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Preparation and Characterization of

Vinyl Ester Monomer–Toughened Epoxy-
Clay Hybrid Nanocomposites: Thermal
and Morphological Properties
a a b a c
A. Chandramohan , M. Mandhakini , K. Dinakaran & M. Alagar
a
Polymer Nanocomposites Lab, Department of Chemical
Engineering, Alagappa College of Technology Campus, Anna
University, Chennai, India
b
Department of Chemistry, Madras Institute of Technology Campus,
Anna University, Chennai, India
c
Department of Applied Science and Technology, Alagappa College
of Technology Campus, Anna University, Chennai, India

Version of record first published: 24 Aug 2012

To cite this article: A. Chandramohan, M. Mandhakini, K. Dinakaran & M. Alagar (2012): Preparation
and Characterization of Vinyl Ester Monomer–Toughened Epoxy-Clay Hybrid Nanocomposites: Thermal
and Morphological Properties, International Journal of Polymer Analysis and Characterization, 17:7,
477-484

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 International Journal of Polymer Anal. Charact., 17: 477–484, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 1023-666X print=1563-5341 online
DOI: 10.1080/1023666X.2012.696399

PREPARATION AND CHARACTERIZATION OF VINYL

ESTER MONOMER–TOUGHENED EPOXY-CLAY
HYBRID NANOCOMPOSITES: THERMAL AND
MORPHOLOGICAL PROPERTIES

A. Chandramohan,1 M. Mandhakini,1 K. Dinakaran,2 and

M. Alagar1,3
1
Polymer Nanocomposites Lab, Department of Chemical Engineering,
Alagappa College of Technology Campus, Anna University, Chennai, India
Downloaded by [Anna University] at 00:47 25 August 2012

2
Department of Chemistry, Madras Institute of Technology Campus,
Anna University, Chennai, India
3
Department of Applied Science and Technology, Alagappa College of
Technology Campus, Anna University, Chennai, India

An intercross-linked network of vinyl ester monomer (VEM)-toughened epoxy-clay hybrid

nanocomposites was developed and characterized using analytical methods. Cyclohexyl-1,
10 -bis[4-(c-2-methylphenoxy)-a-hydroxypropylacrylate]-based VEM was synthesized
from 1,1-bis(3-methyl-4-glycidyloxyphenyl) cyclohexane and acrylic acid. The VEM was
subsequently blended with diglycidyl ether of bisphenol-A (DGEBA) resin cast and cured
with 4,40 -diaminodiphenylmethane (DDM). VEM-toughened epoxy matrices were rein-
forced with organophilic montmorillonite (OMMT) clay yielding hybrid epoxy nanocom-
posites. Data obtained from thermal characterization indicate that the introduction of
VEM into epoxy resin improves thermal properties. The morphological behavior of the
nanocomposite was analyzed by X-ray diffraction (XRD) analysis and transmission
electron microscopy (TEM).

Keywords: Epoxy resin; Flame retardancy; Morphology; Nanocomposites; Vinyl ester monomer

INTRODUCTION
Nanocomposites are attractive because of formulation simplicity, low filler
content, and particularly the special properties imparted by the nanoscale reinforcing
material. Special features of composites are improved stiffness, strength and impact
resistance, high heat deflection temperature, and low liquid and gas permeability.[1,2]
Epoxy resin-based diglycidyl ether of bisphenol-A (DGEBA) has been noted for its
unique properties such as outstanding adhesion to various surfaces, light weight,

Submitted 20 February 2012; accepted 2 April 2012.

The authors acknowledge the financial support offered for completing this research work by the
University Grants Commission (UGC), Government of India.
Correspondence: M. Alagar, Polymer Nanocomposites Lab, Department of Chemical Engineering,
Alagappa College of Technology Campus, Anna University, Chennai - 600 025, India. E-mail:
mkalagar@yahoo.com

477
 478 A. CHANDRAMOHAN ET AL.

high strength, extreme durability, and stability under UV exposure and chemical
resistance.[3] However, the brittle behavior of epoxy resin restricts its utility for
high-performance advanced industrial and engineering applications.[4] In our earlier
work, we have reported the enhanced properties of azomethine, poly sulfones,
soybean oil, caprolactum, bismaleimides, and cyanate ester toughened epoxy
intercross-linked network nanocomposites.[5–11]
In order to enhance their engineering properties, organic matrix resins are often
reinforced with inorganic fillers such as glass fiber, clay, polysilsesquioxane, silica, cer-
amics, and titania, for advanced composite applications. Among inorganic reinforce-
ments, clay is a unique and versatile material available in nanometer scale to prepare
polymer nanocomposites. The most widely used layered silicate for the preparation of
polymer-clay nanocomposites is montmorillonite (MMT), which is comprised of a
multilayer silicate mineral that possesses inorganic cations within its galleries in a
hydrophilic environment. The MMT clay surface is often grafted with cetyltrimethy-
Downloaded by [Anna University] at 00:47 25 August 2012

lammonium ions to make the clay surface organophilic and thus more compatible with
the organic resin. The addition of organophilic MMT clay reduces the brittle behavior
of epoxy resins and enhances their thermo-mechanical properties.[12–15]
In the present work, an attempt is made to improve the toughness and thermal
stability of epoxy by forming intercross-linked polymer networks with a new class of
vinyl ester monomer (VEM). The chemical structure of the VEM monomer is carefully
designed in such a way that the alicyclic ring structure imparts flexibility and strength.
The terminal epoxy groups were functionalized with vinyl ester groups to facilitate
chain extension by a thermally induced reaction. DGEBA toughened with varying
compositions of VEM and clay, hybrid nanocomposites in the form of intercross-linked
polymer networks (ICNs), were developed and characterized by standard methods in
order to evaluate their suitability for the manufacturing high-performance composites.

EXPERIMENTS
Materials
Diglycidyl ether of bisphenol-A, DGEBA (LY556 equivalent weight 180), and
4,40 -diaminodiphenylmethane (DDM) were received from Ciba-Geigy Ltd India.
MMT clay was received from Sigma Aldrich (USA). 1,1-Bis (3-methyl-4-hydroxyphe-
nyl) cyclohexane, 1,1-bis(3-methyl-4-glycidyloxyphenyl) cyclohexane, organophilic
montmorillonite (OMMT) clay, and OMMT clay-reinforced epoxy nanocomposites
were prepared according to reported procedures.[16,17]

Synthesis of Cyclohexyl-1,10 -bis[4-(c-2-methylphenoxy)-a-

hydroxypropylacrylate]
Vinyl ester monomer was prepared using 1,1-bis(3-methyl-4-glycidyloxyphenyl)
cyclohexane and acrylic acid. One mole of 1,1-bis(3-methyl-4-glycidyloxyphenyl)
cyclohexane and 2 moles of acrylic acid were placed in a round-bottomed flask and
mixed at 70
C for 4 h with constant stirring to obtain vinyl ester monomer.[18] The
reactions involved during the preparation of vinyl ester monomer are given in
Scheme 1.
 VEM TOUGHENED EPOXY-CLAY NANOCOMPOSITES 479
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Scheme 1. Synthesis of cyclohexyl-1,10 -bis[4-(c-2-methylphenoxy)-a-hydroxypropylacrylate].

Spectral analysis: infrared (KBr, cm1): 3448, 2935, 2859, 1726, 1636, 1616,
1408, 1295, and 1249.1H nuclear magnetic resonance (NMR) (ppm): d 1.52 (s, 6H),
1.87–1.92 (m, 4H), 2.19 (s, 6H), 2.16–2.17 (m, 4H), 3.98–4.04 (m, 4H), 5.82–5.88
(m, 2H), 6.14 (d, J ¼ 7.14 Hz 4H), 6.34–6.42 (m, 2H), 6.69–6.72 (m, 2H, Ar), and
7.03 (s, 4H, Ar). 13C NMR (ppm CDCl3): d 166.1, 154.0141.4, 131.5, 128.0, 127.9,
126.1, 125.3, and 114.5 (C aromatic); 95.7, 68.4, 65.8 43.2, 37.3, 26.4, 22.9, and
16.5 (aliphatic). EI-MS [Mþ]: 553.

Preparation of Hybrid VEM-Toughened Epoxy Resins

VEM-modified DGEBA epoxy matrices were prepared by dissolving varying
percentages (5%, 10%, and 15% (by weight)) of VEM and a fixed amount of epoxy
resin (100 g) with continuous heating at 80
C for 15 min. The blend obtained was
degassed under vacuum for 30 min and then cooled to 60
C. The stoichiometric
quantity of DDM was then added to the blend with continuous stirring until a
homogeneous liquid was obtained. The product was subjected to vacuum to remove
the entrapped air and poured into a preheated mold. The samples were cured succes-
sively at 120
C for 3 h and post-cured at 180
C for 2 h and finally removed from the
mold and characterized.

Preparation of OMMT Clay-Reinforced Hybrid VEM-Toughened Epoxy

Nanocomposites
The epoxy resin was mechanically stirred with the desired amount of OMMT
(1%, 3%, and 5% (by weight)) at 70
C for 24 h. To the organophilic clay-filled epoxy
resins, VEM 10 wt.% was added separately at 80
C during 15 min with constant
stirring. A stoichiometric amount of DDM (27.2 g) corresponding to the epoxy
equivalent was also added. The product was subjected to vacuum to remove the
 480 A. CHANDRAMOHAN ET AL.

entrapped air and poured into a preheated mold. The samples were cured by the
above described procedure.

TEST METHODS
The glass transition temperature (Tg) of the samples was determined using a
DSC 200 PC differential scanning calorimeter (Netzsch Gerateban GmbH) in the
temperature range between 50
and 400
C at a heating rate of 10
C per minute in
nitrogen atmosphere. Thermogravimetric analysis (TGA) was carried out using a
DSTA 409 PC analyzer (Netzsch Gerateban GmbH) at a heating rate of 10
C per
minute in nitrogen atmosphere. The values of limiting oxygen index (LOI) are calcu-
lated from char yield using the equation LOI ¼ 17.5 þ 0.4r where r is the polymer’s
char yield. X-ray diffraction (XRD) patterns were recorded at room temperature by
monitoring the diffraction angle 2h from 0.5 to 40
at the low angle on a Rich Seifert
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(Model 3000) X-ray powder diffractometer. A JEOL JEM-3010 analytical trans-

mission electron microscope, operating at 300 kV with point-to-point resolution,
was used to study surface characteristics.

RESULTS AND DISCUSSION

Thermal Properties
Differential scanning calorimetric analysis. The values of Tg for
unmodified epoxy resin, VEM-toughened epoxy resin, and organo clay-filled VEM-
toughened epoxy resin were obtained from DSC analysis and are presented in
Table I. The unmodified epoxy system with an addition of clay exhibits enhanced
Tg values due to the presence of clay at the nanoscale level, which decreases the
degradation rate and enhances the curing temperature. It is suggested that the
decrease in Tg values of clay-filled nanocomposites may be due to the interference
of clay with cross-linking density, in addition to epoxy homopolymerization and
the plasticization effect imparted due to the presence of alkylammoniumion in
clay.[19,20] Tg values decrease with an increase in the concentration of VEM content

Table I. Thermal data of clay-filled VEM-toughened DGEBA-based nanocomposites

TGA

DGEBA=VEM=clay Initial 60% Weight Char yield (%) LOI

composition Tg (
C) decomposition (
C) loss (
C) 800
C (%)

100=00=00 160 352 417 12.6 22.5

100=05=00 177 340 403 7.8 20.6
100=10=00 171 354 413 16.5 24.1
100=15=00 168 363 426 23.7 26.9
100=00=01 150 348 433 24.3 27.2
100=00=03 156 356 438 26.1 27.9
100=00=05 161 363 445 31.5 30.1
100=10=01 162 360 449 21.7 26.2
100=10=03 159 368 451 25.2 27.6
100=10=05 152 371 464 29.8 29.5
 VEM TOUGHENED EPOXY-CLAY NANOCOMPOSITES 481

in the unmodified epoxy resin. This may be due to the presence of flexible units,
which in turn decrease the effective cross-linking density, accelerate the reaction rate,
and reduce the curing temperature. This also created an excess free volume in the
matrix system and leads to reduction in the values of Tg, which is associated with
mobility of molecules. The incorporation of organo clay into VEM-toughened epoxy
resin decreases the value of Tg. The decrease of Tg may be due to the catalytic homo-
polymerization of the epoxy and plasticization of organo clay–filled epoxy systems
by the cetyltrimethylammonium ions present on the surface of the organo clay.
Thermogravimetric analysis. The initial degradation temperature, 60%
weight loss temperature, and char yield values of unmodified epoxy, VEM-toughened
epoxy, organo clay–filled epoxy resin and organo clay–filled VEM-toughened epoxy
resin systems were obtained from TGA and are shown in Table I. The incorporation
of VEM into epoxy resins improves thermal stability and enhances the degradation
temperature according to the rise in percentage concentration of VEM. The delay
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in degradation caused by the VEM moiety can be attributed to the cross-linked net-
work and entangled structure of VEM-toughened epoxy systems. The initial degra-
dation temperature of organo clay–filled VEM-toughened epoxy resin is improved
by 19
C compared to the unmodified resin; the char yield at 800
C was also increased.
The degradation temperature of organophilic clay–filled epoxy systems and organo-
philic clay–filled VEM-toughened epoxy systems increases with increased incorpor-
ation of organo clay concentration. The increase in degradation temperature may
be due to the network structure[21] formed between the silicate layers of organo clay
and epoxy resins by the hydrocarbon chain of cetyltrimethylammonium ions present
in the organo clay. Further, the enhancement of thermal stability may be due to the
incorporation of nano silicate layers into epoxy matrices, which act as an insulator
and mass transport barrier to the volatile products generated during decomposition.
Flame retardancy. The flame retardancy of the neat epoxy, VEM-toughened
epoxy, and organo clay–filled VEM-toughened epoxy resin systems in terms of LOI
was calculated from the char yield resulting from TGA analysis[22–24] and is shown in
Table I. Flame-retardant characteristics can be represented by the LOI, and LOI
values increase with an increase in char yield. The LOI values of organo clay–filled
VEM-toughened epoxy materials are higher than that of VEM-toughened epoxy
resin systems due to the presence of inorganic nano silica core, which contributes
to thermal stability.

Morphology
X-ray diffraction analysis. X-ray diffraction analysis of organo clay–filled
hybrid VEM-epoxy nanocomposites is shown in Figure 1. The interlayer distance
was obtained from Bragg’s law, nk ¼ 2d sin h, when 2h ¼ 0–15. The d-spacing
of organo-modified MMT clay is higher than that of the unmodified clay. The
unmodified clay peak is found at 2h ¼ 9.35 (d001 ¼ 0.95 nm) and that of
organo-modified MMT clay at 2h ¼ 3.95 (d001 ¼ 2.23 nm). The increase from 0.95
to 2.23 nm is due to the grafting of cetyltrimethylammonium ions into the clay layer
surface through the ion exchange mechanism. The XRD patterns of organo clay–
filled hybrid VEM-epoxy nanocomposites suggest the formation of intercalated nano
 482 A. CHANDRAMOHAN ET AL.
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Figure 1. XRD patterns of (a) MMT clay, (b) organo-modified MMT clay, (c) epoxy=clay (100:1), (d)
epoxy=VEM=clay (100:10:1), and (e) epoxy=VEM=clay (100:10:5).

hybrids. For epoxy-clay hybrid nanocomposites, the nano size is 0.67 nm. The d001
spacing of organo clay–filled hybrid VEM-epoxy nanocomposites is 0.74–0.76 nm.
The clay layers spread over the whole matrix in an intercalated form that depends
on the interaction of cetyltrimethylammonium with epoxy resin and the swelling
period of the clay. The increase in basal spacing of nano clay platelets in the epoxy
system confirms the formation of intercalated nanocomposites.[25,26] The increase in
spacing of the gallery nano sheets is caused by the spreading of a large amount of
VEM-epoxy resin into the galleries.

Transmission electron microscopy. Transmission electron microscopy

(TEM) images at both low and high magnifications of organo clay–filled

Figure 2. TEM images of (a) epoxy=VEM=clay (100:10:1) at 500 nm and (b) epoxy=VEM=OMMT clay
(100:10:1) at 200 nm.
 VEM TOUGHENED EPOXY-CLAY NANOCOMPOSITES 483

VEM-toughened epoxy system are shown in Figures 2(a) and 2(b). Dark points
observed in the polymer matrix represent the self-aggregation of clay. Other than
the dark points, the heterogeneous phase morphology indicates that the VEM moi-
eties are dispersed within the continuous matrix. A few approximately spherical-like
domains were observed in TEM micrographs, which are due to inconsistencies
within the clay-enriched aggregates and the remainder forming molecular-level dis-
persion into the polymer matrix. TEM results were in good agreement with XRD
results, similar to those reported by others.[27] TEM analyses confirm the involve-
ment of most of the VEM molecules in Michael addition reaction and that the
remaining clay may aggregate prior to further polymerization.

CONCLUSIONS
We have successfully prepared VEM-toughened organo clay–filled epoxy
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intercross-linked nanocomposites. The addition of VEM into epoxy has been found to
impart enhanced thermal properties, namely glass transition temperature and thermal
stability, compared to unmodified epoxy. The glass transition temperature (Tg) decreased
with an increase in the organo clay content in VEM-toughened epoxy resin systems. Char
yield at 800
C for organo clay–filled VEM-toughened epoxy resin is almost doubled
compared to the unmodified system. The formation of intercalated nanocomposites
was confirmed by XRD analysis. TEM images show that the agglomerates of nano clay
were broken down to form small particles consisting of several clay platelets. The
VEM-toughened epoxy resins and clay nanocomposites developed in this study can be
used as coatings, insulating materials, and matrix resins for fabrication of advanced
composite components for a varying range of industrial and engineering applications.

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