Progress in Organic Coatings 66 (2009) 17

Contents lists available at ScienceDirect

Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Development and characterization of phosphorus-containing siliconized

epoxy resin coatings
S. Ananda Kumar a, , Z. Denchev b
a
b

Department of Chemistry, Anna University, Chennai 600 025, India

IPC Institute for Polymers and Composites, Department of Polymer Engineering, University of Minho, Guimares 4800-058, Portugal

a r t i c l e

i n f o

Article history:
Received 16 January 2009
Received in revised form 9 April 2009
Accepted 17 April 2009
Keywords:
Epoxy resin
Siliconized epoxy resin
Phosphorus bismaleimides
Thermal stability
Flame retardancy
Limiting oxygen index

a b s t r a c t
The objective of the present work is the development and characterization of siliconized
epoxy-phosphorus based bismaleimide coating systems using diglycidylether terminated poly (dimethylsiloxane) (DGTPDMS) and phosphorus-containing bismaleimide (PBMI) as chemical modiers for
epoxy resin. Phosphorus-containing diamine (DOPO-NH2 ) was synthesized from 9,10-dihydro-9-oxa10-phosphaphenanthrene-10-oxide (DOPO) and 4,4 -diaminobenzophenone (DABP), which was utilized
in the preparation of phosphorus-containing bismaleimide (PBMI) with maleic anhydride. Siliconized
epoxy prepolymer was prepared using epoxy resin and functionally terminated polydimethylsiloxane.
The purity and structural conformation of these materials were ascertained from FTIR and NMR spectral
studies. The prepared siliconized epoxy prepolymer was blended with varying percentages of PBMI using
diaminodiphenylsulfone (DDS) and diaminodiphenylmethane (DDM) as curing agents. The siliconized
epoxy and bismaleimide modied epoxy and siliconized epoxy coating materials were characterized by
dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA), heat distortion temperature (HDT) and Limiting oxygen index (LOI).
2009 Elsevier B.V. All rights reserved.

1. Introduction
Synthetic polymers are playing an increasingly important role
in daily life. Epoxy resins with a unique combination of properties have occupied a dominant place in the development of high
performance materials [1]. At the same time, the more demanding
requirements of the end users for higher temperatures of use and
greater resistance to oxidation of these materials push the existing
technology and knowledge to their limits. Such challenging requirements have attracted the researchers into the relatively new eld of
organicinorganic hybrid polymers. The amalgamation of organicinorganic entity into a single polymer offers a unique combination
of properties of both constituents such as improved toughness,
exibility, ame and moisture resistance, good processability and
thermo-oxidative stability [13].
In recent years, silicone compounds are considered to be among
the best modiers for epoxy resins, owing to their superior thermal
and thermo-oxidative stability, excellent moisture resistance, partial ionic nature, low surface energy, good ame retardancy and the
possible free rotation of chains about the Si-O bonds offering unique
exibility, as well as the good hydrophobicity and compressivity
[2]. However, their use is limited because of inferior mechanical

Corresponding author. Tel.: +91 44 42013108; fax: +91 44 22203543.

E-mail address: sri anand 72@yahoo.com (S.A. Kumar).
0300-9440/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2009.04.004

properties and compatibility between silicone and carbon based

polymers. Epoxy and polysiloxane systems are immiscible and their
compounding is difcult [2]. To solve this problem, several families of modied polysiloxanes, such as siloxane-(diglycidyl ether
of Bisphenol-A) DGEBA epoxy copolymer, hydroxyether-siloxane
copolymer, vinyl group containing polysiloxane and hydroxyl terminated polydimethylsiloxane have been blended with epoxy resin
[1,4,5]. Although the incorporation of the said compounds into
the epoxy resin enhances its thermal stability and toughness, it
reduces the glass transition temperature and the stressstrain properties. Hence, suitable polymeric toughening materials are needed
to improve the impact resistance and enhance the strain to fracture while retaining the thermal stability and stiffness of the epoxy
system. To achieve this, previous researchers considered that the
development of an inter-crosslinked polymer network having exible and rigid molecular segments could be an attractive method
[3].
Reportedly, the modication of epoxy resins with polyimides or
imido compounds can be a convenient approach of enhancing the
moisture resistance, glass transition temperature and the thermal
stability of epoxy resin [6]. Epoxy resins modied with maleimide
compounds, e.g. bismaleimide (BMI) have attracted attention, due
to their similar curing and processing conditions [3,68]. In addition to this, BMI-modied epoxy resins by either physical blending
or chemical reactions have been reported to show good ame retardant properties [8]. However, bismaleimide has poor solubility and

S.A. Kumar, Z. Denchev / Progress in Organic Coatings 66 (2009) 17

Scheme 1. Synthesis of m-2DOPO-2NH2 .

processability. Hence, phosphorus moiety is incorporated into BMI,

which acts as a ame retardant and plasticizer [9].
Summarizing, the development of high performance composites based on thermosetting polymers can only be achieved by
improving the properties such as high temperature, ame resistance, moisture resistance and damage tolerance by using resins,
curing agents and co-monomers with new backbone chemistries,
which provide networks with enhanced properties [10].
In the present work an attempt is made to improve
the ame resistance, moisture resistance and the thermomechanical behaviour of some epoxy resins by forming
intercrosslinked network with di-glycidylether-terminated poly(dimethylsiloxane) (DGTPDMS) and phosphorus-containing
bismaleimides (PBMI) using di-aminodiphenylsulphone (DDS)
and di-aminodiphenylmethane (DDM) as curing agents. All properties with relevance to thermo-mechanical stability and ame
retardancy of the cured resin systems were characterized.
2. Experimental
2.1. Materials
Epoxy resin GY250 representing diglycidyl ether of bisphenolA (DGEBA) with Epoxy equivalent weight (EEW) 180190
and Viscosity about 10,000 cP was obtained from Huntsman
(USA). The organo-phosphorus compound 9,10-dihydro-9-oxa10-phosphaphenanthrene-10-oxide (DOPO) was purchased
from
ADD-ABT
(Netherlands).
4,4 -diaminobenzophenone
(DDS)
and
4,4 (DABP),
4,4 -diamino-diphenylsulphone
diaminodiphenylmethane (DDM) were obtained from Alfa-Aesar
(Germany). Diglycidylether-terminated polydimethylsiloxane)
(DGTPDMS) was purchased from Merck (Germany). Dimethylformamide (DMF) and tetrahydrofuran (THF) (Sisco Research
Laboratories, India) were used as received.
2.2. Synthesis of phosphorus-containing diamine
(m-2DOPO-2NH2 )
The synthesis is shown in Scheme 1. DOPO and DABP were mixed
together in a 250 ml round bottomed ask while heating to 180 C

and stirring for 3 h causing the thickening of the reaction mixture.

After cooling down to 100 C, toluene was added into the ask. The
precipitate formed was ltered off and washed with toluene. The
obtained solid product was then recrystallized from THF to get nal
powder product (yield 60%, Mp 324325 C) [9].

2.3. Synthesis of phosphorus-containing bismaleimide (PBMI)

In a three-necked ask tted with paddle stirrer, reux condenser and nitrogen inlet, DMF, 1.0 mol of maleic anhydride and
0.5 mol of m-2DOPO-2NH2 were added. Rapid formation of precipitate of bismaleimic acid occurred on mixing the reactants together.
The synthesis is described in Scheme 2. The mixture was allowed
to stand for 30 min under stirring to complete the reaction. Then,
1 g of nickel acetate and 25 ml of triethylamine were added and
the entire mixture was reuxed. By means of pressure-equalizing
funnel, acetic anhydride was added to the reuxing mixture and
the heating was continued for an additional 3 h. The mixture was
diluted with 500 ml of water and chilled to crystallize the bismaleimide. The resulting bismaleimide was ltered and washed
with DMF.

2.4. Preparation of siliconized epoxy-bismaleimide

inter-crosslinked networks
Epoxy resin was mixed with xed amount (10%) of DGTPDMS at
90 C for 15 min with constant stirring. Then calculated amount (0,
5 and 10 wt%) of PBMI was dissolved in siliconized epoxy system
at 125 C under vigorous stirring. After complete dissolution, stoichiometric amount of DDM and DDS was added separately and
the agitation was continued at 90 C until a homogenous mixture was obtained. The products (DDM and DDS cured samples)
were subjected to vacuum to remove the trapped air and then
cast and cured at 120 C for 3 h and post cured at 180 C for 2 h
for DDM cured samples and for DDS cured samples, curing was
carried out at 140 C for 3 h and post curing at 200 C for 2 h.
Finally the castings were removed from the mould and characterized.

S.A. Kumar, Z. Denchev / Progress in Organic Coatings 66 (2009) 17

Fig. 1. FT-IR spectrum of DOPO-NH2 .

Scheme 2. Synthesis of PBMI.

2.5. Test methods

Fig. 2. FT-IR spectrum of PMBI.

FT-IR spectra were recorded using Perkin-Elmer 781 infrared

spectrometer with KBr pellets for solid samples. 1 H and 13 C NMR
spectra were recorded on a Bruker 300 MHz NMR spectrometer with dimethylsulfoxide-d6 (DMSO-d6) as solvent. Dynamic
mechanical thermal analysis (DMTA) was carried out using PerkinElmer 7 series thermal analysis system in air at a heating rate
of 10 K/min at a frequency of 10 Hz. Thermogravimetric analysis
(TGA) was carried out using Thermal Analyst 2000 (TA instruments
USA) at a heating rate of 10 C/min in an inert atmosphere. The
Heat deection temperature (HDT) and moisture absorption study
were carried out as per ASTM D648-72 and ASTM D570 standards,
respectively.

and (P-Ph) at 1596 cm1 are also observed. 1 H and 13 C NMR of

the synthesized m-2DOPO-2NH2 and PBMI are given in Figs. 36,
respectively. The chemical shifts corresponding to the amine protons and aromatic protons of m-2DOPO-2NH2 are observed at
= 3.45 ppm and = 6.626.09 ppm, respectively and the 13 C NMR
spectrum of m-2DOPO-2NH2 shows the chemical shift in the range
of 116148 ppm for aromatic carbons. The 1 H-NMR spectra of
the PBMI show the chemical shift in the range of 7.187.37 ppm
for aromatic protons. The 13 C NMR spectra of PBMI show the
chemical shifts corresponding to the existence of (Caromatic ) at

3. Results and discussion

3.1. Structural characterization of m-2DOPO-2 NH2
The FTIR spectra of m-2DOPO-2NH2 (Fig. 1.) with characteristic peaks are as follows. IR (KBr): 1186 and 930 cm1 (P-O-Ph),
1210 cm1 ( P O), 1447 cm1 (P-Ph) and 35003300 cm1 (NH2 )
conrmed the formation of m-2DOPO-2NH2 . The disappearance of
distinctive absorption peak at 2384 cm1 for P-H stretch in DOPO
and the disappearance of peaks in the range of 17101630 cm1
for C O in DABP demonstrates the reaction of DOPO and DABP.
The IR spectrum of PBMI showed (Fig. 2) strong absorptions at
1708 cm1 and 3405 cm1 are due to the imide group present in
PBMI. Absorptions due to ( C H) at 3097 cm1 , ( C N C ) at
1323 and 1117 cm1 , (P-O-Ph) at 925 cm1 , ( P O) at 1203 cm1

Fig. 3.

H NMR spectrum of DOPO-NH2 .

S.A. Kumar, Z. Denchev / Progress in Organic Coatings 66 (2009) 17

Fig. 4.

13

C NMR spectra of DOPO-NH2 .

Fig. 7. DMTA curves of PBMI-modied epoxy and siliconized epoxy systems cured
with DDS.

Fig. 5.

H NMR spectrum of PBMI.

126.8 ppm, 129.1 ppm and 129.5 ppm, while (C C) at 134.6 ppm,
and for (N-C aromatic) at 140.6 and (C O) at 169.9 ppm respectively.
3.2. Dynamic mechanical thermal analysis (DMTA)
The loss tangent spectrum (tan ) of cured samples was determined using a dynamic mechanical thermal analyzer. The main data
extracted from these runs were the glass transition temperatures
corresponding to the temperature location of the maximum value
of tan . The Tg , tan and the storage modulus data of the composites
are given in Table 1. The Tg for unmodied epoxy was found to be
177 C. A slight decrease in Tg was observed with the incorporation
of siloxane into epoxy system. For example, the Tg of 10% siloxane modied system was 165 C. The silicon-containing epoxy resin
possessed relatively high Epoxy equivalent weight (EEW) values,
which result with cured resins with low crosslink density, consequently to lower the Tg of the resin. The low Tg of the siliconized

Fig. 6.

13

C NMR spectra of PBMI.

epoxy system may also result from the free rotation of -Si-O-Silinkage [5,11]. The single Tg value obtained for the siliconized epoxy
system indicated the formation of intercrosslinked networks [2,5].
The value of Tg increased with increase in PBMI addition into epoxy
and siliconized epoxy systems. The increased Tg values may be due
to the homopolymerization of PBMI rather than Michael addition
reaction, since Michael addition reaction leads to the formation of
thermally weak amine linkage and ultimately reduce the crosslink
density due to chain extension [1214]. Homopolymerization reaction of PBMI leads to the formation of thermally stable CC linkage.
The single Tg value obtained for all the PBMI-modied epoxy and
siliconized epoxy system conrmed the formation of intercrosslinking network. Furthermore, it has been reported that incorporating
the bulky and rigid DOPO group into epoxy chain would increase
the rotational barrier of epoxy, thus therefore increasing the Tg
of the polymer [9]. The higher crosslink density was conrmed
by the greater height of the delta relaxational curve observed in
Figs. 7 and 8, which is indicative of the greater relaxational strength.
The storage modulus also increased with increasing the concentration of PBMI in epoxy and siliconized epoxy systems. It is well
known that the crosslink density is proportionate to the storage
modulus according to rubber elasticity theory [15]. In addition,
from the DMA curves of the modied epoxy resins, it was found
that both tan and storage modulus E curves of these systems displayed a single transition course implying good compatibility of the
system.

Fig. 8. DMTA curves of PBMI-modied epoxy and siliconized epoxy systems cured
with DDM.

S.A. Kumar, Z. Denchev / Progress in Organic Coatings 66 (2009) 17

Table 1
The DMA and HDT values of PBMI modied epoxy and siliconized epoxy resin.
Matrix system

Epoxy/DGTPDMS/PBMI

Glass transition
temperature (Tg , C)

tan

Storage
modulus (MPa)

Heat distortion
temperature (HDT, C)

Curative

A
B
C
D
E
F
G
H
I
J

100/00/00
100/00/00
100/10/00
100/10/00
100/00/10
100/00/10
100/10/05
100/10/05
100/10/10
100/10/10

177
173
165
152
215
195
187
182
191
190

0.299
0.258
0.226
0.228
1.61
0.35
0.33
0.34
0.40
0.37

2450
2580
2230
2400
2850
2800
2700
2770
2790
2750

165
163
146
142
244
215
178
174
195
186

DDS
DDM
DDS
DDM
DDS
DDM
DDS
DDM
DDS
DDM

3.3. Heat distortion temperature (HDT)

HDT values for epoxy, siloxane modied epoxy, PBMI modied
epoxy and siliconized epoxy systems are presented in Table 1. It was
evident that HDT decreased with increasing siloxane concentration.
This may be due to the reduced crosslink density caused by the
presence of exible -Si-O-Si- linkage. However, HDT increased for
PBMI modied epoxy and siliconized epoxy systems with increasing PBMI concentration. The enhancement in the value of HDT for
PBMI modied systems may be due to high crosslink density and
rigidity imparted by the heterocyclic structure [16].
3.4. Thermal gravimetric analysis (TGA)
Thermal gravimetric analysis determined the thermal degradation temperatures, char yields and percentages of weight loss
of the epoxy matrix systems. The TGA curves of the unmodied,
siliconized, PBMI modied epoxy and siliconized epoxy systems
cured by means of DDS are shown in Fig. 9. The incorporation of a
siloxane moiety into the epoxy resin improved its thermal stability
and raised the degradation temperature according to its percentage
concentration. The presence of siloxane skeleton in the epoxy system delays the degradation process so that more thermal energy
is required to attain the same percentage weight loss than that
required for unmodied epoxy system [2,5].
The delay in degradation caused by the siloxane moiety may
be attributed to its partial ionic nature and high bond energy of
-Si-O-Si- linkage [2,5,17]. For example, the initial degradation temperature (IDT) and the temperature required for 50% weight loss
of unmodied epoxy system are 395 C and 425 C, respectively,
whereas the IDT and the temperature required to attain the same

Fig. 9. TGA curves of PBMI-modied epoxy and siliconized epoxy systems cured
with DDS.

percentage weight loss for the 10% DGTPDMS modied epoxy systems are enhanced to 400 C and 440 C, respectively (Fig. 9). It
was observed that the IDT and 50% weight loss of 10% PBMI modied epoxy systems were reduced to 377 C and 400 C, due to the
presence of phosphorus moiety in BMI, which decomposes at low
temperatures. On heating, the phosphorus groups in the thermosetted resins rst decomposed to form a phosphorus rich residue,
which prevented further decomposition of the resins by raising the
decomposition temperature and consequently resulted in higher
char yield [5,18].
The degradation temperature of PBMI modied siliconized
epoxy system was higher when compared with that of PBMI modied epoxy system. This may be attributed to the formation of
intercrosslinking network and the synergistic effect of PBMI and
DGTPDMS [19]. The char yield of modied epoxy matrices was
higher than that of the unmodied epoxy resin. This phenomenon
indicated that the modied epoxy matrices possessed better thermal stability during high temperature condition [20]. Similar trend
was observed for the PBMI modied epoxy and siliconized epoxy
system cured with DDM (Fig. 10). The IDT, 50% weight loss, char
residue, LOI and % moisture uptake of the modied epoxy matrices
are given in Table 2.
3.5. Limiting oxygen index test
Flame resistance can be evaluated from the char residue on
pyrolysis. Van Krevelen [21] has established a linear relationship between Limiting Oxygen Index (LOI) and char residue for
halogen free polymers. A higher char yield will enhance the
ame retardance. The increased char yield limits the combustible
carbon-containing gases, decreases the exothermic effect due to
pyrolysis reactions, as well as decreases the thermal conductivity

Fig. 10. TGA curves of PBMI modied epoxy and siliconized epoxy systems cured
with DDM.

S.A. Kumar, Z. Denchev / Progress in Organic Coatings 66 (2009) 17

Table 2
TGA, LOI and moisture absorption values of PBMI modied epoxy and siliconized epoxy systems.
Matrix system

Epoxy/DGTPDMS/PBMI
COMPOSITION

Curing agents

Initial Degradation
Temperature (IDT, C)

50% weight
loss ( C)

Char
residue

Limiting oxygen
index (LOI)

Moisture
absorption

A
B
C
D
E
F
G
H
I
J

100/00/00
100/00/00
100/10/00
100/10/00
100/00/10
100/00/10
100/10/05
100/10/05
100/10/10
100/10/10

DDS
DDM
DDS
DDM
DDS
DDM
DDS
DDM
DDS
DDM

395
390
400
400
377
340
382
360
392
380

425
404
440
415
400
392
410
399
418
408

3.92
2.98
7.43
6.5
21.19
20.14
14.8
12.35
17.88
16.87

19
18.69
20.47
20.1
25.97
25.56
23.42
22.44
24.6
24.25

0.1251
0.1243
0.1125
0.1122
0.0789
0.0783
0.0655
0.0643
0.0582
0.0573

at the surface of the burning materials [22]. The LOI values of

modied epoxy matrix systems are given in Table 2. The LOI value
of unmodied epoxy was increased from 19 to 25 by the incorporation of siloxane and PBMI in to the epoxy resin. The enhancement
in LOI values, was more probably related to the char enrichment
of phosphorus and the char protecting effect of siloxane moiety
[5,2329]. Furthermore, a material with a LOI value of 21 or above
was rated as ame retardant materials [5]. Thus, incorporating
simultaneously silicone and phosphorus into the epoxy resin
would render these epoxies as ame retardant polymers.

phenomenon indicated that the modied epoxy matrices possess a

better thermal stability at high temperature conditions. DGTPDMS
and PBMI incorporation into the epoxy resin decreased the moisture
absorption, due to the inherent water repellant nature of the siloxane moiety and the negligible water absorption of bismaleimide.
A novel approach for the modication of epoxy resins with excellent thermo-mechanical properties as well as ame and moisture
resistance was proposed involving simultaneous incorporation of
siloxane, phosphorus and maleimido-containing skeleton into the
epoxy resins.

3.6. Moisture absorption behaviour

Acknowledgements

The moisture absorption characteristics of the unmodied

epoxy system, siliconized epoxy systems and PBMI modied epoxy
and siliconized epoxy systems are presented in Table 2. The presence of moisture in the matrix materials affects the electrical
insulation characteristics and mechanical properties at elevated
temperatures [24]. The siloxane incorporation into epoxy system
reduced the moisture absorption behaviour. For example, the percentage of moisture uptake for unmodied epoxy system is 0.1251,
whereas for 10% siloxane modied systems, it becomes 0.1125. The
reduction of this parameter was due to the inherent hydrophobic
nature of -Si-O-Si- linkage. Because of the free rotation and ionic
polarization of the Si-O bond, the siloxane chain is able to align itself
accordingly resulting in hydrophobic properties [25]. The inclusion
of PBMI into the epoxy and siliconized epoxy systems reduced the
moisture uptake due to the rigid aromatic hydrophobic structure
[26]. The moisture resistance property increased with increasing
PBMI content and it was observed that the PBMI incorporation
plays an important role in improving the resistance to moisture
absorption of siliconized epoxy matrix systems. This may be due
to the combined effect of PBMI and siloxane, since both are having
negligible tendency to absorb moisture.

One of the authors S. Ananda Kumar is grateful to DST

(Department of Science and Technology, INDIA, Grant No. SR/S1/PC11/2006 dtd.06.09.2006) & FCT (Portuguese foundation for Science
and Technology, Grant No. SFRH/BPD/14515/2003) for nancial
assistance to carryout this work. S. Ananda Kumar is also grateful to Ofce of Naval Research Global for sponsoring his visit to
The Netherlands to present this work in COSi 2008. The authors
are thankful to Anna University for providing necessary facility to
carryout this work.

4. Conclusion
PBMI modied epoxy and siliconized epoxy intercrosslinked
networks having varied concentrations of PBMI were prepared and
studied. The thermal properties, namely Tg , HDT and the thermal
stability of PBMI modied epoxy and siliconized epoxy matrices have been compared with those of unmodied epoxy system.
The glass transition temperature of both epoxy and siliconized
epoxy system increased with increasing PBMI concentration. This
conrmed that the homopolymerization reaction of PBMI would
predominate over Michael addition reaction. The incorporation of
DGTPDMS and PBMI into the epoxy resin enhanced the thermal stability and increased degradation temperature of epoxy resin due
to the formation of intercrosslinking network between siliconized
epoxy and bismaleimides. The char yields of modied epoxy matrices were higher than that of the unmodied epoxy resin. This

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