Polymer Bulletin (2022) 79:477–501

https://doi.org/10.1007/s00289-020-03511-x

ORIGINAL PAPER

High‑performance gum rosin‑modified hyperbranched

vinyl ester resin derived from multifunctional
pentaerythritol

Shipra Jaswal1 · Tamanna Thakur1 · Bharti Gaur1 · A. S. Singha1

Received: 24 April 2020 / Revised: 10 November 2020 / Accepted: 4 December 2020 /

Published online: 2 January 2021
© The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature 2021

Abstract
In this article, gum rosin-based hyperbranched vinyl ester resin (VPEMPAE) was
synthesized from maleic anhydride-modified gum rosin adduct (MPA). This adduct
(MPA) was reacted with pentaerythritol to obtain esterified adduct (PEMPA). The
PEMPA adduct was epoxidized using epichlorohydrin and KOH as a catalyst to
give epoxy resin (PEMPAE). The epoxide rings were then reacted with methacrylic
acid to synthesize vinyl ester resin (VPEMPAE). The lignin modeled compounds
(LMCs), methacrylated eugenol (ME), and methacrylated guaiacol (MG) were used
as bio-based reactive monomers for vinyl ester resin. The chemical structures of
all the products were studied using FT-IR, 1H-NMR, 13C-NMR, and DEPT-135°
spectroscopic analysis. The dynamic curing study of cured samples was done using
DSC. Thermogravimetric analysis of these samples was performed using TGA at a
heating rate of 10 °C min−1. Mechanical properties such as compression, flexural,
and tensile strengths of VPEMPAE samples were also determined using a universal
testing machine. Some preliminary coating tests were also performed to determine
the chemical resistance of these cured resins and morphological studies on these
coatings were also conducted using SEM. The results of this study showed better
performance of rosin-derived vinyl ester resin cured with reactive diluent ME as
compared to MG and commercially based styrene.

Keywords Rosin · Vinyl ester · Thermal stability · Chemical resistance · Bio-based

* Bharti Gaur
bhartigaur@gmail.com
1
Department of Chemistry, National Institute of Technology, Hamirpur,
Himachal Pradesh 177005, India

13
Vol.:(0123456789)
478 Polymer Bulletin (2022) 79:477–501

Introduction

In the past few decades, immense research has been devoted to developing new
bio-based and eco-friendly polymeric materials from a renewable resource, pre-
dominantly due to two reasons viz. the environmental threat caused by global
warming and dwindling petroleum resources. Plant products can play an essen-
tial role in the greening of conventional petroleum-based vinyl ester resins. In
the past few years, gum rosin holds considerable attention as a source of scaffold
material for polymer production. Rosin acid extracted from the pine tree is being
used as raw material for the adhesive and coating industries since ancient times
either as such or as converted derivatives. Gum rosin consists of mainly abietic
acid (approx. 90%), and its isomers are abundantly available as exudates of pines
and conifers. Gum rosin is a mixture of eight analogous rosin acids consisting of
three fused six-carbon rings and a single carboxylic acid group which is distin-
guished by double bonds present in phenanthrene ring with varying positions [1,
2]. The composition of these isomers varies according to the method of collec-
tion, tree species, and the production location. Moreover, the larger hydrogenated
phenanthrene ring present in rosin acids exhibits similar rigidity as petroleum-
derived cycloaliphatic or aromatic compounds thus can be used as an exceptional
green alternative for petroleum-based vinyl ester resin [3, 4].
Vinyl ester (VE) resins are a promising class of thermoset resin in the com-
posite industry as an alternative to epoxy resins, phenolic, polyesters, and poly-
imide resins owing to their exceptional handling characteristics and ease of cure.
VERs are the polyadditional polymerized products of epoxy resins and ethyleni-
cally unsaturated carboxylic acids consisting of ester groups and C=C bonds at
the end chain of the polymer. These structoterminal unsaturated groups are highly
reactive and can cause rapid cross-linking with or without reactive monomers
(viz. styrene, vinyl toluene, acrylates) to give products of desired properties [5,
6]. Since these resins have significantly high viscosity, reactive monomers, or
diluents are used in resin formulations that provide resin with workable viscos-
ity levels. VER systems using reactive diluents are preferred as they delay the
gelation process of neat vinyl ester resins and offer high-performance polymers
with enhanced mechanical strength, hardness, percent elongation, cross-link
density, resistance to chemicals, surface finishing, and scratch resistance [7, 8].
Owing to these exceptionally outstanding properties, vinyl ester resins show the
advantages of both epoxy and polyester resins. Compared to epoxy resins, vinyl
esters acquire benefits of low cost, lesser viscosity, easy to operate, low or room
temperature curing using a catalyst, coatability with no seasonal restrictions [9,
10]. VERs could also retain most of the enviable epoxy resin properties. They
offer superior mechanical strength and thermal stability, electrical properties,
good adhesion and resistance to acid, alkali, and salts, corrosion resistance, flame
retardancy, low shrinkage, air drying, impact resistance [11–13]. These are often
used in applications that require high strength, heat performance, and corrosion
resistance which include marine, industrial, building, and construction [14–16].
Due to over-pressing environmental issues, there is an urgent need to develop

13
Polymer Bulletin (2022) 79:477–501 479

green polymeric materials. Since vinyl ester resins constitute a major compo-
nent for numerous industrial applications, a bio-based vinyl ester resin in place of
petroleum-based vinyl ester resin can serve to reduce the human footprints on the
environment [17–20].
Gum rosin is being explored as potential raw material for generating a new series
of matrix resin that could replace the present-day petroleum-based resin by many
researchers over the years. Atta et al. have reported the synthesis of tetra functional
epoxy resins by reacting diethanolamine with Diels–Alder adducts of rosin ketone [25].
Gum rosin-derived polyamide and gum rosin-based acid anhydrides have also been
used as curatives for various epoxy resins, and these bio-based curatives also proved as
a better replacement for petroleum-based epoxy curing agents [3, 26]. Gum rosin has
poor resistance to water and alkalis. It is sensitive to oxygen in the air and is tacky to
touch. To overcome these problems, in this article, gum rosin has been modified to pro-
duce adduct (MPA) with maleic anhydride via Diels–Alder reaction which was further
esterified using pentaerythritol (PEMPA). This introduces pendant hydroxyl groups of
pentaerythritol on the backbone of the resin in the presence of a suitable catalyst, which
in turn increases the functionality, and flexibility of gum rosin-based VER. PEMPA
was then epoxidized using epichlorohydrin to form epoxy resin (PEMPAE). Vinyl ester
resin (VPEMPAE) was prepared by methacrylating gum rosin-based epoxy resin.
In this work, non-volatile reactive monomers obtained by methacrylation of
lignin model compounds have been used as viable and bio-based aspirants to
entirely replace styrene as reactive monomer. Since the Federal Environmental Pro-
tection Agency (EPA) of the USA has designated styrene as hazardous and cancer-
causing air pollutants due to its high volatility, thus it is urgent to get its substitute
without letting go of its outstanding performance and processability [21]. Lignin is
an aromatic affluent, bio-renewable alternate having the potential to give way single-
ring aromatic compounds as selectively broken down. It has been reported by Joseph
et al. [22] that under the experimental conditions, styrene took approximately 3 h to
get fully evaporated at 30 °C whereas only 0.9 and 1.35% of methacrylated euge-
nol (ME) and methacrylated guaiacol (MG), respectively, was evaporated at 30 °C
after 18 h. This fact demonstrates the exceptionally lower volatilities of ME and MG
as compared to styrene. MG and ME were productively exploited as low viscosity,
non-volatile reactive monomers to decrease the viscosity of vinyl ester resins to a
workable level. The purpose of the present research article is to exploit the novel
applications of rosin in the greening of conventional petroleum-based vinyl ester
resins and to study the thermal and mechanical performance of the above-formed
vinyl ester resin using bio-based and non-volatile methacrylated lignin-modeled
compounds (LMCs) as reactive monomers.

Experimental

Materials

Gum rosin (ww grade), maleic anhydride (99% pure, LobaChemie Pvt. Ltd., India),
p-toluenesulfonic acid (p-TSA) (98% pure, LobaChemie Pvt. Ltd., India), and

13
480 Polymer Bulletin (2022) 79:477–501

pentaerythritol (98% pure, LobaChemie Pvt. Ltd., India) were used for the synthesis
of maleopimaric acid (MPA) adducts and esterification of adduct with pentaeryth-
ritol. Epichlorohydrin L.R. grade (99% pure, LobaChemie Pvt. Ltd., India), sodium
hydroxide pellets (85% pure, Avra Synthesis Pvt. Ltd., India) were used for the syn-
thesizing epoxy resin. Methacrylic acid (99% pure, LobaChemie Pvt. Ltd., India)
and triphenylphosphine (99% pure, LobaChemie Pvt. Ltd., India) were used for the
preparation of vinyl ester resin. Eugenol (99% pure, LobaChemie Pvt. Ltd., India),
Guaiacol (99% pure, LobaChemie Pvt. Ltd., India), Methacrylic anhydride (99%
pure, LobaChemie Pvt. Ltd., India), and 4-dimethyl aminopyridine (DMAP) (98%
pure, Alfa Aesar, UK) were used for the synthesis of methacrylated eugenol (ME)
and methacrylated guaiacol (MG). Styrene (Thermo Fisher Scientific, US), meth-
acrylated guaiacol (MG), and methacrylated eugenol (ME) were used as reactive
diluents in this study.

Synthesis of rosin‑based vinyl ester resin (VPEMPAE)

The synthetic scheme of rosin-based vinyl ester resin (VPEMPAE) is presented in

Scheme 1. Firstly, abietic acid (10 g) was isomerized to levopimaric acid at 180 °C
for 3 h which was then reacted with maleic anhydride (2.35 g), p-TSA (0.46 g), and
acetic acid (30 ml) at 120 °C for 12 h to give adduct (MPA) via Diels–Alder reac-
tion. This MPA (10 g) was further esterified using pentaerythritol (6.4 g), Xylene
(10 ml), and p-TSA (1 wt%) and refluxed until 6 mol of water were collected to form
an esterified adduct (PEMPA) that introduces pendant hydroxyl groups of pentae-
rythritol on the backbone of the MPA. PEMPA (30 g) was then epoxidized using
epichlorohydrin (272 ml) and KOH (116 g) to form epoxy resin (PEMPAE). The
detailed procedure for the synthesis of epoxy resin PEMPAE and structural charac-
terization of MPA, PEMPA, and PEMPAE is reported in our previous study [23].
Vinyl ester resin was synthesized by reacting MPA-based epoxy resin (PEMPAE)
and methacrylic acid (1:0.9 molar ratio) in the presence of catalyst triphenylphos-
phine (1 phr by weight of epoxy resin) and inhibitor hydroquinone (200 ppm) at
85 ± 1 °C for three and a half hours to get a product with an acid value of ~ 7 mg
of KOH/gm solids calculated according to ASTM D 1636. Triphenylphosphine had
been used as a catalyst (1 phr by weight of epoxy resin) in the esterification of epoxy
resin because it acted effectively at moderately elevated temperatures [2, 27–29].
The reaction was carried out at 85 ± 1 °C in the presence of approximately 200 ppm
of hydroquinone, as it prevented the premature gelation of vinyl ester resins. It has
been reported that it is impracticable to esterify the epoxy resin on the whole as
the gelation of the product was attained before the acid value approaches to 10 mg
KOH/g solid [30]. Hence, esterification reactions are always carried out in excess of
epoxide resin.

Synthesis of bio‑based reactive monomers

The synthetic route for the synthesis of lignin model compound-based reactive mon-
omers methacrylated guaiacol (MG) and methacrylated eugenol (ME) is presented

13
Polymer Bulletin (2022) 79:477–501 481

Scheme 1  Synthetic route for VPEMPAE vinyl ester resin

13
482 Polymer Bulletin (2022) 79:477–501

Scheme 2  Synthetic route for Methacrylated Eugenol (ME) and Methacrylated Guaiacol (MG)

in Scheme 2. These reactive monomers were synthesized according to the procedure

described in our previous study [24].

Curing procedure

The rosin-derived vinyl ester resin (VPEMPAE) was cured using three different
reactive monomers styrene/methacrylated guaiacol (MG)/methacrylated eugenol
(ME) and benzoyl peroxide as a free radical initiator in 10/4/0.2 (w/w), respectively.
Half of the weighed amount of each reactive monomer was mixed with the resin
and the other half with the benzoyl peroxide in separate flasks. The flasks were
then sealed and kept under refrigeration to avoid premature polymerization before
use. Then, equal amounts of the solutions were taken in a beaker and stirred vigor-
ously with a glass rod at 30 °C until a uniform mixture is formed. The mixture was
then poured into molds with cavity size 100 × 10 × 5 mm. The curing of resin was
achieved at a particular temperature determined from the DSC scan at which appre-
ciable rate of curing was observed for each sample. The samples were cured under a
load of 100 kg/cm2 in a compression molding machine, for particular time duration
determined from the isothermal DSC scan. The samples were cut apart with the help
of a metallurgical saw into different sized strips required for the type of test to be
carried out according to the test specifications.
The samples for curing studies were prepared using 10/4/0.2 (w/w) of resin, sty-
rene, and benzoyl peroxide, respectively, at room temperature.

Characterization

Structural characterization

The structure of the synthesized vinyl ester resin (VPEMPAE) was characterized
using FT-IR, 1H-NMR, and 13C-NMR spectroscopic methods. For FT-IR, the sam-
ples were dissolved in chloroform and recorded via Perkin Elmer-Spectrum RX-
IFTIR (U.S.) Spectrometer by subsequent evaporation of the solvent on KBr disk.
Bruker Avance II 400 (U.S.) NMR spectrometer was used to record the 1H-NMR
and 13C-NMR spectra using deuterated C ­ DCl3 as solvent and TMS as an internal
standard.

13
Polymer Bulletin (2022) 79:477–501 483

Determination of physical properties

The refractive indices of the VPEMPAE samples containing styrene, MG, and ME
were measured via A.KRUSS Optronic Abbe’s refractometer AR2008 (Germany).
Viscosities of the VPEMPAE samples containing 40% wt/wt styrene, MG, and ME
were measured by using Brookfield viscometer (LVDV II + Pro, Brookfield, USA)
using spindle no. L62 at 120 rpm. Density measurements were done using a Pyc-
nometer at 20 °C.

Gel permeation chromatography (GPC)

For molecular weight determination of rosin-based vinyl ester resin (VPEMPAE),

Perkin Elmer turbo matrix-40 (U.S.) Gel permeation Chromatograph was used
wherein; tetrahydrofuran was used as a mobile as well as a stationary phase and
cross-linked polystyrene column was used for GPC calibration.

DSC and TGA analysis

Dynamic DSC scans were recorded on Perkin Elmer Diamond (U.S.) Differential
Scanning Calorimeter with a programmed heating rate of 10 °C min−1 from room
temperature to the completion of exothermic reactions. From the dynamic DSC
scans, a temperature for each sample was selected which showed an appreciable
rate of curing. Isothermal DSC runs were carried out at that particular temperature
to determine the apparent time required for the completion of curing. The curing
conditions determined were then used to cure the respective samples and subse-
quently evaluate their decomposition behavior. For thermogravimetric analysis, SII
6300 EXSTAR TG/DTA(U.S.) was used for recording TG/DTA/DTG traces of the
samples cured isothermally at a heating rate of 10 °C min−1 in nitrogen atmosphere
(flow rate = 200 ­mLmin−1) having sample size 11 ± 5 mg. The quantitative estima-
tion of relative thermal stability of the cured vinyl ester resins was done by compar-
ing the temperatures for a particular amount of weight loss.

Mechanical Behavior

The samples for the analysis mechanical performance were prepared by mixing
10/4/0.2 (wt/wt) of the vinyl ester resin, styrene, MG, and ME as reactive mono-
mers, respectively, and free radical initiator-benzoyl peroxide in a beaker. The mix-
ture was then poured into specially designed molds of dimension (150 × 150 × 5.0
­mm3) and cured at a temperature determined from the DSC scan for a particular
sample under a load of 100 kg/cm2 for 12 h in a compression-molding machine.
The samples were cut apart with the help of a metallurgical saw into different sizes
required for the type of the test to be carried out according to the test specifications.
For the analysis of the mechanical performance of all the samples such as ten-
sile, compressive, and flexural strength, Hounsfield-25KN H50KS (U.K.) universal
testing machine at a testing speed of 2 mm/min was used. For determining the ten-
sile strength (ASTM D3039), the span length was fixed as 50 mm. In the case of

13
484 Polymer Bulletin (2022) 79:477–501

compressive strength (ASTM D3410), the test specimens were held between two
platforms of the machine, and the compressive load was applied over 25-mm span
length. The three-point flexural strength (ASTM D790) was determined by fixing
the span length to 50 mm. The impact tests (ASTM D256) were also carried out
for these samples using a plastic impact tester Tinius Olsen IT 406 (U.S.A) that
ascertains the notch impact strength of the material by shattering the notched speci-
men with a pendulum hammer, measuring the spent energy and relating to the cross
section of the specimen. The depth under the notch is 2 mm. Three replicates of
each sample were used for the measurement of each mechanical property. The mean
value and standard deviation of each mechanical property were determined.

Chemical resistance analysis

For chemical resistance analysis of cured vinyl ester resins, coating samples were
prepared and applied on one side of the mild steel specimen (15 cm × 10 cm) with a
total dry film thickness of 250 ± 10 µm (measured using vernier caliper with accu-
racy of 10 µm) via hand layup method and another side of which was coated using
coal tar epoxy primer for protection against corrosion. The coated specimens, three
samples for each resin system, were subjected to the chemical environment of acid,
alkali, and salt solutions and were dipped in 1 M HCl, 1 M NaOH, and 1 M NaCl
aqueous solutions for 90 days. The chemical resistance analysis was done by evalu-
ating the % weight loss of the cured samples after subjecting to different chemical
environments using Eq. (1):
Wi − Wf
% Weight Loss = , (1)
Wi

where Wi is the weight of the cured sample before dipping into different aqueous
solutions and Wf is the weight of the dry sample after dipping into different aqueous
solutions. The morphology of cured resin samples was also studied using Scanning
Electron Microscopy. This study differentiates the changes that appeared on the sur-
face of the cured resins due to chemical exposure to different solutions. This study
was performed using the JSM-6610 Scanning electron microscope.

Results and discussion

Scheme 1 shows the reaction scheme for the synthesis of gum rosin-based vinyl
ester resin (VPEMPAE) with methacrylic acid-catalyzed with triphenylphosphine.
Vinyl ester resin with acid value ~ 7 mg KOH/g solid was obtained and further used
for studying the thermal and mechanical behavior using styrene (Sty), methacrylated
guaiacol (MG), and methacylated eugenol (ME) as reactive diluents. Figure 1 illus-
trates the variation in the acid value with reaction time. The figure clearly shows the
decrease in acid value with the reaction time, and this behavior is usually observed
in catalyzed polyesterification reactions. The not linear plot in the initial phase of
the reaction shows the decrease in acid value that was due to the greater availability

13
Polymer Bulletin (2022) 79:477–501 485

Fig. 1  Acid value versus reaction time graph for VPEMPAE

of the reactive sites and a larger possibility of the acid group to react with epoxide
groups.

FT‑IR

FT-IR spectrum [Fig. 2a] of MPA showed a broad absorption peak ranging from
3300 to 3500 cm−1 due to carboxylic –OH stretching present in MPA. Two stretch-
ing bands in the carbonyl region at 1843 and 1779 cm−1 displayed the presence of
anhydride group which confirmed the Diels–Alder reaction between gum rosin and
maleic anhydride and lead to the formation of MPA [3]. Figure 2b shows the FT-IR
spectra PEMPA, where the disappearance of the anhydride peaks and appearance
of the peak due to > C=O– of ester groups at 1730 cm−1 confirmed the esterifica-
tion reaction. The FT-IR spectra of epoxy resin PEMPAE i.e., Figure 2c shows the
characteristic band due to symmetrical stretching or ring breathing frequency of
epoxy ring at 1253 cm−1 and asymmetrical C–O–C stretching in the epoxy ring at
1174 cm−1 [31]. FT-IR spectra of VPEMPAE in Fig. 2d shows the appearance of a
distinguished broad absorption band due to secondary hydroxyl group at 3433 cm−1,
peaks at 1715 and 1170 cm−1 due to carbonyl groups of methacrylate, and peak at
1631 cm−1 due to C=C stretching of methacrylate groups that confirm the synthesis
of VPEMPAE [27].

1
H‑NMR

In the 1H-NMR spectrum of VPEMPAE in Fig. 3, eminent peaks at 5.9 and 6.1 ppm
because of vinylic protons and peak at 2.1 ppm owing to –CH3 of methacrylate
group were observed. Since, it is practically difficult to esterify all the epoxy groups
present in PEMPAE as a result of which proton resonance signals at 2.6, 2.9, and
3.3–3.4 ppm due to –CH2, –CH, and O–CH2 protons of the residual epoxy ring were
observed too.

13
486 Polymer Bulletin (2022) 79:477–501

Fig. 2  FTIR spectra of all the synthesized products a MPA, b PEMPA, c PEMPAE, and d VPEMPAE

13
C‑NMR

Figure 4 shows the 13C-NMR spectrum of VPEMPAE in which resonance sig-

nals for –CH3 and =CH2 of methacrylate group appeared at 18.2 and 125.1 ppm,
respectively. The resonance signal of –C=O carbon of methacrylate group which
appears at 173 ppm in methacrylic acid was observed to be shifted upfield
to 167.42 ppm when ester linkage is formed in vinyl ester resin (VPEMPAE).
Moreover, the appearance of a peak at 135 and 129.5 due to –C–, =CH and peaks
from 15–54 ppm due to the –CH3, –CH2, and –CH carbons present in gum rosin,
respectively, were observed whereas resonance signals from 65–77 ppm were
observed due to the –O-CH2– carbons present in the VPEMPAE.

13
Polymer Bulletin (2022) 79:477–501 487

Fig. 3  1H-NMR spectra of Vinyl ester resin (VPEMPAE)

Fig. 4  13C-NMR spectra of Vinyl ester resin (VPEMPAE)

Molecular weight determination by 1H‑NMR and GPC

The molecular weight of vinyl ester resin (VPEMPAE) has also been worked
out by calculating the number of methacrylate groups present in the vinyl ester
resin molecule. The number of methacrylate groups (A) was evaluated using the
1
H-NMR spectroscopic technique by taking the ratio of the integration of –CH3
protons present on the gum rosin moiety which were observed between 0.5 and
1.3 ppm to the =CH2 proton of the methacrylate group (proton 2) that appeared at
5.5 and 6.1 ppm.

13
488 Polymer Bulletin (2022) 79:477–501

Fig. 5  GPC of Vinyl ester resin (VPEMPAE)

Table 1  GPC determined Samples Mw (g/mol) Mn (g/mol)

molecular weights of
synthesized products GPC 1
H-NMR

MPA 398.6 332.2 –

PEMPA 772.9 589.4 –
PEMPAE 1277.5 910.5 1260.12
VPEMPAE 2052.3 1368.4 1965.32

Integration of − CH3 protons (present on gum rosin) 2.05

A= = = 8.2 (2)
Integration of methylene proton (proton 2) 0.25

The value of methacrylate group (A) was utilized to calculate the molecular
weight of VPEMPAE using the formula (1260.12 + 86A), where 1260.12 g/mol
is the molecular weight of PEMPAE, 86 is the molecular weight of one meth-
acrylate group, and A is the total methacrylate groups present in VPEMPAE.
Using 1H-NMR spectroscopy, the molecular weight of VPEMPAE is found to be
1965.32 g/mol, which is comparable to the value obtained from the GPC graph
of the VPEMPAE as shown in Fig. 5. The molecular weight of VPEMPAE and
its precursors determined from the GPC technique are tabulated in Table 1.
Table 2 shows the physiochemical properties i.e., density, viscosity, and
refractive index of all the reactive monomers and VPEMPAE resin samples con-
taining these reactive monomers.

13
Polymer Bulletin (2022) 79:477–501 489

Table 2  Physiochemical properties of VPEMPAE resin

Properties MG ME Sty VPEMPAE + MG VPEMPAE + ME VPEMPAE + Sty

Density (in g/cm3 at 1.24 1.20 0.91 1.062 1.067 1.002

25 °C)
Viscosity (in cps at 19.37 29.62 0.75 3450 3465 3324
25 °C)
Refractive Index 1.544 1.54 1.516 1.380 1.387 1.432

Dynamic curing behavior

The vinyl ester resins exhibit varied curing behavior with different reactive mono-
mers. Figure 6 displays the typical DSC curves for the curing of gum rosin-based
vinyl ester resin (VPEMPAE) with methacrylated eugenol (ME), methacrylated
guaiacol (MG), and styrene (40% w/w), respectively, at a heating rate of 10°Cmin−1.
As the Fig. 6a–c shows, the heat flow for the curing of VPEMPAE with MG, ME,
and styrene reactive monomers, respectively, exhibited a single exothermic peak

Fig. 6  DSC scans of Vinyl ester resin (VPEMPAE) with a MG, b ME and c Styrene

13
490 Polymer Bulletin (2022) 79:477–501

with the exothermic transitions in the temperature range of 85–150°C. Generally,

under similar curing conditions, the onset (Ti) and peak temperatures (Tp) indicate
the reactivity of the reactive diluents with vinyl ester resin throughout curing reac-
tions. For VPEMPAE samples containing styrene, MG, and ME, the DSC curves
showed onset temperatures (Ti) as 90.9 °C, 83.6 °C, and 84.3 °C and peak tempera-
tures (Tp) as 114.3 °C, 98.46 °C, and 104.46 °C, respectively.
Table 3 summarizes the DSC curing exothermic temperatures and the ener-
gies corresponding to these exotherms (ΔH) for all the cured vinyl ester resin
systems. It was observed that the exothermic transitions for VPEMPAE samples
containing ME and MG ensues lower onset and peak temperatures as compared
to styrene as a reactive diluent which signifies that bio-based ME and MG reac-
tive diluents offer higher reactivity to VPEMPAE than commercial-based styrene
throughout curing reactions in the presence of benzoyl peroxide (BP) as free
radical initiator. Scheme 3 shows the proposed cross-linking of synthesized VER
with different reactive monomers. The reason for higher reactivity of ME and
MG reactive monomers must be attributed to the greater resonance stability and
steric factors of styrene free radical which might hinder the curing of the vinyl
ester with styrene. Moreover, methacrylate radicals in MG and ME have more
polarity as compared to styrene, hence, showed high reactivity toward the vinylic
C=C of methacrylate group present in the VPEMPAE. These results were com-
pared to the rosin-derived trimethylol-based vinyl ester resin (VTMPAE) synthe-
sized in our previous study [23] which showed onset temperatures as 97.7, 91.9,
and 94.5 °C and peak temperatures as 119.4, 105.5, and 110.3 °C when cured
with styrene, MG, and ME reactive monomers. The VTMPAE samples showed
higher temperature curing as compared to cured VPEMPAE samples which must
be due to the higher functionality in VPEMAPE that increases the cross-linking
sites thereby increasing the reactivity of vinyl ester resin. Sultania M. et al. [18]
reported the curing performance of cardanol-based vinyl ester resins with styrene
as a reactive monomer that displayed the curing temperature range of 96–128 °C
that is higher than that of rosin-based vinyl ester resin (VPEMPAE). Also, PEM-
PAE epoxy resin, a precursor of VPEMPAE, cured with imidoamine curing agent
and commercial DDE curing agent in our previous study [31], showed high tem-
perature curing in a temperature range of 72–180 °C as compared to VPEMPAE
cured with MG, ME, and styrene that ensures the higher reactivity of vinyl ester
resins as compared to epoxy resins. Furthermore, it is apparent from Table 3
that the enthalpy of the reaction (ΔH) for the VPEMPAE sample containing MG
and ME was lower than the samples containing styrene which signified a higher

Table 3  DSC results of cured vinyl ester resin samples

Sample Onset temp. (in Peak temp. (in °C) End set temp. (in ΔH (J/g)
°C) °C)

VPEMPAE + MG 83.6 98.4 111.7 62.3

VPEMPAE + ME 87.3 113.4 143.2 75.1
VPEMPAE + Sty 89.8 114.3 142.8 80.3

13
Polymer Bulletin (2022) 79:477–501 491

Scheme 3  Proposed cross-linked structure for vinyl ester resin (VPEMPAE) with MG/ME/Sty

degree of cross-linking or curing in the VPEMPAE sample containing MG and

ME than the samples containing styrene as reactive monomers [32]. The DTA of
cured vinyl ester resins was carried out to determine the residual curing and the
absence of exotherm in the DTA run validates the complete curing of the vinyl
ester samples [33].

13
492 Polymer Bulletin (2022) 79:477–501

Thermal stability

The thermal stability of thermosetting resins is an important aspect in determining

its end use and thermal performance is significantly influenced by the physical struc-
ture, chemical composition, and the secondary interactions between the molecular
chains, etc. The thermal performances of gum rosin-based vinyl ester resin sam-
ples (VPEMPAE) containing methacrylated guaiacol (MG), methacrylated eugenol
(ME), and styrene as reactive diluents and benzoyl peroxide as free radical initia-
tor were evaluated by thermogravimetric analysis (TGA) in a nitrogen atmosphere.
Typical thermogravimetric (TGA) and Derivative Thermogravimetric (DTG) curves
for isothermally cured VPEMPAE samples containing styrene, MG, and ME as
reactive monomers are shown in Fig. 7a, b, respectively. A noticeable single step
weight loss in the TG curve of VPEMPAE containing methacrylated guaiacol (MG),
methacrylated eugenol (ME), and styrene as reactive monomers indicated single-
step decomposition behavior. The rate of degradation at a particular temperature can
be evaluated as the tangential slope of a TGA curve. Generally, the initial decom-
position temperature (IDT) and the temperature at which maximum decomposi-
tion occurs (Tmax) are of major importance. Higher IDT and Tmax indicate the better
cross-linked network structure of the cured VPEMPAE samples containing different
reactive diluents. The cured VPEMPAE samples containing styrene, MG, and ME
showed IDT at 305, 335, and 340 °C and Tmax at 403, 399, and 410 °C, respec-
tively, which is evident from the DTG curves in Fig. 7b. The initial small percentage
of weight loss shown by VPEMPAE-MG and VPEMPAE-STY samples at 100 °C
may be attributed to the loss of moisture or unreacted reactive diluents present in
the samples. Also, from Table 4, on comparing the temperatures upon which 5 and
10% weight loss occurred (T5% and T10%, respectively) in cured VPEMPAE samples
containing styrene, MG, and ME, it can be further corroborated that the thermal
stability of ME cured resin sample was highest as compared to that of other two
VPEMPAE samples cured with styrene and MG, respectively, which might be due
to the presence of two free radical reactive sites i.e., allylic group as well as vinylic
group of methacrylate, present in ME. ME has the potential ability to undergo copo-
lymerization with C=C of VPEMPAE using both of its allylic and vinylic free radi-
cal reactive sites, and this might correspond to increased cross-link density which
results in the highest thermal stability of the cured VPEMPAE sample containing
ME. However, on comparing the temperatures at which 20% weight loss of the sam-
ples incurred (T20%) from Table 4, rapid decomposition of cured VPEMPAE sam-
ple containing ME was observed due to the instability of ester linkages present in
the cross-linked array of VPEMPAE containing ME whereas styrene cured VPEM-
PAE samples degraded slowly since there is an absence of ester linkages. Thus, the
results show that rosin-based vinyl ester resin containing bio-based methacrylated
eugenol and methacrylated guaiacol as reactive monomers give rise to more stable
resin thermosets as compared to the commercial-based styrene. The obtained results
were compared to a previously reported study [5] in which cardanol-based vinyl
ester resins were synthesized and cured using styrene and glycidyl methacrylate as
reactive diluents. The samples in the study exhibited initial thermal decomposition
at 210 °C and maximum decomposition up to 460 °C which shows lesser thermal

13
Polymer Bulletin (2022) 79:477–501 493

Fig. 7  a TGA and b DTG curves for cured Vinyl ester resin (VPEMPAE) with different reactive mono-
mers

Table 4  TGA studies of various cured vinyl ester resin samples

Name of sample IDT (°C) Tmax (°C) FDT (°C) Temperatures Activation Char yield
(°C) at weight energy(ΔE) (%) ( at
loss (%) (KJ/mol) 700 °C)
5% 10% 20%

VPEMPAE + MG 335 403 455 293 322 355 311 6.12

VPEMPAE + ME 340 410 460 300 342 371 325 8.87
VPEMPAE + STY 305 399 450 277 335 373 279 5.91

13
494 Polymer Bulletin (2022) 79:477–501

stability of cardanol-based vinyl ester as compared to rosin-based vinyl ester resin.

Furthermore, the pentaerythritol-based vinyl ester showed higher thermal perfor-
mance than trimethylol-based vinyl ester resin cured with MG, ME, and styrene in
our previous reported article [23]. The cured VTMPAE samples exhibited lower
IDT and Tmax values as compared to VPEMPAE samples, and this must be due to
the higher cross-linked structure of cured resins formed by VPEMPAE resin. The
thermal properties of pentaerythritol-based vinyl ester resin were also compared to
pentaerythritol-based epoxy resins cured with different curing agents in our previous
study [31] which showed thermal stability of cured epoxy resins to a temperature
range of 150–405 °C whereas the cured vinyl ester resin exhibited thermal stability
to 300–460 °C temperature range.
The activation energy of the thermal degradation reaction was calculated from
TGA data by a method independent of heating rates and sample size reported by
Dharwadkar and Kharkhanawala [42]. The equation for Ea is given as:
Ea 100𝜃
ln ln (1 − 𝛼)−1 =
[ ]
( ) +C (3)
RTi2 Tf − Ti

where α is degrading fraction, Ti is initial decomposition temperature, Tf is the

temperature at which maximum decomposition occurs; θ is the difference of final
decomposition temperature and temperature under consideration; R is gas constant;
C is constant. Ea is evaluated by plotting ln [ln (1-α)−1] vs θ giving a straight line
with slope m.
Ea 100
m= ( ) (4)
RTi2 T f − Ti

Thus, activation energies of decomposition for all the samples were evaluated by
Eqs. (3) and (4) and listed in Table 4. The activation energies and the char residue
were also found to be higher in the case of rosin-based vinyl ester resin samples
cured with different reactive monomers. These results indicate that rosin-derived
vinyl ester resin thermosets have enhanced performance than epoxy resin thermosets
thus could be a preferred choice for thermoset industries.

Mechanical characterization of VPEMPAE samples

The mechanical behavior of the vinyl ester resins greatly depends on the structure
and composition of the reactive monomers. Secondary interactions between the pol-
ymer chains and the cross-link density of the cured vinyl ester resin system also
influence the mechanical behavior of the vinyl ester resin samples [34]. As shown in
Fig. 8, the VPEMPAE samples cured using bio-based MG and ME reactive mono-
mers showed better mechanical strength as they exhibited higher values for flexural,
impact strength and young’s modulus, and comparable results for compression and
tensile strength than VPEMPAE samples with commercial-based styrene as reactive
monomer. Table 5 summarizes the values for various mechanical tests performed on
different vinyl ester resin samples. The mean and standard deviation values have also

13
Polymer Bulletin (2022) 79:477–501 495

Fig. 8  Comparison of the compressive, flexural, and tensile strength of VPEMPAE samples containing
Styrene, MG, and ME

been provided. From this data, it is clear that the values for flexural strength, impact
strength, and young’s modulus are substantially greater in case of the VPEMPAE
samples cured with MG as compared to the VPEMPAE samples cured with ME and
styrene. Whereas in case of compression and tensile strength, considering the stand-
ard deviations, the results are statistically equal or comparable for samples cured
with MG, ME, and Styrene. The reason for excellent flexural and impact strength
in case of VPEMPAE samples cured with MG as compared to the ME and styrene
might be the high reactivity of the vinylic double bond (C=C) of the methacrylate
group of MG that results in the greater cross-link network structure with enhanced
cross-link density and also concords with the DSC results. Moreover, the increased
polymeric chain interactions among the secondary hydroxyl group of VPEMPAE
and carbonyl group of MG due to intermolecular hydrogen bonding and polar attrac-
tion tends to reduce the chain mobility and resist the deformation and VPEMPAE
matrix breakup. This also contributes to the superior mechanical performance of
VPEMPAE samples containing bio-based and eco-friendly lignin-based reactive
monomers MG and ME than that of the styrene. Although ME may have shown
elevated mechanical performance than MG but owing to its potential capability to
undergo copolymerization via two cross-linkable functionalities i.e., allylic group as
well as vinylic group, the cross-link density increased to its maximum limit which
led to the fragility in the VPEMPAE samples containing ME, and hence, waning
of the mechanical performance of these samples. However, the mechanical perfor-
mance of VPEMPAE samples cured with ME was still found to be higher than the
styrene due to the presence of more reactive methacrylate free radical present in
ME which resulted in the formation of the better cross-linked network. Siva et al.
[35] performed mechanical tests on vinyl ester resins based on commercial DGEBA
and styrene/α-methyl styrene as reactive diluents and exhibited tensile strength
as 30–35 MPa and flexural strength as 68–78 MPa for varying ratios of resin and

13
 496

13
Table 5  Mechanical tests of cured vinyl ester resin samples
Samples Compression Strength Flexural Strength Tensile Strength (MPa) Impact Strength (J) Tensile Strain (∆l/l) Young’s
(MPa) (MPa) Modulus
(GPa)
X1, ­X2, ­X3 SD X1, ­X2, ­X3 SD X1, ­X2, ­X3 SD X1, ­X2, ­X3 SD ­(10−3) X1, ­X2, ­X3 SD ­(10−3)
Mean(Xn ) Mean(Xn ) Mean(Xn ) Mean(Xn ) Mean(Xn )
­(10−3)

VPEMPAE + MG X1 = 52.5 3.4 X1 = 114.5 1.8 X1 = 59.4 1.9 X1 = 1.001 3.6 X1 = 7.3 0.2 83.6
X2 = 45.4 X2 = 117.7 X2 = 64.6 ­X2 = 1.006 X2 = 7.2
X3 = 47.5 X3 = 114.6 X3 = 60.5 X3 = 1.008 X3 = 7.7
Xn = 48.5 Xn = 115.6 Xn = 61.5 Xn = 1.005 Xn = 7.4
VPEMPAE + ME X1 = 40.5 3.6 X1 = 88.4 1.6 X1 = 55.4 1.5 X1 = 0.956 1.9 X1 = 14.2 0.4 40.6
X2 = 41.6 X2 = 91.6 X2 = 57.1 X2 = 0.954 X2 = 13.5
X3 = 47.5 X3 = 89.1 X3 = 58.5 X3 = 0.952 X3 = 14.3
Xn = 43.2 Xn = 89.7 Xn = 57 Xn = 0.954 Xn = 14.0
VPEMPAE + STY X1 = 42.6 1.9 X1 = 75.3 3.5 X1 = 49.5 1.6 X1 = 0.909 2.6 X1 = 43.2 3. 2 12.8
X2 = 39.5 X2 = 76.7 X2 = 50.0 ­X2 = 0.914 X2 = 38.5
X3 = 38.8 X3 = 82.6 X3 = 52.6 X3 = 0.913 X3 = 37.6
Xn = 40.3 Xn = 78.25 Xn = 50.7 Xn = 0.912 Xn = 39.7
Polymer Bulletin (2022) 79:477–501
Polymer Bulletin (2022) 79:477–501 497

diluents. These values were found to be far lesser than rosin-based VPEMPAE
cured with MG/ME/styrene. Furthermore, the pentaerythritol-based vinyl ester resin
showed superior mechanical performance than trimethylol-based vinyl ester resin
(VTMPAE) when cured with different reactive monomers. The reason for this may
be attributed to the increased functional end groups i.e., nine secondary hydroxyl
groups present in VPEMPAE, which in turn increased the secondary interactions
between VPEMPAE and reactive monomers and formed stronger cross-linked struc-
ture than VTMPAE samples which contained six secondary hydroxyl groups in its
polymer backbone. When compared with rosin-derived PEMPAE epoxy resin cured
with different curing a gents, cured VPEMPAE resins displayed better tensile and
flexural strength and comparable compression strength that reveals vinyl ester resins
lead to strong and tough thermosetting materials than epoxy resins.

Chemical resistance

In general, the chemical resistance of the polymer towards hydrolysis by acids, alka-
lis, and chemicals depends on the chemical structure of both polymer and reactive
monomer. Chemical resistance of any polymeric material can also be controlled by
the degree of cross-linking or curing, nature of the cross-linking formed during cur-
ing, the polarity of the functional groups present in the polymer and reactive mono-
mer in addition to the secondary interactions i.e., hydrogen bonding formed between
the polymer and reactive monomer. Among these, cross-linking is the most impor-
tant factor that prevents the polymeric chains from dissolving in a solvent. A highly
cross-linked network formed by the polymer reduces the free volume and thereby
minimizing the segmental mobility of the polymer chain array that averts the perme-
ation of solvent molecules to the polymer chains. Chemical resistance studies have
been carried out in terms of percent weight loss by plunging the VPEMPAE-coated
mild steel panels to chemical exposure of 1 M HCl, 1 M NaOH, and 1 M NaCl
aqueous solutions for 90 days. Table 6 includes the mean values along with their
standard deviations for the weight loss incurred while determining the chemical

Table 6  Chemical resistance of cured vinyl ester resin samples in terms of % weight loss
Aqueous Solu- No. of days Chemical resistance in terms of (% wt. loss) of the samples
tion (1 M)
VPEMPAE + MG VPEMPAE + ME VPEMPAE + Sty

HCl 30 0.15 ± 0.02 0.05 ± 0.01 0.19 ± 0.02

60 0.40 ± 0.02 0.20 ± 0.02 0.58 ± 0.02
90 0.81 ± 0.03 0.99 ± 0.04 0.85 ± 0.03
NaOH 30 0.12 ± 0.01 0.20 ± 0.03 0.38 ± 0.03
60 0.39 ± 0.01 0.85 ± 0.01 0.42 ± 0.02
90 1.05 ± 0.02 1.09 ± 0.02 0.97 ± 0.02
NaCl 30 0.22 ± 0.04 0.18 ± 0.02 0.23 ± 0.03
60 0.39 ± 0.02 0.25 ± 0.03 0.38 ± 0.01
90 0.65 ± 0.03 0.57 ± 0.01 0.78 ± 0.03

13
498 Polymer Bulletin (2022) 79:477–501

resistance of VPEMPAE resin samples having styrene, ME, and MG as reactive

monomers. As the data illustrates, the cured vinyl ester resin samples containing ME
showed high acid, base, and salt resistance as compared to that of samples contain-
ing styrene and MG, which could be ascribed to an enhanced degree of cross-linking
in the vinyl ester cured with ME. On comparing the chemical resistance of cured
trimethylolpropane-modified gum rosin-based vinyl ester resin (VTMPAE) samples
with pentaerythritol-modified gum rosin-based vinyl ester resin (VPEMPAE) sam-
ples, it was observed that the cured VPEMPAE samples showed more resistance to
the chemical environment as compared to that of VTMPAE samples. The reason for
this might be due to the increased functional end groups in VPEMPAE which in turn
increased the secondary interactions between VPEMPAE and reactive monomers
and formed a stronger cross-linked network structure than VTMPAE samples in its
polymer backbone. This also prevented the permeation of the solvent molecules into
the cross-linked network. Furthermore, vinyl esters displayed much higher resist-
ance to chemical exposure as compared to pentaerythritol-based epoxy-coated sam-
ples cured with amine-based curatives [31], and the disintegration rate was observed
to be ten times higher in the case of epoxy resins. This comparison validates that
vinyl ester resins are a much finer option over epoxy resins for potential applications
in coating industries.

Evaluation of surface morphology by SEM

The mild steel panels coated with cured VPEMPAE resin samples taken for the
chemical resistance study by plunging the panels in different chemical solutions
were also scrutinized for morphological or physical damage that occurred by the
chemical exposure via Scanning Electron Microscopy (SEM). The SEM images
(a–c) given in Fig. 9 shows the surface morphology of VPEMPAE samples con-
taining styrene (a), MG (b), and ME (c) before immersing into chemical solutions
whereas images (d–f), (g–i), and (j–l) shows damage occurred after immersing into
1 M HCl, 1 M NaOH, and 1 M NaCl, respectively. The SEM images evidently show
that maximum deterioration or cracks appeared on the surface of cured VPEMPAE
with styrene as reactive monomer after being exposed to different chemical solu-
tions. Whereas, mere roughness on the surface of samples cured with MG and ME,
revealed bio-based MG and ME cured vinyl ester resins provided high resistance to
the chemical environment as compared to petroleum-derived styrene. This study has
shown conformity with weight loss in percent (%) of the cured VPEMPAE samples
during the chemical resistance analysis.

Conclusion

This research article reports the outcomes of experimental analysis on thermome-

chanical properties and chemical resistant behavior of rosin-derived multifunctional
vinyl ester resin using bio-based methacrylated guaiacol (MG) and methacrylated
eugenol (ME) and commercial-based styrene as reactive monomers. The synthetic

13
Polymer Bulletin (2022) 79:477–501 499

Fig. 9  SEM images of cured VPEMPAE samples containing Styrene, MG and ME as reactive mono-
mers. a–c Styrene, MG, and ME (unexposed). d–f Styrene, MG and ME (exposed to 1 M HCl). g–i Sty-
rene, MG, and ME (exposed to 1 M NaOH) and j–l Styrene, MG, and ME (exposed to 1 M NaCl)

structures of gum rosin-based vinyl ester resin (VPEMPAE) and LMC-based reac-
tive diluents MG and ME were confirmed via FT-IR, 1H-NMR, and 13C-NMR spec-
troscopic methods. The curing study of gum rosin-derived vinyl ester resin samples
showed greater reactivity of LMC-based reactive monomers (MG/ME) towards
VPEMPAE as compared to that of petroleum-based reactive monomer i.e., styrene.
The VPEMPAE samples containing MG & ME showed better thermal stability and
mechanical strength i.e., tensile, flexural, impact, and compression strength than the
samples containing styrene. These results indicated that the LMC-based reactive

13
500 Polymer Bulletin (2022) 79:477–501

monomers i.e.- MG and ME are an excellent alternate to styrene whereas, vinyl ester
resin cured with ME exhibited the finest performance among all three reactive mon-
omers. The properties of pentaerythritol-based vinyl ester resin (VPEMPAE) were
compared to trimethylol-based VTMPAE where VPEMPAE due to more numbers of
pendant double bonds of the ester groups showed a superior performance that illus-
trates the role of functionality in the performance of vinyl ester resin thermosets. In
addition, the results were compared to pentaerythritol-based epoxy resin cured with
amine curatives. The vinyl ester resins displayed a superior thermal, mechanical, and
chemical performance that signifies vinyl ester resins are more advantageous over
epoxy resins for coatings and thermosetting industries. The thermal stability of the
gum rosin-based vinyl ester resin samples was found to be higher than conventional
petroleum-based vinyl ester resins. Mechanical strength was found to be comparable
in both cases. This suggested that gum rosin as monomer provided a new avenue to
synthesize a novel bio-based vinyl ester resin for replacing the conventional petro-
leum-based vinyl ester resins and addressing the environmental issues largely.

Funding None.

Data Availability The datasets analyzed during the current study are available in the Mendeley Dataset
repository, https​://doi.org/10.17632​/wkchj​tx63t​.2, https​://data.mende​ley.com/datas​ets/wkchj​tx63t​/2

Compliance with ethical standards

Conflict of interest The authors have no conflicts to declare.

References
1. Coppen JW, Hone GA (1995) Gum naval stores: turpentine and rosin from pine resin. Food and
Agriculture Organisation of the United Nations, Rome
2. Chen GF (1992) Developments in the field of rosin chemistry and its implications in coatings. Prog
Org Coatings 20:139–167
3. Liu X, Xin W, Zhang J (2009) Rosin-based acid anhydrides as alternatives to petrochemical curing
agents. Green Chem 11:1018
4. La Scala JJ, Logan MS, Sands JM, Palmese GR (2008) Composites based on bimodal vinyl ester
resins with low hazardous air pollutant contents. Compos Sci Technol 68:1869–1876
5. Garg MS, Srivastava D (2014) Effect of glycidyl methacrylate (GMA) content on thermal and
mechanical properties of ternary blend systems based on cardanol-based vinyl ester resin, styrene
and glycidyl methacrylate. Prog Org Coatings 77:1208–1220
6. Jaswal S, Gaur B (2014) New trends in vinyl ester resins. Rev Chem Eng 30:567–581
7. Malik M, Choudhary V, Varma IK (2001) Effect of oxirane groups on curing behavior and thermal
stability of vinyl ester resins. J Appl Polym Sci 82:416–423
8. Division of Paint (1990) Plastics, and printing ink chemistry. Chem Eng News Arch 26:475–478
9. Gaur B, Rai JSP (1992) Curing and decomposition behaviour of vinyl ester resins. Polymer (Guildf)
33:4210–4214
10. Zhang X, Bitaraf V, Wei S, Guo Z (2015) Pyrolysis of heavy oil in the presence of supercritical
water: the reaction kinetics in different phases. AICHE J 61:857–866
11. Johnson RDJ, Arumugaprabu V, Ko TJ (2018) Mechanical property, wear characteristics, machining
and moisture absorption studies on vinyl ester composites—a review. Silicon pp 1–16

13
Polymer Bulletin (2022) 79:477–501 501

12. Cui HW, Suganuma K, Uchida H (2015) Using the Ozawa method to study the thermally initiated
curing kinetics of vinyl ester resin. RSC Adv 5:2677–2683
13. Dev S, Shah PN, Zhang Y et al (2017) Synthesis and mechanical properties of flame retardant vinyl
ester resin for structural composites. Polymer (Guildf) 133:20–29
14. Brown JR, Mathys Z (1997) Reinforcement and matrix effects on the combustion properties of glass
reinforced polymer composites. Compos Part A Appl Sci Manuf 28:675–681
15. Mouritz AP, Mathys Z (1999) Post-fire mechanical properties of marine polymer composites. Com-
pos Struct 47:643–653
16. Zhang S, Ye L, Mai YW (2000) Study on polymer composite strengthening systems for concrete
columns. Appl Compos Mater 7:125–138
17. Jin L, Agag T, Ishida H (2013) Use of allyl-functional benzoxazine monomers as replacement for
styrene in vinyl ester resins. Polym Int 62:71–78
18. Sultania M, Rai JSP, Srivastava D (2010) Studies on the synthesis and curing of epoxidized novolac
vinyl ester resin from renewable resource material. Eur Polym J 46:2019–2032
19. Bobade SK, Paluvai NR, Mohanty S, Nayak SK (2016) Bio-based thermosetting resins for future
generation: a review. Polym Plast Technol Eng 55:1863–1896
20. Yadav SK, Schmalbach KM, Kinaci E et al (2018) Recent advances in plant-based vinyl ester resins
and reactive diluents. Eur Polym J 98:199–215
21. La Scala JJ, Orlicki JA, Winston C et al (2005) The use of bimodal blends of vinyl ester monomers
to improve resin processing and toughen polymer properties. Polymer (Guildf) 46:2908–2921
22. Stanzione JF, Sadler JM, Scala J La, Wool RP (2012) Lignin model compounds as bio-based reac-
tive diluents for liquid molding resins. 21005:1–8
23. Jaswal S, Gaur B (2015) Structure-property correlation study of bio-based multifunctional vinyl
ester resin in presence of methacrylated lignin model compounds. Polym Sci Ser B 57:417–433
24. Jaswal S, Gaur B (2015) Green methacrylated lignin model compounds as reactive monomers with
low VOC emission for thermosetting resins. Green Process Synth 4:191–202
25. Atta AM, Mansour R, Abdou MI, El-Sayed AM (2005) Synthesis and characterization of tetra-func-
tional epoxy resins from rosin. J Polym Res 12:127–138
26. Xiao-an NIEZ, Yi-gang MI, Xia W, Chang Gui-fu L (2013) Study on synthesis and performance of
rosin-derived polyamide as epoxy curing agent. J For Prod Ind 2:5–11
27. Atta AM, El-Saeed SM, Farag RK (2006) New vinyl ester resins based on rosin for coating applica-
tions. React Funct Polym 66:1596–1608
28. Jaswal S, Gaur B (2013) Curing and decomposition behaviour of cresol novolac based vinyl ester
resin. Chem Eng Trans 32:1591–1596
29. Mohan P (2013) A critical review: the modification, properties, and applications of epoxy resins.
Polym Plast Technol Eng 52:107–125
30. Agrawal S, Singhal R, Rai JSP (1999) Curing and rheological behavior of vinyl ester resins prepared
in the presence of tertiary amines. J Macromol Sci Pure Appl Chem 36(A):741–757
31. Thakur T, Jaswal S, Parihar S, Gaur B, Singha AS (2020) Bio-based epoxy thermosets with rosin
derived imidoamine curing agents and their structure-property relationships. Express Polym Lett
14:512–529
32. Smith CA (1987) Characterisation of polymers used in printed circuit board manufacture. Polym
Test 7:79–84
33. Sharma P, Kukreja P, Choudhary V, Narula AK (2005) Curing and thermal behaviour of epoxy resin
in the presence of aromatic imide-amines. Indian J Eng Mater Sci 12:259–264
34. Nazareth Da Silva AL, Teixeira SCS, Widal ACC, Coutinho FMB (2001) Mechanical properties
of polymer composites based on commercial epoxy vinyl ester resin and glass fiber. Polym Test
20:895–899
35. Siva P, Varma IK, Patel DM, Sinha TJM (1994) Effect of structure on properties of vinyl ester res-
ins. Bull Mater Sci 17:1095–1101

Publisher’s Note Springer Nature remains neutral with regard to jurisdictional claims in published
maps and institutional affiliations.

13