample ID P% First
DGEBA/DDS 0 .60
IIP1/DDS 0.78 9.5
IIP2/DDS 1.60 6.3
IIP3/DDS 2.49 2.1
DGEBA/PN 0 .80
IIP1/PN 0.67 53
IIP2/PN 1.41 19.2
IIP3/PN 2.23 2.1
a
The burning time before fire after they are fired for 10 s.
cient to sustain combustion of the specimen after
ignition. Thus, the flame-retardant properties of
these cured epoxy resins were further examined
by measuring the LOI and the results are shown
in Table III. Table III demonstrates that a higher
LOI value was obtained with a higher phosphorus
content. For the DDS curing system the LOI in-
creased from 22 to 28 when the phosphorus con-
tent was increased from 0 to 1.60%. For the PN
curing system the LOI increased from 21 to 27
when the phosphorus content was increased from
0 to 2.23%. A material with an LOI of 26 or higher
was rated as a flame-retardant material; thus,
incorporating 1.60% of phosphorus for the DDS
curing system (2.23% phosphorus for PN curing
system) into the epoxy chain would make these
epoxies flame-retardant polymers. The higher
LOI of IIP/DDS than the IIP/PN system at a given
phosphorus level may attributed to a nitrogen–
phosphorus synergistic effect because the nitro-
gen content in the DDS (N% 5 11.2%) was higher
than that of PN (N% 5 0). Thus, the flame retar-
dancy was IIP/DDS system . IIP/PN system
. DGEBA/DDS . DGEBA/PN. The UL-94 verti-
cal test provided another indicator to evaluate the
flame retardancy. As shown in Table III, the V-1
grade for UL-94 can be achieved for IIP1/DDS and
IIP2/PN and V-0 grade can be achieved for IIP2/
DDS and IIP3/PN. This result is also consistent
with the LOI measurement.
CONCLUSION
Novel phosphorus-containing epoxy resins (1–3%
phosphorus content) were synthesized by the re-
action of DOPO with DGEBA. DSC, LC, and EEW
UL-94
Second Grade LOI
— V-2 22
5.3 V-1 25
3.1 V-0 28
0.9 V-0 30
— HB 21
— V-2 23
4.5 V-1 25
1.1 V-0 27
titration were used to trace the reaction between
the DOPO and epoxy and the reaction was com-
pleted at about 300 min under 160°C. The flame
retardancy of the final products was examined by
an LOI measurement and UL-94 vertical test. A
V-1 grade for the UL-94 can be achieved for IIP1/
DDS (P% 5 0.78, LOI 5 25) and IIP2/PN (P%
5 1.41, LOI 5 25) and a V-0 grade can be
achieved for IIP2/DDS (P% 5 1.6%, LOI 5 28) and
IIP3/PN (P% 5 2.23, LOI 5 27). TGA showed that
the thermal stability of cured epoxy decreased
with increasing phosphorus content while char
yield increased with increasing phosphorus con-
tent. Although the thermal stability decreased
with increasing phosphorus content, theses cured
resins still have high thermal stability compared
with other phosphorus-containing polymers. In-
corporation of DOPO into the epoxy will reduce its
functionality, which consequently reduces its
crosslink density and rigidity. Thus, the order of
the T g was DGEBA/DDS . IIP1/DDS . IIP2/DDS
. IIP3/DDS and the height of the loss tangent
was DGEBA/DDS , IIP1/DDS , IIP2/DDS
, IIP3/DDS. These properties should make this
epoxy attractive for practical applications such as
flame-retardant laminates. Our work on other
physical properties (such as the dielectric con-
stant, dissipation factor, blister resistance, and
other electrical properties) of the resulting resins
is continuing.
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