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New trends in vinyl ester resins

Article  in  Reviews in Chemical Engineering · September 2014

DOI: 10.1515/revce-2014-0012

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 Rev Chem Eng 2014; aop

Shipra Jaswal and Bharti Gaur*

New trends in vinyl ester resins

Abstract: Vinyl ester resins (VERs) are high-performance (Figure 1). Shell Chemical Co. first commercialized these
unsaturated resins derived by the addition reaction of var- resins in 1965 under the trade name Epocryl. Dow Chemi-
ious epoxide resins with α-β unsaturated carboxylic acids. cal Co. then introduced a similar series of resins under the
These resins have always been classified under unsatu- name Derakane. VERs are used in place of UPE resins since
rated polyester resins. However, VERs have remarkable the unreacted carbon-carbon double bonds and the ester
corrosion resistance and superior physical properties as group, present in the backbone of UPE resins after curing,
compared with these conventional polyester resins, which provide sites for hydrolytic attack, oxidation, and halo-
make VERs a class of their own and hallmark of today’s genation, which make the cured UPE resin unsuitable for
resin industries. Hence, there is a need to review the avail- aggressive environments (Mallision 1987, Cheremisinoff
able literature on this important class of thermosetting and Cheremisinoff 1995, Juska and Puckett 1997), whereas
resins separately. In this article, an attempt is made to in VERs, the ester linkages are present only at the terminal
review the state of the art of VERs, including synthesis, ends of the chains. VERs incorporate the thermal stability
characterization, curing, thermal, chemical, oxidative and mechanical strength of the epoxy backbone, and the
properties, and applications. The main focus is on the lat- presence of double bonds at the chain ends provides it the
est developments in this area. ease of cure that is comparable with that in UPE resins.
These resins are costlier than UPE resins but are still widely
Keywords: corrosion resistance; cross-linking reactions; used since they have excellent chemical resistance, low
mechanical properties; thermosetting resins; vinyl ester water absorption, as well as low shrinkage during cure as
resins. compared with polyester resins. Moreover, unlike epoxy
resins, vinyl esters (VEs) have controlled cure rate and do
DOI 10.1515/revce-2014-0012
not need any curing agent to form a cured network. Neat
Received February 20, 2014; accepted July 14, 2014 VERs having high viscosity (105 cps) may vary from semi-
solid to solid. Reactive or nonreactive diluents are used to
provide workable viscosity levels and enhanced reactiv-
ity (Varma et  al. 1985, Bhatnagar and Varma 1989, Gaur
and Rai 1992a,b, Choudhary and Varma 1993, Malik et al.
1 Introduction 2001) to control the cross-link density and affect strength,
percentage elongation, hardness, chemical resistance,
Vinyl ester resins (VERs) are widely used thermosetting
scratch resistance, and surface finish. The physical and
resins in solvent storage tanks, sewer pipes, building and
handling properties of VERs depend on the source of
construction, coating, automobile structural parts, swim-
vinyl termination (methacrylate or acrylate), the amount
ming pools, and marine composites (Brown and Mathys
and type of co-reactant, and the molecular weight of the
1997, Mouritz and Mathys 1999, Varma and Gupta 2000,
resin backbone. Although acrylate VERs are more suscep-
Zhang et  al. 2000, Brody and Gillespie 2005) because of
tible to hydrolysis than methacrylate VERs are, they are
their low cost, excellent chemical and corrosion resist-
preferred in radiation cure inks and coatings because of
ance, outstanding heat performance, favorable mechani-
better reactivity (Launikitis 1982). The use of other unsatu-
cal properties, and better processibility. These are the
rated acids such as crotonic and cinnamic acids has also
addition products of epoxy resins and α-β unsaturated
been reported ( Jackson 1980, Zaske 1998). Although con-
carboxylic acids (Young 1976, Launikitis 1982) and are
siderable work has been done on VERs, a comprehensive
structurally similar to unsaturated polyester (UPE) resins
review dealing with the state of the art of these resins has
not been published. In this paper, an attempt was made to
review the synthesis, characterization, and physicochemi-
*Corresponding author: Bharti Gaur, Department of Chemistry,
cal, thermal, and mechanical properties of VERs.
National Institute of Technology, NIT Hamirpur (H.P.) 177005, India,
e-mail: [email protected]
VERs with wide structural variation can be prepared
Shipra Jaswal: Department of Chemistry, National Institute of by the reaction of different epoxide resins with various
Technology, NIT Hamirpur (H.P.) 177005, India unsaturated acids (Figure 2).
2      S. Jaswal and B. Gaur: Vinyl ester resins

CH3
HO CH2 CH O C C O CH2 C CH2 O C CH CH C OH
CH3 O O CH3 O O
n

Unsaturated polyester resin

CH3 CH3 CH3

H2C C C O CH2 CH CH2 O C O CH2 CH CH2 O C C CH2
O OH CH3 OH O
n

Figure 1 VER based on BPA epoxy.

Synthesis of VERs is usually catalyzed by tertiary 3 Bio-based VERs

amines, phosphines, and alkalies or -onium salts (Jackson
1980, Rao et al. 1986, Peter et al. 1991, Boutevin et al. 1993,
Ecofriendly VERs using renewable sources, e.g., cardanol
Zaske 1998, Aggarwal et al. 1999, Gawdzik and Matynia 2001,
from cashew nut, can be synthesized to reduce viscosity,
Srivastava et  al. 2002, Pal et  al. 2003) in the temperature
curing time, and concentration of styrene (Sultania et al.
range of 80–110°C and taking reactants in stoichiometric
2010). VERs prepared from rosin-acid-based epoxy resin
ratio. Complete esterification of the epoxy resin in practice
have been reported, with improved coating abilities of
is difficult because of gelation of the product before an acid
VERs due to faster drying and better chemical resistance
value below 10 is attained. Therefore, an excess of epoxide
(Atta et al. 2006). Carbohydrate-derived isosorbide can be
resin is always employed in the esterification reactions
used as core scaffold to synthesize novel and innovative
(Sandner and Schreiber 1992, Wheelar 1955). The reaction
VERs with extremely low viscosity. These can fulfill the
is monitored by determining the acid value and by Fourier
requirement of high-performance composite resin since
transform infra red spectroscopy (FTIR), proton nuclear
these have higher cross-link density and give a high Tg
magnetic resonance (1H NMR), and Carbon-13 nuclear mag-
value of 245 ± 9°C compared with any other commercially
netic resonance spectroscopy (13C NMR) performed on the
available VERs. These have the potential to be used as
samples withdrawn at regular intervals (Boutevin et  al.
viscosity modifiers without adversely affecting any other
1993, Aggarwal et  al. 1999, Gawdzik and Matynia 2001,
qualities of the matrix material for high-performance
Malik et al. 2001, Srivastava et al. 2002).
composite resin (Sadler et  al. 2013). Aliphatic matrix
resins derived from cycloaliphatic VER and glutaric acid
showed reduced UV absorption. These can be used to
2 Next-generation VERs obtain coatings and fiber-reinforced composites with
extreme durability to sunlight (Starr et al. 2001). Photo-
VERs in the neat form are highly viscous and, when used stabilization of VER was also reported by synthesized
with reactive diluents, show low viscosity during curing, interpenetrating polymer network modified lignin (Rosu
which leads to wastage of material and results into com- et al. 2009).
posite starving of matrix resin in certain applications such In order to obtain the starting material for the syn-
as sheet molding composites (SMCs). Structural modifica- thesis of VERs from a renewable source, use of mycrene,
tions of VERs can be done to get workable viscosity levels which is an oily liquid obtained by cracking on β-pinene of
without using reactive diluents. It has been reported by turpentine, has been reported by Yang et al. (2013). These
Oprea et al. (2000) that the reaction of secondary hydroxyl mycrene-based VERs have rapid curing (∼50 s) in the pres-
group of VER with diisocyanate gives a resin with low vis- ence of UV light. These resins also show excellent thermal
cosity. On the contrary, chemical modification of the side stability and good shore hardness. Attempts have also been
hydroxyl groups by dicarboxylic acid anhydrides produced made by Li et al. (2013) to obtain VE bio-copolymer derived
half ester acids using pyridine as catalyst, which led to from dimer fatty acid polymerized with glycidyl meth-
thickening of resin during cure, as reported by Rao et al. acylate and maleic anhydride modified dimer fatty acid
(1987) and Swisher and Grams (1971). In order to obtain a polymerized with glycidyl methacrylate resin. These were
product that shows faster cross-linking ability in UV light, further copolymerized with styrene and have been shown
Wang (2003) synthesized siloxane-based epoxy acrylates. to exhibit superior mechanical and thermal properties.
 S. Jaswal and B. Gaur: Vinyl ester resins      3

CH 3 CH 3

CH 2 CH CH 2 O C O CH 2 CH CH 2 O C O CH 2 CH CH 2

O CH 3 OH CH 3 O
n

Diglycidyl Ether of Bisphenol A

CH3 CH3

CH2 CH CH2 O C O CH2 CH CH2 O C O CH2 CH CH2

O CH3 OH CH3 O
n

Diepoxidized Hydrogenated Bisphenol A

O O O
C O CH2

Cycloaliphatic Epoxy
O O
CH 2 CH CH 2 CH 2 CH CH 2
N CH 2 N
CH 2 CH CH 2 CH 2 CH CH 2
O O
Tetraglycidyl Methylene Dianiline

O O
CH 2 CH CH 2 O CH CH 2
CH 2
N S N
CH 2 CH CH2 O CH 2 CH CH2
O O
Tetra Glycidyl Sulphone Dianiline
O
O CH 2 CH CH 2

O O
CH 2 CH CH 2 O CH O CH 2 CH CH2

Tri Glycidyl Triphenylmethane

O O O
O CH 2 CH CH 2 O CH 2 CH CH 2 O CH 2 CH CH 2

CH 2 CH 2

n
Epoxy Novolac

Unsaturated Acids
Acrylic acid: CH2 CH COOH

Methacrylic acid: CH2 CH COOH

CH3
Crotonic acid: CH3 CH CH COOH

Cinnamic acid: CH CH COOH

Figure 2 List of different epoxy resins and unsaturated acids used for VER synthesis.

4 Curing of VERs styrene, divinyl benzene, methyl methacrylate, etc., in

order to reduce its viscosity. These react with the back-
VER is dissolved in a reactive cross-linking monomer such bone polymer in the presence of organic peroxides and
as styrene, vinyl toluene, α-methyl styrene, p-tert-butyl hydroperoxides or azo and diazo compounds as free
4      S. Jaswal and B. Gaur: Vinyl ester resins

radical initiators to form a three-dimensional cross-linked the fully cured VE resin as polystyrene chains are either
network. It has been reported that fatty acid monomers entangled within the matrix or that each chain is indepen-
obtained from renewable resources (La Scala et al. 2004a) dently grafted to the matrix (Ganem et al. 1994).
and bimodal blends of VE monomers (La Scala et al. The cessation of the consumption of the methacrylate
2004b, 2005) can replace styrene as reactive diluent to double bond of VE led to the suggestion of biphasic struc-
reduce emission up to 78% (La Scala et al. 2004c). At low ture and, subsequently, to the belief in the formation of
temperature, promoters such as tertiary amines and salts microgel with the occurrence of polymerization-induced
of metals like cobalt octoate or naphthenate can be used phase separation in VE/styrene systems. Atomic force
to fasten the decomposition of initiators (Saunders 1973). microscopy photographs of cured VE/styrene system also
A mixture of initiators is used when a large temperature endorsed the theory of microgel formation by showing
increase is expected (Zaske 1998). Inhibitors like hydro- nodular morphology (Ziaee and Palmese 1999) or closely
quinone, tertiary butyl catechol, and toluhydroquinone packed microgels around 100  nm in diameter (Brill and
are added in very small amounts (in ppm) to the resin for- Palmese 2000) during the early stages of curing reaction.
mulations to inhibit premature gelation by consuming free Clusters of coral-like microgels with a maximum size of
radicals that occur naturally in the resin. This improves the 4 μm were also observed by Li et  al. (2004) using scan-
shelf life of the resins. ning electron microscope on the fractured surface of a
The curing of VER containing styrene as reactive sample cured at 80°C. The density of clusters was found
monomer involves three possible reactive paths: styrene- to decrease when the isothermal curing temperature was
VE copolymerization, styrene homopolymerization, and increased to 120°C. It was also observed that after curing,
VE homopolymerization. During the curing process, the the biphasic structure disappeared (Li et  al. 2004). Rey
physical state of thermoset resins changes from liquid et  al. (2000) investigated the morphological changes
to gel and, ultimately, to a glassy solid. It is believed that during the course of copolymerization reaction between
the heterogeneity of free radical cross-linking systems tetraethoxylated bisphenol-A (BPA) dimethacrylate and
during such reaction is an inherent result of the physi- styrene or divinyl benzene. They reported the formation
cal aspects of the free radical reaction and is explained of microgels using dynamic light scattering. Aggrega-
through widely accepted microgel theory (Saunders 1973, tion of microgels of diameter between 19 and 40 nm into
Yang and Suspense 1991, Hsu and Lee 1993a,b, Chiu and clusters was observed up to the gel point, after which
Lee 1995, Chen and Yu 1998). The curing of VE/styrene, the macroscopic network is developed. The size of the
like vinyl-divinyl system (Dusek and Spevacek 1980), cluster was found to be greater for divinyl benzene due to
shows an induction period due to the presence of inhibi- the large number of pendant double bonds as compared
tors and cage effect (Ziaee and Palmese 1999), in which with styrene. It was also observed that with increasing
the inhibitor consumes the free radicals and very little cure temperature, the size of the microgels and clusters
polymerization takes place. In stage I, which is the period became smaller. The two-phase structure of VE matri-
of accelerated propagation, the styrene monomer was ces, unlike that of UPE resins, was found to be organized
found to react at a slower rate than the VE monomer. The rather than random structured, which gives excellent
kinetics of copolymerization is thought to be governed by hydrolytic stability to VE resins (Mortaigne et  al. 1997).
the intrinsic reactivity of the styrene and VE double bonds Various methods employed to study the curing behavior of
and not by diffusion. In stage II, the polymerization rate VERs are differential scanning calorimetry (DSC) (Chang
is dominated by Trommsdorff effect (Dua et  al. 1999). 1992, Lee and Lee 1994, Cook et al. 1997), infrared (Ganem
According to Ganem and Mortaigne (1993), the polymeri- and Mortaigne 1993, Brill et  al. 1996, Li et  al. 1999, Brill
zation of VE monomer decreases and polymerization of and Palmese 2000), gel time studies (Abadie et al. 2002),
styrene increases throughout this stage. The reason for dynamic mechanical thermal analysis (DMTA) (Scott et al.
this is attributed to the higher mobility of the styrene mol- 2002a), torsional braid analysis (Stone et  al. 2000), and
ecule in the entire network, owing to its smaller size. The thermal scanning rheometry (Martin et al. 2000).
VE double bond at the end of stage II becomes immobile A variety of kinetic models have been used to relate
in the network due to its larger size. Toward the end of the the rate of the cure reactions of the thermosetting resins
reaction, i.e., during stage III, the VE ceases to react while to time, temperature, and the extent of cure. These kinetic
the rate of consumption of styrene continues to increase, models may be autocatalytic (Lee and Lee 1994, Auad
which leads to the formation of polystyrene until vitrifi- et al. 1999) or mechanistic (Kamal and Sourour 1973, Rey
cation takes place (Ganem and Mortaigne 1993, Dua et al. et  al. 2000). Of these two models, mechanistic models,
1999). The polystyrene formed cannot be extracted from despite giving better prediction and interpretation of the
 S. Jaswal and B. Gaur: Vinyl ester resins      5

curing reaction, are not easy to use in the process simu- reaction. Due to vitrification at low temperature, it was
lation (Yang and Lee 2001). Autocatalytic models are, observed that with an increase in isothermal cure tempera-
however, generally preferred to mechanistic models since ture, there was an increase in heat of cure and a decrease in
these are expressed by a relatively simple rate equation residual heat during postcuring and net effect on the total
and are developed ignoring the details of how reactive heat of cure was minimal. As in the dynamic conditions,
species take part in the reaction. The autocatalytic model the resin cures thoroughly above the glass transition tem-
developed by Kamal and Sourour (1973) is being used by perature (Tg) and vitrification does not take place; the heat
many workers. of cure is found to be more than the total heat of cure under
VERs exhibit autoacceleration in the polymerization isothermal conditions. The effect of different reactive dilu-
rate, which results into a single peak and cessation in ents on the curing behavior of VERs has been studied by
polymerization before the full conversion; i.e., vitrifica- many researchers ( Jackson 1980, Varma et al. 1985, Bhat-
tion takes place (Mousa and Karger-Kocsis 2000). Many nagar and Varma 1989, Gaur and Rai 1992a, Choudhary and
workers though have observed two overlapping peaks or a Varma 1993, Malik et  al. 2001). The addition of α-methyl
shoulder in isothermal DSC scans (Lem and Han 1984, Lee styrene in VER increased the gel time and suppressed the
and Lee 1994, Cook et al. 1997, Mousa and Karger-Kocsis peak exotherm (Bhatnagar and Varma 1989). Typical DSC
2000). Li et al. (1999) and Yang and Lee (2001) suggested scans (Gaur and Rai 1992b) for the curing of VERs contain-
that the first peak was observed due to the copolymeriza- ing methyl, ethyl, and butyl acrylates at a program rate of
tion between styrene and VE double bonds, whereas the 10°C min-1 are given in Figure  3. Less polar ethyl acrylate
second peak was caused by the homopolymerization of was found to be more reactive to VER as compared with
styrene monomers. It has been reported that with increas- methyl and butyl acrylate due to large differences in the
ing styrene content, the overall isothermal rate of curing polarity of acrylates.
of VERs decreased and the shape of DSC isotherm also The effect of concentration of styrene on thermome-
changed from one peak to two. It has been reported by Li chanical properties has also been studied using the DMTA
et al. (1999) that promoter concentrations and cure tem- technique. Glass transition temperature, Tg, can be deter-
peratures affected the reaction rates but did not change mined with significant levels of sensitivity by monitoring
the copolymerization mechanism between styrene and the changes in the storage modulus, E′, loss modulus, E″,
VER and therefore did not influence the structure forma-
tion of copolymer. On the contrary, according to Ziaee and
Palmese (1999), the selection of cure temperature does
affect the structure of the VER/styrene network. They
Exothermic

compared the curing behavior of this system at 30°C and

90°C, respectively, by considering the reactivity ratios
of VE and styrene at these two different temperatures. It
has been reported that at 30°C, both active styrene and
VE prefer to react with VE double rather than a styrene
monomer. However at 90°C, an active VE prefers to react
Heat flow

3
with styrene monomer while active styrene still prefers to
react with VE double bond, thus yielding different struc-
tures at two different cure temperatures.
According to Lem and Han (1984), the first exotherm
1
Endothermic

peak arises from the cross-linking reaction that starts at

lower temperatures with free radicals generated through
a reversible complex formation between the initiator and
2
the promoter. However, according to Cook et  al. (1997),
the shoulder or the first smaller peak may be due to short-
term polymerization, attributed to H2O2 (present as impu-
rity in methyl ethyl ketone peroxide) initiation followed 40 60 80 100 120 140 160 180
by a broad maximum in the polymerization rate due to Temperature (°C)

Trommsdorff effect. Figure 3 DSC scans for the curing reaction at 10°C min-1 of VERs
An increase in isothermal cure temperature (Lem and containing 40 wt% of (1) methyl acrylate, (2) ethyl acrylate, and
Han 1984, Dhulipala et al. 1993) accelerated the rate of the (3) butyl acrylate.
6      S. Jaswal and B. Gaur: Vinyl ester resins

or the loss tangent, tan δ, as a function of temperature. It be cured in light using various photoinitiators at room
has been reported that the Tg and the temperature of the temperature. It has been reported that photoinitiators
tan δ maximum were not significantly affected by styrene like bis-acylphosphine oxide, its blends with α-hydroxy
content. The magnitude of the rubbery modulus was found ketones, and camphorquionone/amine in the VER/
to increase while the tan δ maximum decreased with the styrene system were found to provide the fastest curing,
increased cross-link density (cross-linkable methacrylate best through-cure of the composites and gel coatings,
group) (Scott et al. 2002a). The effect of cure temperature high styrene incorporation yields, and good mechanical
on dynamic mechanical properties has been investigated properties (Cook 1992, Baikerikar and Scranton 2001, Sitz-
by Cook et al. (1997). They found that for the samples cured mann et al. 2001, Scott et al. 2002b, 2003a,b), which lead
at room temperature, two apparent glass transition regions to significant productivity enhancements. However, rate
at approximately 65°C and 115°C were exhibited in the of photopolymerization varied with the type of monomer
DMTA trace. In contrast, only one transition was observed used as reactive diluents due to the different reactivity of
for the “fully” cured sample. The reason for this anoma- these monomers.
lous behavior was attributed to the additional cure that
occurred on further heating during the DMTA experiment,
which provided sufficient molecular mobility to recom-
mence the curing process, causing a shift in the transi- 6 Effect of low-profile additives
tion region and an increase in the modulus. Martin et al.
(2000) determined gel time and vitrification time using the To improve fracture resistance and to control volume
DMTA technique. According to them, gel time is the time shrinkage of VER, they are usually blended or reacted
at which the maximum in tan δ curve appears and corre- with different thermoplastics and nonreactive additives
sponds to the difference between the storage and the loss or modifiers such as PVAc, PMMA, and polyurethane-
modulus, i.e., the time at which the resin begins to cross- based low-profile additives (LPAs). The mechanism of
link, generating maximum difference between the elastic shrinkage control has been studied extensively in the
and the viscous behavior. The second maximum in tan δ case of UPE resins. PVAc initially forms soluble or stable
curve gives the vitrification time (Figure 4). The viscoelas- dispersion with UPE resin before cure. During curing at
tic behavior of the material in this time interval is due to concentrations higher than the critical value at around 5
the increase in either the storage or the loss modulus. wt% PVAc levels, a co-continuous structure is obtained
as PVAc is pushed to the surface of the growing microgel
particle, which reduces the tendency of the resin particles
to coalesce, which leads to the formation of continuous
5 Photopolymerization of VERs PVAc phase interpenetrating the cross-linked network
phase (Han and Lem 1983, Bucknall et  al. 1985, 1991a,b,
VERs are the most common thermosetting resins used for
Suspene et al. 1991, Lucas et al. 1993, Kinkelaar et al. 1994,
the fiber-reinforced polymer (FRP) composites that can
Cook et  al. 1998). Although LPAs do not show the same
shrinkage control efficiency in VER as in UPE when cured
1.4 80 at low temperatures, they are effective in reducing the
η′′ 400 surface defects and internal stresses (Cao and Lee 2003)
1.2 η′
tan δ due to shrinkage by thermal expansion of thermoplas-
60
1.0 tic phase and development of void structure within this
η′′ (kPa-s)

300
phase. Saturated polyester formed from block copolymer
η′ (kPa-s)

0.8
tan δ

40 of dibasic acid and an ethylene oxide/propylene oxide can

0.6 200
be used as LPA for the high-temperature SMCs using VER
0.4 20 as polymer matrix. The addition of polyester showed good
100
physical properties and zero shrinkage for these compos-
0.2
ites (Cook et  al. 1998). It is observed that increased LPA
0 0
0.0 concentration, low initial heating rate, and high peak
0 20 40 60 80 100 120 140 temperature were considered to be the most desirable
Time (min)
conditions for shrinkage control. The curing behavior of
Figure 4 Storage modulus (G′), loss modulus (G″), and tan δ vs. VERs is not affected significantly by the presence of PVAc
time for the VER from DMTA. or its phase precipitation. Conversely, it has been reported
 S. Jaswal and B. Gaur: Vinyl ester resins      7

elsewhere that the addition of LPA decreased the rate of results in an increase in strength and stiffness than curing
cure and also the final degree of cure of the resin (Han in natural conditions.
and Lem 1984).

8 Rubber toughening of VERs

7 Mechanical properties
VERs are limited by their brittleness (Pantano et al. 2002),
VERs are preferred materials for structural composites especially when good impact behavior is needed. One of
due to their excellent mechanical properties and tough- the methods used to increase toughness is the modifica-
ness (Table 1) (Cassis and Talbot 1998). The rigidity of the tion of the resin with high-molecular-weight reactive liquid
prepolymer, the type and concentration of reactive dilu- rubbers such as polybutadiene, butadiene acrylonitrile
ents, and the cross-link density are the major contributing copolymer, polyepichlorohydrin, and polyacrylates, with
factors to the mechanical strength of the cured VER. It has molecular weights in the range of 2000–5000 gmol-1 (Ullett
been observed that an increase in the cross-link density and Chartoff 1995, Auad et  al. 2001, 2002, 2003). During
results in an increase in the glass transition temperature cure, the discrete rubber-rich second phase formed in the
and modulus (Scott et al. 2002a) and a decrease in strain- matrix improves its fracture toughness provided that this
to-break and impact energy (Cassis and Talbot 1998). The second phase meets certain criteria relative to size, shape,
VERs produced by epoxy novolac with methacrylic acid volume fraction, dispersion, and adhesion. However, poor
provide more unsaturation sites than BPA-based VERs do miscibility and poor reactivity of rubber with resin are sig-
and produce greater toughness, resiliency, solvent resist- nificant problems in achieving a suitable morphology for
ance, and heat resistance due to epoxy backbone of dif- toughening. A nonhomogeneous mass is formed that is
ferent molecular weights. Dilution with styrene resulted undesirable for the composite processing and resin control
in a decrease in glass transition temperature (Choudhary during cure. Attempts were made to improve the compat-
and Varma 1993) and tensile strength and an increase in ibility of rubber with VER by increasing the temperature,
the elongation of neat resin casting and glass-fiber-rein- ultrasonic treatment, and use of surfactants (Dreeman et al.
forced laminates. Cure temperature, cure formulation, 1999); however, they failed to improve compatibility. The
and curing method also affect the mechanical properties use of butadiene-acrylonitrile (VTBN)/epoxy-terminated
of VERs. Ziaee and Palmese (1999) found that the fracture butadieneacrylonitrile-based rubber modifier without the
toughness of BPA-based VER samples cured at 30°C using use of compatibilizers has been reported. These modifi-
cumyl hydroperoxide as initiator and cobalt naphthen- ers, while limiting plasticization of the resin matrix, gave
ate as promoter and then post cured at 125°C was three a system increased fracture toughness and stress intensity
times greater than for the samples cured using the same factor (Dreeman et al. 1999, Robinette et al. 2004).
formulation at 90°C and post cured at 125°C. Ganglani Siebert et  al. (1996) were able to obtain an approxi-
et al. (2002) reported that using N,N-dimethyl aniline as mately 540% increase in stress intensity factor with high
an accelerator during cure lowers the tensile strength, rubber levels, which also led to significant plasticization
fracture toughness, and strain-at-break and results in of the resin matrix. However, a limited amount of rubber
maximum methacrylate conversion. Benzoyl peroxide should be added so that the modulus and the strength
was debated to be a better initiator as compared with of base resin will not be affected (Achary et  al. 1991,
cumyl hydroperoxide. Microwave curing in a shorter time Ullett and Chartoff 1995, Auad et  al. 2001). Modification

Table 1 Mechanical properties of cured UPE resins and VERs (Malik et al. 2000).

Property   Ortho-  Iso-  BPA  Chlorendic  BPA-based  40 wt% fiber-glass-reinforced

resin resin fumarate VE resin BPA-based VE resin

Tensile strength (MPa)   55  75  40  20  80  160

Tensile modulus (GPa)   3.45  3.38  2.83  3.38  3.5–3.9  11.0
Elongation at break (%)  2.1  3.3  1.4  –  4.0  –
Flexural strength (MPa)   80  130  110  120  140  220
Flexural modulus (GPa)   3.45  3.59  3.38  3.93  3.7  9.0
Heat distortion   80  90  130  140  100  –
temperature (°C)
8      S. Jaswal and B. Gaur: Vinyl ester resins

of low-molecular-weight hydroxy terminated polybuta- especially in areas demanding electrical and corrosion
dienes (HTPB) through reaction with diisocyanate gave a resistance. Although fillers and reinforcements improve
more compatible resin system, which led to improvements the stability of the composites at high temperatures, the
in adhesion and mechanical strength (Achary et al. 1991, resin, at some point, begins to dissociate chemically. The
Pham and Burchill 1995). End capping of polybutadiene cross-linked resins, irrespective of the composition of VE
with various end groups and the mechanical test results or the vinyl monomer, undergo spontaneous decomposi-
for the VER toughened with modified polybutadiene are tion at temperatures of around 300°C, which is a char-
listed in Tables 2 and 3, respectively (Pham and Burch- acteristic of the vinyl polymers. Single-step degradation
ill 1995), which shows that with increasing length of the has been obtained using a thermogravimetric analyzer
end groups, the ability to provide a tougher cured resin (TGA) for cured VER containing 40 wt% styrene as dilu-
improves such that the energy to propagate a slow crack ents (Gaur and Rai 1992a, Agarwal et al. 2002). Two-step
increases 10 times. Addition of only 5% modified rubber degradation thermogravimetry scan was reported when
led to a 2- to 3-fold increase in stress intensity factor and a mixture of styrene and methyl methacrylate was used
10-fold increase in energy required for fracture in VERs. (Agarwal et  al. 2003). The decomposition behavior of
Toughening of VER matrix is also reported to be carried epoxy novolac-based VER samples of varied acid values
out by blending the resin with core-shell polymer addi- (11–48  mg KOH g-1 solid) containing 40 wt% of styrene
tive with a polybutadiene core, which is useful for typical as reactive diluent using TGA (Gaur and Rai 1992a) showed
structural commercial materials, e.g., polymer concrete the cured product with the lowest acid value precur-
with increased flexural strength (Burchill et al. 2001). Sat- sor to be the most thermally stable, with a lifetime of
urated elastomeric comb copolymers prepared with the 16.58  years at 400°C. In VE, networks based on BPA
backbone of polyacrylate with a carboxyl group at each cured in the presence of benzoyl peroxide and exposed
end and pendant chains derived from the macromer of to UV with λ  ≥  300 nm in the presence of oxygen formed
polycaprolactone in a manner analogous to that of CTBN unstable hydroperoxides, which led to the fragmentation
have also been reported as reactive modifiers to improve of VE network into highly volatile low-molecular-weight
the toughness or flexibility of thermosetting resins, includ- products (Rosu et al. 2008).
ing epoxy resins and VERs (Yu 1996). Due to the absence of
double bonds, these reactive modifiers are preferred to the
conventional CTBN elastomers as these are more resistant
to UV light and thermooxidative degradation and can be
10 Chemical resistance and water
used at elevated temperatures. absorption
VERs are used to handle most hot, highly chlorinated,
and acid mixtures even at a high temperature due to the
9 Thermal, oxidative, and better chemical and solvent resistance of VERs compared
photostability with other thermoset resins ( Jacob 2003). The excellent
acid base resistance of epoxy-based methacrylated VERs
VERs containing fillers and reinforcements are com- is due to their low ester content and protection of the ester
monly used in elevated temperature applications, linkages by the methyl shield of the methacrylate group.

Table 2 Polybutadiene end capped with various chain ends [Pham and Burchill 1995].

PB1 HTPB end capped with MDI, i.e., bis(4-isocyanatophenyl) methane. Free isocyanate.
(MDI-PB-MDI)
PB2 HTPB end capped with MDI. Excess isocyanate was neutralized with hydroxylpropylmethacrylate (HPM).
(HPM-MDI-PB-MDI-HPM)
PB3 HTPB end capped with MDI. Excess isocyanate was neutralized with triethylene glycol (TG).
(TG-MDI-PB-MDI-TG)
PB4 HTPB end capped with CRM (MDI terminated-terminated polypropylene glycol). Excess of isocyanate was neutralized with methanol (Me).
(Me-CRM-PB-CRM-Me)
PB5 HTPB end capped with MDI. Excess isocyanate was neutralized with TG-MDI-TG.
(TG-MDI-TG-MDI-PB-MDI-TG-MDI-TG)
 S. Jaswal and B. Gaur: Vinyl ester resins      9

Table 3 Mechanical test results for VERs toughened with modified polybutadiene (Pham and Burchill 1995).

Samples   KIci  KIca  GIci  GIca  Ksen  E

Derakane 411-15 (BPA-based VE resin)  0.72  0.63  157  122  1.12  2.82
5 wt% HTPB   1.20  0.65  560  163  1.02  2.24
5 wt% PB1   1.86  0.89  1369  314  1.46  2.08
5 wt% PB2   1.67  0.82  1051  253  1.44  2.32
5 wt% PB3   1.91  0.82  1390  258  1.44  2.36
10 wt% PB3   2.36  2.36  2571  2571  1.63  1.95
5 wt% PB4   2.22  2.22  1948  1948  1.56  2.10
5 wt% PB5   2.04  2.04  1751  1751  1.61  2.13
5 wt% PB3   2.59  2.59  3749  3749  1.75  1.33

The VERs are found to be the most resistant in acidic envi- have a self-protective ability to smartly resist mechani-
ronments and distilled water, with better retention of the cal and chemical damages caused by external aggressive
mechanical properties (Lee et  al. 1992, Ghorbel and Val- environment. VERs containing TiO2 particles have been
entin 1993, Valea et al. 1999, Kumosa et al. 2001). The VER reported as a self-healing coating material for aluminum
samples copolymerized with styrene (45 wt%) at room alloy 5083, which guard the metal surface. In case of abra-
temperature absorbed less water (0.8 wt%) than did the sion to the coating, the aluminum is said to react with BPA,
samples without styrene. The amount of water absorbed which is a chemical precursor of VER, and forms a barrier
also increased with the increase in temperature. Karbhari at the damaged part, where these rutile particles serve as
and Wang (2004) used DMTA to observe that the exposure receptacles for the BPA. This diminishes the damage by
of glass-fiber-reinforced VE composites to water initially the external hostile conditions on the surface (Stankie-
caused plasticization, resulting in a decrease in the inten- wicz et al. 2013). Although the same coating was not found
sity of the loss tangent (tan δ) peak as well as a decrease to be effective in inhibiting the corrosion of carbon steel,
in the glass transition temperature. Subsequent to this, a three-layered coating consisting of superabsorbent
lower-molecular-weight species gets leached out, result- polymer mixed with VER sandwiched in between the top
ing in an increase in the glass transition temperature and and base layers consisting of pure VER showed better
a change in the loss tangent profile. This phenomenon polarizing resistance (Yabuki and Okumura 2012). Modi-
could be termed as antiplasticization effect. The response fication in the base resin by reaction of the secondary
of these resins to an alkaline solution showed an initial hydroxyl group of triglycidyl ether of m-amino-phenol-
increase in brittleness due to moisture induced after based VERs with isocyanurate to obtain urethane linkages
curing, followed by the effect of plasticization. Rubber- resulted in a coating that showed superior adhesion to
modified VER is shown to have property retention similar the steel panels and exhibited good chemical resistance
to that of standard BPA-based VER except for the lower to various acids, alkalies, water, and organic solvent as
solvent resistance to low-molecular-weight solvents such compared with that of triacrylated derivatives (Patel et al.
as ethanol and toluene (Kardenetz et  al. 1985). The cure 1999). VER composites with different types of fillers have
schedule also influences the resistance of the resin toward also been explored as high-performance coatings. Ehsani
different solvents. It is observed that the resin samples et al. (2013) has reported the use of glass flakes (GFs) as
that are not subjected to post curing are more easily reinforcement fillers to enhance the physical properties
attacked by solvents brought in contact with them (Valea (i.e., modulus, thermal expansion, thermal and electrical
et al. 1998). conductivity, and magnetic recording) of VER composite
used for coating applications. A study of GF-reinforced
polymer composite using DMTA in the temperature range
of 25–180°C showed that in increasing the GF content from
11 Applications 5 parts per hundred resin (phr) to 15 phr, there was an
increase in storage modulus, whereas higher thermal sta-
11.1 VERs as coatings and adhesives bility was obtained with 25 phr GF content due to thicker
GF-enriched char layer build up on the surface of the com-
The use of VERs as coating material has gained increasing posite. As the filler content was increased from 0 phr to 15
popularity since the 1990s. Nowadays, VERs are being used phr, a decrease in reaction enthalpy and glass transition
as new-generation self-healing coatings. These coatings temperature of the composite system was observed.
10      S. Jaswal and B. Gaur: Vinyl ester resins

VER is a promising class of thermosetting matrices not only showed lesser shrinkage but also gave the com-
used as adhesives with high strength and toughness, posite better fracture toughness.
enduring service at high temperatures and chemical con- E-glass and Kevlar-49 fiber-reinforced VE laminates
frontation for structural bonding applications as well as have been reported to be used in ballistic applications
in repair applications. It has been reported that liquid (Panda et  al. 1994). It has also been described that by
crystalline VER synthesized from p-(2,3-epoxypropoxy)- optimization of loading of short aramid fibers and exter-
α-methylstilbene as epoxy monomer showed excellent nal variables (standoff resistance, impingement angle,
adhesive strength for aluminum substrate (Ambrogi et al. erodent size, impact velocity, etc.), erosion or wear perfor-
2002). The methacrylate group of the resin acts like Lewis mance enhancement of short aramid-fiber-reinforced VER
acid and interacts with aluminum oxide that acts as a composite can be successfully achieved (Kumar et al. 2011)
Lewis base, both through the carbon-carbon double bond A comparative study of the chemical and thermal
and through carbon-oxygen double bond present on the behavior of two main types of thermosetting polymers,
resin. It is believed that the resin shows adhesion to the i.e., polyester resin and VER, showed that the VER cure
oxide layer immediately before the curing reaction occurs reaction proceeded more slowly, because of which it
and thus provides a stable structure after cure. was able to form a more compact structure; as a result,
the VE/glass fiber composite gave better chemical resist-
ance against seawater (Visco et al. 2011). In order to use
11.2 VERs as matrix for composite materials these resins as matrix for preparing composites with high
dielectric strength, hollow glass microballoons were used
Polymer matrix composites and especially FRPs are as fillers to obtain syntactic foams in order to develop inte-
widely utilized in construction applications, including grated circuit boards having good mechanical strength
industrial and agricultural buildings, due to their high (Shunmugasamy et al. 2013).
mechanical strength, tailored design through controlled In the present era, the use of natural fiber reinforce-
anisotropy, chemical and thermal stability, acoustical ments has also gained substantial attention in composite
characteristics, light transmission and translucency, technology as a low-cost, lightweight, and environmental-
electromagnetic transparency, electrical nonconduc- friendly alternative to other synthetic fibers. The mechani-
tivity, etc. (Taranu 2009). VERs, which are the leading cal, chemical, and thermal properties of VER composites
candidate among thermosetting polymers, can serve as unified with naturally obtained cellulose, cotton, and luffa
matrix material for producing fiber-reinforced compos- cylindrical fibers have also been investigated. Cellulose
ites, short fiber-reinforced composites, as well as par- fabricated VER composites showed a gradual increase in
ticulate composites. These thermoset resins are shown to water uptake, tensile modulus, and flexural strength with
have very good adhesion to glass fibers, aramid fibers, an increase in cellulose fiber volume fraction in composites
as well as carbon fibers. Composites based on VERs are (Alhuthali and Low 2013a). The thermal and mechanical
used in a variety of engineering applications and espe- behaviors of alkali-treated and -untreated cotton-fiber-
cially for wear-sensitive applications. A comparison of reinforced VE composites have also been reported by
the tribological properties of the composite produced by Shahedefar and Rezadoust (2013). It was observed that the
using glass fiber and carbon fiber, respectively, showed use of alkali-treated cotton fiber to reinforce VER improved
that carbon-reinforced VER composites show supe- the tensile strength and elongation-at-break of composites
rior wear resistance and lower coefficient of friction as by 5% and 25%, respectively, as compared with that of
compared with glass-fiber-reinforced VER composites untreated cotton fiber composites due to increased surface
(Suresha et al. 2010). The influence of aluminum ceramic roughness by the removal of wax and oil from the surface
particulate on the tribological characteristics of E-glass- of the fibers. Attempts have also been made by Siqueira
fiber-based VER composites has also been studied by and Botaro (2013) to replace synthetic fibers by fibrous
Chauhan et  al. (2013). The minimization of erosion or mat of Luffa cylindrica ripe fruit as reinforcement and alu-
wear performance was also observed in hybrid VER com- minum hydroxide as polymer additive to prepare VER com-
posites consisting of short glass and carbon fiber (1:1) posites. These fibers of L. cylindrica were modified with
with different fiber weight fractions (from 20 wt% to 1,2,4,5-benzenetetracarboxylic dianhydride and NaOH
50 wt%) (Kumar et  al. 2012). Ku et  al. (2007) were able (mercerization) to increase the interfacial compatibility,
to reduce the shrinkage of the VE composite contain- adhesiveness, and wettability between L. cylindrica fibers
ing flyash as particulate filler by curing the composite and VE matrix. These composites obtained also showed
sample in the presence of microwave. Microwave curing improved thermal and mechanical properties.
 S. Jaswal and B. Gaur: Vinyl ester resins      11

11.3 Nanostructured VER composites et  al. (2009) has reported that due to the low electrical
percolation threshold of VER as matrix, high aspect ratios
Polymer nanocomposites are polymer matrix composites of carbon nanotubes were maintained during nanocom-
in which the reinforcement has at least one of its dimen- posite formation and an electrically conductive network
sions in the nanometer range. These composites show was formed throughout the laminate, which in turn led to
superior mechanical, thermal, electrical, optical, and the utilization of carbon nanotubes as in situ sensors for
other properties at relatively low reinforcement volume detecting deformation and damage in advance naval com-
fractions. The transition from microparticles to nano- posite structures.
particles yields dramatic changes in physical properties. Halloysite nanotubes (HNTs), which originate from
Nanoscale materials have a large surface area for a given naturally deposited alumiosilicate [Al2Si2O5 (OH)4.H2O]
volume, and many properties (chemical and physical) and have chemical analogy to kaolin, have been unified
are governed by surfaces and surface properties (Luo and with VERs to reduce water uptake and amplify thermal
Daniel 2003, Thostenson et al. 2005). The use of organic and mechanical properties. HNTs have also been found to
or inorganic nanofillers such as carbon nanofibers, cel- be effective in increasing the toughness of the material.
lulose fibers, titanium oxide nanoparticles, etc., has It has also been reported that this nanocomposite attains
become ubiquitous in the present-day matrix materials good thermal stability and flame retardancy due to the
for developing nanocomposites. Efforts are always being hollow tubular structure of HNTs as well as the presence
made in order to develop material with better macro- of Fe2O3 as impurity (Alhuthali and Low 2013b). Improved
scale properties. Jang et  al. (2012) has studied the inter- toughness properties of VER nanocomposites containing
facial interactions between the surfaces of oxidized vapor polypropylene mesofibers have been reported by Liang
grown carbon nanofiber (VGCNF) and VE monomer and et al. (2011).
reported the formation of 5–10 Å stiffer interphase, which
affected the interfacial adhesive bonding. This bonding
could be increased by increasing the polar interactions
between the matrix and oxidized VGCNFs. Nanocompos- 12 Conclusion
ites developed by Shahrajabian et  al. (2013) using TiO2
nanoparticles showed excellent mechanical and thermal VERs either in the pure form or in compounded form
properties, which were seen to increase after the compos- with fillers have use in a wide range of applications. The
ites were exposed to electron beam. Recycled cellulose growth of VERs has also been boosted because of their
fiber sheet based VE-containing nanoclay filler eco-nano- excellent handling characteristics and easy cure. These
composites were developed and were further investigated are the prime candidates for composites in transporta-
for water uptake and mechanical and thermal proper- tion and infrastructure applications for construction of
ties. Nanoclay addition to the polymer matrix decreased parts of automobiles, polymer concretes, reinforcements
water uptake and increased thermal stability, mechanical for bridges, etc., due to their excellent thermal perfor-
strength, and fire-resisting properties due to better inter- mance and mechanical properties. Because of their
facial interactions between fiber and matrix, although it inherent resistance to chloride attack and long service
was observed that the addition made the nanocomposite life, composites of VERs are adopted by the paper and
brittle (Alhuthali et al. 2012). Chaturvedi et al. (2013) has pulp industries as well. VERs based on epoxy novolacs
described the development of graphene-reinforced VE are used for chemical storage tanks, pipes and ducting,
nanocomposites. Graphene sheets can be used to resolve fume extraction system, and gas cleaning units, as these
the serious concerns related to the use of carbon nano- resins show superior chemical resistance at high tem-
tubes, primarily the cost and limited production. Multi- peratures. These have high tensile elongation along
walled carbon nanotube unified VER nanostructures can with superior corrosion resistance, which makes them
become an emerging electrically conductive polymeric a promising material for producing lining and coating
system (Yurdakul et  al. 2010). Multiwalled carbon nano- with outstanding adhesion to other types of plastics
tube-VE cross-linking nanostructures have also been used and conventional materials such as steel and concrete.
for bipolar plates in proton exchange membrane fuel cells. VERs also have a variety of applications in optical fiber
This unique system showed significant enhancement in coating, topcoats for metal containers, UV curing inks,
performance of the fuel cell due to better dispersion of as well as printed circuit boards (Radhakrishnan and
carbon nanotubes into the matrix, higher mechanical Pethrick 1994, Bajpai et  al. 2004, Chattopadhyay et  al.
strength, and superior electrical conductivity. Thostenson 2005).
12      S. Jaswal and B. Gaur: Vinyl ester resins

Brill RP, Mccullough RL, Palmese GR. Effect of resin formulation

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Shipra Jaswal received her bachelor’s degree in 2006 and master’s Bharti Gaur is an associate professor in the Department of Chemis-
degree in 2008 from Himachal Pardesh University, Shimla, try, National Institute of Technology-Hamirpur, Himachal Pradesh,
Himachal Pradesh, India. She is currently pursuing her PhD on the India. She received her BSc degree from St. Bedes College Shimla in
synthesis of hyperbranched vinyl ester resins based on natural 1986. She completed her postgraduate studies in organic chemistry
products from the National Institute of Technology, Hamirpur, from Sardar Patel University, Anand, Gujarat, India, in 1988. She
Himachal Pradesh, India. She is also working in a project as women obtained her PhD degree from HBTI Kanpur, India, in 1993. She has
scientist under Women Scientist Scheme-A, approved by Depart- worked as a scientist in IIT Delhi for 2 years, where she filed two
ment of Science and Technology, New Delhi, India. She has three patents in the area of energetic binders for solid rocket propellants.
publications in national and international conferences. She has taught in a number of undergraduate and postgraduate
institutes before joining NIT Hamirpur as an assistant profes-
sor in 2010. She has more than 25 research papers in national
and international journals and conferences. Her current research
interests include microbial fuel cell, synthesis of proton exchange
membrane for fuel cells, nanocomposites, synthesis of adhesives,
and coatings.

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