J Therm Anal Calorim
DOI 10.1007/s10973-017-6403-4
Thermodynamics and kinetics of one-step curing process for vinyl
ester-unsaturated polyester resin in low shrinkage
Haoqiang Sheng1 • Xiaojun Wang1 • Zhigang Pan1 • Xu Chen1
Received: 21 December 2016 / Accepted: 11 April 2017
 Akadémiai Kiadó, Budapest, Hungary 2017
Abstract Vinyl ester-unsaturated polyester resin (VER)
with adipic acid presented the lowest shrinkage and highest
flexural strength among VER with CaCO3, polymer vinyl
acetate (PVAc), or adipic acid after curing. The Gibbs free
energy change of adipic acid/VER specimen was the highest
among pure VER, CaCO3/VER, PVAc/VER, and adipic acid/
VER, indicating the lowest polymerization spontaneity of
adipic acid/VER. Semiquantitative Fourier transform infra-
red proved that adipic acid did not consume during the curing
process. With the presence of adipic acid, traditional two-step
curing process of VER glue changed to a one-step curing
process with a slower reaction rate constant via the analysis of
the curing kinetics. 1H nuclear magnetic resonance and
dynamic differential scanning calorimetry (DSC) show the
existence of hydrogen bonding between VER and adipic acid.
The network structure formed by hydrogen bonding of VER
and adipic acid inhibited the cross-linking between unsatu-
rated polyester and styrene, leading to the decrease of curing
degree of adipic acid/VER. Thermogravimetric was applied
to demonstrate the thermal decomposition behavior of adipic
acid for VER, identifying the inefficient curing of adipic acid/
VER characterized by DSC.
Keywords Thermodynamics  Kinetics  One-step curing
process  Vinyl ester-unsaturated polyester resin (VER) 
Adipic acid  Low shrinkage
& Xiaojun Wang
xjwang@njtech.edu.cn
1
College of Materials Science and Engineering, Nanjing Tech
University, Nanjing 210009, China
Introduction
Low-shrinkage unsaturated polyester resin (LS-UPR) is
widely used in the manufacture of high-precision sheet-
molding compounds and bulk-molding compounds due to
the products made from LS-UPR presenting excellent
specialties, such as smooth surface, small ripple, and low
shrinkage. Generally, cured UPR (including vinyl ester-
unsaturated polyester resin; VER) exhibits 7–8% of the
volume shrinkage [1–3]. The volume shrinkage of cured
UPR specimens is controlled in 2–5% by adding low-
shrinkage additives (LSAs), such as thermoplastic macro-
molecular low-shrinkage additive or filler low-shrinkage
additive [4–6]. LSAs are designed to reduce the thermal
shrinkage of UPR or replace part of UPR [7, 8]. Polymer
vinyl acetate (PVAc) and CaCO3 are two commercial and
most applied LSAs.
Recently, small-molecule low-shrinkage additives
become a focus of new LSAs applied in thermosetting
resins. Yan et al. used 2,2-dimethylmalonic acid as a small-
molecule LSA for UPR, and proposed a mechanism of
polymer ester’s pre-esterification to reduce cross-linking
density of UPR [9]. Hong et al. [10, 11] presented succinic
acid, as a LSA, reducing the volume shrinkage of VER
through the pre-esterification and the optimal polymeriza-
tion of UPR.
In this work, the volume shrinkage and the flexural
strength of VER, CaCO3/VER, PVAc/VER, and adipic
acid/VER were detected. Behaviors of adipic acid in VER
were characterized by semiquantitative Fourier transform
infrared (FTIR), 1H nuclear magnetic resonance (1H
NMR), and dynamic differential scanning calorimetry
(DSC). The Gibbs free energy change, viz the spontaneity
of polymerization, of VER, CaCO3/VER, PVAc/VER, and
adipic acid/VER was analyzed by isothermal DSC.
123

Kinetics parameters of various curing reaction, such as the
apparent activation energy (E), the pre-exponential factor
(A), the reaction orders (n), and the reaction rate constant
(k) of four specimens, were obtained through the detection
and the calculation of non-isothermal DSC. From isother-
mal DSC and non-isothermal DSC experimental results,
curing degree of different cured specimen was obtained to
deduce the effective anti-shrinkage of adipic acid. Differ-
ent thermal decomposition temperatures were detected by
thermogravimetric (TG) experiment to explain the change
of curing degree.
Experimental
Materials
The vinyl ester-unsaturated polyester resin (VER) used in
the work was a styrene solution (containing 32–35 mass%
VER), synthesized by the reaction of methacrylic acid with
bisphenol A epoxy resin, and obtained from Jinling Aliancys
Resins Co. Ltd., China. The number-average molecular
weight (Mn) of VER was 3000 g mol-1. The polar macro-
molecule LSA used in this study was PVAc of styrene
solution, containing 32–35 mass% PVAc, obtained from
Jinling Aliancys Resins Co. Ltd., China. The filler LSA used
in this work was calcium carbonate (CaCO3) produced by
Nanjing Omya Fine Chemical Co. Ltd., China, with purity of
more than 99.5%. The average particle size of CaCO3 (D97)
was 20 lm. The small-molecule LSA used in this work was
adipic acid (purity of more than 99.5%) produced by Jiangsu
Yonghua Fine Chemical Co. Ltd., China. The initiator was
methyl ethyl ketone peroxide (MEKP) (containing more
than 33 mass% MEKP) from Akzo Nobel N.V Co. Ltd.,
China. The promoter used in this study was cobalt naph-
thenate containing about 1 mass% cobalt obtained from
Akzo Nobel N.V. Co. Ltd., China.
Preparation of the specimens
All the cured VER specimens were prepared according to
ISO 3672-2:2000 and the formulation was set as 100
resin: 1 initiator: 0.5 promoter: X LSA. X was set as 3, 6,
9, 12, 15 and 18 phr (parts per hundreds of resin), in
order to reduce the effect of LSAs on the flexural strength
of cured VER specimens. At 25 ± 2 C, the resin and a
LSA were mixed in a beaker according to the mass ratio
of 100: X, and the resin glue was stirred at 200 rpm for
5 min. The promoter cobalt naphthenate (0.5 phr) was
added into the resin glue and stirred for 5 min. After that,
the initiator MEKP (1.0 phr) was added and stirred for
5 min uniformly. Later, the resin glue was poured into a
123
H. Sheng et al.
mold (120 9 15 9 6 mm3). The specimens were cured
for 2 h at 80 ± 1 C, released after cooling down to room
temperature, and were measured or characterized. The
specimen of VER glue was an uncured sample, and cured
VER specimen indicated a cured sample.
Property testing
According to ISO 3521:1997/Cor.1:2003(E) ‘‘Plastics
Unsaturated Polyester and Epoxy Resins-Determination of
Overall Volume Shrinkage,’’ the volume shrinkage of the
cured VER specimens was measured at 23 ± 0.1 C.
According to ISO 178-2010 ‘‘Plastic-Determination of
Flexural Properties,’’ the flexural strength of the cured VER
specimens was measured by electronic universal testing
machine CMT 5254 (made by Shenzhen SANS Measure-
ment Technology Co. Ltd., China, with the maximum flex-
ural force of 100 kN and the accuracy of 0.5%), at the
ambient temperature of 23 ± 2 C and relative humidity of
50 ± 5%.
FTIR experiments
The specimens were characterized by a FTIR spectrometer
(Nicolet Nexus 670) with a resolution of 2 cm-1. Solid
samples were made into KBr plate by grinding with KBr,
and glue specimens were coated on the KBr plate (less than
2 mm in thickness). Thirty-two scans from 4000 to
400 cm-1 were taken for each sample. The spectrum
baseline was linear-corrected automatically by FTIR
spectrometer. Integral peak area of a function group was
obtained for semiquantitative FTIR spectrum and com-
pared each other [12].
DSC experiments
An instrument NETZSCH DSC204 DSC was used for
measuring the curing process of various VER specimens by
isothermal DSC and non-isothermal DSC. Specimens were
sealed in an aluminum sample pan. Under the conditions of
nitrogen gas flow of 30 mL min-1, the mass of the VER
glue used was 5–10 mg (including isothermal DSC and
non-isothermal DSC experiment), and the modulation of
temperature for DSC was ±0.1 C.
The isothermal DSC was performed at 80 C for 1 h
under the nitrogen atmosphere. The curing reaction heat
measured in the isothermal scan was marked as QP. Once
an isothermal DSC was completed, the specimen was
cooled quickly to a temperature of 30 C. QR, which was
the residual heat of curing of the cooled specimens, was
measured by a non-isothermal DSC experiment of the
Thermodynamics and kinetics of one-step curing process for vinyl ester-unsaturated polyester…
cooled specimen heating from 30 to 200 C at a rate of
10 C min-1. The value of QP or QR was the average value
obtained by three parallel experiments separately.
The non-isothermal DSC scans were carried out from 30
to 200 C at heating rates of 2.5, 5, 10, and 20 C min-1
under nitrogen atmosphere to obtain exothermic curves of
uncured VER glue specimen.
The dynamic DSC scans were carried out from 30 to
200 C at a heating rate of 2 C min-1 under nitrogen
atmosphere to obtain the exothermic curves of VER glue
and adipic acid/VER glue both without the initiator and
promoter.
The curing degree a could be calculated by the formula
a ¼ QQTP (where QT is the total curing reaction heat,
QT = QP ? QR).
According to the references [13, 14] and the Kissinger
model, the value of E could be obtained through the linear
 
slope (-E/R) of the plotted line by the formula ln Tb2 ¼

P
ln AR
E  E
RTP (where b is the heating rate of non-isothermal
DSC, Tp is the curing peak temperature of exothermic
peak, A is the pre-exponential factor of the polymerization
reaction, E is the apparent activation energy of the curing
reaction, and R is the gas constant) and the linear fitting of
 
1 b
TP to ln TP2
. The reaction order n was calculated by the

content of CaCO3 being 3 phr, the flexural strength of
Crane formula ddðð1=T
ln bÞ
¼  nR E
þ 2TP :
PÞ
1
H NMR experiments
1
H nuclear magnetic resonance (1H NMR) spectrum was
obtained by a Bruker Avance 400 MHz (9.37T) NMR
spectrometer equipped with 5-mm broad band observe
(BBO) probe to analyze the effect of adipic acid on VER.
The adipic acid, VER glue, and adipic acid/VER glue were,
respectively, dissolved in acetone-d for testing by 1H
NMR. The standard pulse sequence was used with a delay
time of 1 s to obtain spectra. The spectra were registered
after 32 scans. Chemical shifts are referenced to the reso-
nance of TMS.
TG experiments
Thermogravimetric curve was obtained by using an
instrument Netzsch STA 449C (with a sensitivity of
±0.1 C) for cured VER specimens. A specimen was
sealed in an aluminum sample pan. The proportion of LSAs
(CaCO3, PVAc and adipic acid) was all 12 phr. The
specimen with a mass of 5–10 mg was measured from 40
to 600 C at a heating rate of 10 C min-1 under the
conditions of nitrogen gas flow of 30 mL min-1.
Results and discussion
Volume shrinkage and flexural strength of VER
with different LSAs
In this experiment, the changes in volume shrinkage and
flexural strength of cured VER specimens with the pres-
ence of CaCO3, PVAc, and adipic acid were detected and
compared.
The anti-shrinkage effects of CaCO3, PVAc, and adipic
acid on cured VER specimens are shown in Fig. 1. Fig-
ure 1 shows that the volume shrinkage of the cured VER
specimen without LSA is 7.35 ± 0.09%. On the other
hand, the volume shrinkage decreases with LSA’s content
increase for cured CaCO3/VER specimen, cured PVAc/
VER specimen, and cured adipic acid/VER specimen, and
the volume shrinkage of cured adipic acid/VER specimen
is the lowest. Therefore, the anti-shrinkage effect of adipic
acid was obviously better than those of CaCO3 and PVAc.
The relations between the flexural strength of adipic acid
and LSAs of CaCO3 or PVAc are exhibited in Fig. 2.
Figure 2 shows that the flexural strength of cured VER
specimen without LSA is 108 ± 1 MPa, while the flexural
strength of cured CaCO3/VER specimen increases and
decreases with the content of CaCO3 increasing. As of the
cured CaCO3/VER specimen is 116 ± 5 MPa. It is attrib-
uted to CaCO3 particles and polymer chains twining to
improve the interface strength between VER and CaCO3
[15, 16]. As of the content of CaCO3 higher than 3 phr, the
flexural strength of cured CaCO3/VER specimen reduces to
41 ± 3 MPa, due to the CaCO3 powder agglomerates
[15, 16]. The flexural strength of cured PVAc/VER spec-
imen reduces with the content of PVAc increasing, due to
8
CaCO3/VER
7
PVAc/VER
Adipic acid/VER
6
Volume shrinkage/%
5
4
3
2
1
0
0 3 6 9 12 15 18
Content of LSA/phr
Fig. 1 Volume shrinkage of VER specimens with CaCO3, PVAc and
adipic acid
123

120
CaCO3/VER
PVAc/VER
Adipic acid/VER
100
Flexural strength/MPa
80
60
40
0 3 6 9 12 15
Content of LSA/phr
Fig. 2 Flexural strength of VER specimens with CaCO3, PVAc and
adipic acid
large number of micro voids in the cured resin specimen
[17, 18]. Although the flexural strength of cured adipic
acid/VER specimen reduced with the content of adipic acid
increase, the flexural strength of cured adipic acid/VER
specimen was the highest of the three cured VER speci-
mens as of the content of adipic acid higher than 9 phr.
Therefore, considering the volume shrinkage and flexural
strength of cured adipic acid/VER specimen, adipic acid
was found to be the most effective LSA in this experiment
and its optimal addition was 12 phr.
Semiquantitative Fourier transform infrared
(FTIR) experiment
The semiquantitative FTIR spectra of adipic acid, VER
glue, cured VER specimen, VER glue with 12 phr adipic
acid, and cured VER specimen with 12 phr adipic acid,
also VER glue with 18 phr adipic acid and cured VER
specimen with 18 phr adipic acid, are shown in Fig. 3. The
structure of adipic acid and VER is shown in Fig. 4.
The ratio of peak integral area for the stretching vibra-
tion of hydroxyl group peak (–OH, at 3440 cm-1) in adipic
acid to that of carbonyl group peak (–C=O, at 1680 cm-1)
was 1.5 in spectrum (a). The ratio of peak integral area of
lateral alcoholic hydroxyl group peak (at 3440 cm-1) to
peak integral area of carbonyl group peak (at 1680 cm-1)
was 3.1 for VER glue [see spectrum (b)]. After the curing
process of VER, the ratio of peak integral area of the lateral
alcoholic hydroxyl group peak to peak integral area of
carbonyl group peak remains the same, compared FTIR
spectra of (b) with (c). This result illustrates that the
quantity of the lateral alcoholic hydroxyl group was con-
stant as the quantity of carbonyl group is stable in VER
curing process.
123
H. Sheng et al.
(a)
(b)
(c)
Transmittance
(d)
(e)
(f)
(g)
4000 3500 3000 2500 2000 1500 1000 500
18 Wavenumber/cm–1
Fig. 3 Semiquantitative FTIR spectra of a adipic acid, b the VER
glue, c the cured VER specimen, d the VER glue with 12 phr adipic
acid, e the cured VER specimen with 12 phr adipic acid, f the VER
glue with 18 phr adipic acid, and g the cured VER specimen with
18 phr
As of the content of adipic acid was 12 phr or 18 phr,
comparing the FTIR spectra (d) and (e), and the FTIR
spectra (f) and (g), the ratio of peak integral area of
stretching vibration of the hydroxyl group peak (at
3440 cm-1) to peak integral area of carbonyl group peak
(at 1680 cm-1) is about 2.8–2.9 for adipic acid/VER glue
and cured adipic acid/VER. It is obvious that both the total
amount of carbonyl group and the total amount of hydroxyl
group remained the same during the curing process.
Therefore, it is deduced that no carboxyl group (–COOH)
of adipic acid reacted with lateral alcoholic hydroxyl group
(–OH) of the VER in the curing process of VER.
Although there was no esterification reaction happened
between adipic acid and VER, the volume shrinkage and
the flexural strength of adipic acid/VER specimen were
both obviously improved. It is revealed that adipic acid had
an important effect on the curing process of VER. As for a
thermosetting resin, it is necessary to explore the specific
curing process of VER through thermodynamics and
kinetics.
Curing thermodynamics of vinyl ester resin with low
shrinkage
From isothermal DSC, the QP values of VER specimen,
CaCO3/VER specimen, PVAc/VER specimen and adipic
acid/VER specimen were obtained, and the corresponding
curing reaction enthalpy change (DH) calculated by for-
mula of DH ¼ QP  Mn are listed in Table 1. The poly-
merization entropy change of the alkene (DS) is
approximately equal to the value of the entropy change of
the single molecule, and its range is -100 to
-120 J mol-1 K-1 [19]. Hence, changes of curing reaction
Thermodynamics and kinetics of one-step curing process for vinyl ester-unsaturated polyester…
Fig. 4 Structure of adipic acid
and VER
O CH3
H2C C C O CH2
CH3
Table 1 Parameters for the curing thermodynamics of the VER specimen, the CaCO3/VER specimen, the PVAc/VER specimen, and the adipic
acid/VER specimen at 80 C
Specimen QP/J g-1 DH/kJ mol-1
VER 136 -408
CaCO3/VER 116 -348
PVAc/VER 117 -350
Adipic acid/VER 99 -296
Gibbs free energy DG of four specimens could be obtained
by a formula of Gibbs free energy change
DG ¼ DH  TDS, where DG is the Gibbs free energy
change, DH is the enthalpy change, DS is the entropy
change, and T is the absolute temperature. In Table 1, the
Gibbs free energy change DG of the four specimens is less
than zero, indicating that the curing reaction of the four
specimens could be carried out spontaneously in the
experiment. The average Gibbs free energy change (DG) of
adipic acid/VER specimen is -258 kJ mol-1 (see
Table 1), which reveals that the spontaneity of polymer-
ization reaction of adipic acid/VER specimen is the lowest
of four VER specimens under the same reaction conditions.
In conclusion, curing process of four VER specimens
could continue spontaneously, while the spontaneity of
polymerization reaction of LSAs/VER specimens was
lower than that of pure VER specimen. Therefore, it is
necessary to explore the anti-shrinkage mechanism of
adipic acid via the analysis of curing kinetics.
Curing kinetics of vinyl ester resin with low
shrinkage
The specimens of VER, CaCO3/VER, PVAc/VER, and
adipic acid/VER (the content of LSA is 12 phr) were
measured by non-isothermal DSC at heating rates of 2.5, 5,
10, and 20 C min-1, respectively, to investigate the curing
kinetics of VER with low shrinkage under different con-
dition. Their corresponding curing curves of non-isother-
mal DSC are shown in Fig. 5.
Figure 5 shows that the curing curves of non-isothermal
DSC of VER specimen, CaCO3/VER specimen, and PVAc/
VER specimen exhibit two exothermic peaks at various
heating rates. The first exothermic peak of the DSC curve
attributes to the cross-linking polymerization stage
O O
HO C CH2 CH2 CH2 CH2 C OH
O
CH2 CH O C O n CH2 CH CH2 O C C CH2
OH CH3 OH CH3
DS/J mol-1 K-1 DG/kJ mol-1 DG /kJ mol-1
-100 to -120 -373 to -366 -370
-100 to -120 -339 to -332 -336
-100 to -120 -314 to -308 -311
-100 to -120 -261 to -254 -258
between the unsaturated polyester chains and the styrene
molecules. The second exothermic peak belongs to the heat
of homo-polymerization stage of styrene [20, 21]. How-
ever, there is only one exothermic peak in the curing curve
of adipic acid/VER specimen, indicating that the curing
process of VER with adipic acid changed to a one-step
polymerization, different from those traditional ones of
VER specimen, CaCO3/VER specimen and PVAc/VER
specimen. One-step polymerization of VER with adipic
acid also appears one exothermic peak for the isothermal
DSC curve of adipic acid/VER in Fig. 6.
1
H NMR and dynamic DSC were used in the study to
investigate the influence of adipic acid on VER curing
process. In 1H NMR experiment, VER glues with 12 phr
adipic acid dissolved in acetone-d at concentrations of
8.65, 18.22, and 37.49 mM, respectively. Their 1H NMR
spectra are shown in Fig. 7.
There is an unobvious wide polymer peak at 2.9 ppm in
the 1H NMR of VER (shown in Fig. 7b), corresponding to
a small amount of self-winding structure of the VER
[22, 23]. This self-winding structure of the unsaturated
polyester was attributed to the formation of hydrogen
bonds between the C=O group and the –OH group of the
unsaturated polyester itself in the VER (see Fig. 8).
Comparing Fig. 7a, it shows that the –COOH peak of
adipic acid at 10.6 ppm disappeared with the addition of
adipic acid in VER (shown in Fig. 7c–e), which was
attributed to the O–H protons of adipic acid formed a
hydrogen bond with the oxygen atom of C=O in the
unsaturated polyester.
Since adipic acid was a smaller molecule with easier
motion in the resin glue, adipic acid preferentially formed a
hydrogen bond with unsaturated polyester rather than the
hydrogen bonds formed inside unsaturated polyester itself.
Accordingly, the network structure of unsaturated polyester
123
 H. Sheng et al.

(a) (b)
3 –1 3 2.5 °C min–1
2.5 °C min Exo
Exo 5 °C min–1
5 °C min–1
10 °C min–1
10 °C min–1
20 °C min–1

Heat flow/mW mg–1

Heat flow/mW mg–1

2 VER 2 CaCO3/VER
20 °C min–1

1 1

0 0

–1 –1

40 60 80 100 120 140 160 180 200 40 60 80 100 120 140 160 180 200
Temperature/°C Temperature/°C

(c) (d)
3 2.5 °C min–1 3 2.5 °C min–1
Exo –1 Exo 5 °C min–1
5 °C min
10 °C min–1 10 °C min–1
20 °C min–1

Heat flow/mW mg–1

Heat flow/mW mg–1

2 PV Ac/VER 20 °C min–1 2 Adipic acid/VER

1 1

0 0

–1 –1

40 60 80 100 120 140 160 180 200 40 60 80 100 120 140 160 180 200
Temperature/°C Temperature/°C

Fig. 5 Non-isothermal DSC curves of a the VER specimen, b the CaCO3/VER specimen, c the PVAc/VER specimen and d the adipic acid/VER
specimen at heating rates of 2.5, 5, 10 and 20 C min-1

(a)

(a)
(b)
*
(b)

(c) *
(c)

(d) *

(d)
(e) *
40 60 80 100 120 140 160 180 200 12 11 10 9 8 7 6 5 4 3 2 1 0
Temperature/°C Chemical shift/ppm

Fig. 6 Isothermal DSC curves of a the VER specimen, b the CaCO3/ Fig. 7 1H NMR spectra of a adipic acid, b the VER glue and the
VER specimen, c the PVAc/VER specimen and d the adipic acid/ adipic acid/VER glue at concentrations of c 8.65 mM, d 18.22 mM
VER specimen at 80 C and e 37.49 mM

123
Thermodynamics and kinetics of one-step curing process for vinyl ester-unsaturated polyester…

Fig. 8 Schematic diagram of O CH3 O

VER hydrogen bond H2C C C O CH2 CH2 CH O C O nCH2 CH CH2 O C C CH2
CH3 O CH3 OH CH3
H
O CH3 O
H2C C C O CH2 CH2 CH O C O nCH2 CH CH2 O C C CH2
CH3 OH CH3 O CH3
H
O CH3 O
H2C C C O CH2 CH2 CH O C O nCH2 CH CH2 O C C CH2
CH3 OH CH3 OH CH3

S S
S S S Styrene

S
Unsaturated polyester
S
S
Hydrogen bond
S
S

in VER formed easily with the presence of adipic acid
leading to the polymerization peak higher. Adipic acid was
regarded as a ‘‘link bridge’’ constructing between two
unsaturated polyesters liner polymer. (see Fig. 9).
The wide polymer peak of network structure at 2.9 ppm
(see Fig. 7c–e) becomes wider and wider with the con-
centration of adipic acid/VER from 8.65 to 37.49 Mm,
indicating that the size of network structure of unsaturated
polyester in VER bonded by hydrogen bonds enlarged with
the content of adipic acid.
Dynamic DSC curves of VER and adipic acid/VER are
shown in Fig. 10. In Fig. 10, VER specimen exhibits only
one endothermic peak in the temperature range of
32–105 C at a heating rate of 2 C min-1 from 30 to
200 C. The endothermic peak belonged to the hydrogen
bonding fracture between unsaturated polyester and
unsaturated polyester of VER. However, adipic acid/VER
specimen exhibits two endothermic peaks from 30 to
200 C in Fig. 9. The first one (31–105 C) belongs to the
hydrogen bonding fracture between unsaturated polyester
and unsaturated polyester of VER, and the second one
(116–155 C) attributes to the hydrogen bonding fracture
between adipic acid and unsaturated polyester of VER.
As the short chain of adipic acid weakened the steric
the hydrogen bonding between adipic acid and unsaturated
polyester of VER is higher than that of pure VER.
Therefore, the polymerization between unsaturated
polyester and styrene in VER glue was inhibited due to the
network structure of unsaturated polyester in VER via
hydrogen bonding. This retardation coincided with the
subsequent styrene self-polymerization and featured a one-
step curing in the non-isothermal DSC curve.
In that case, the curing kinetics of the traditional two-
step curing process for VER specimen, CaCO3/VER
specimen and PVAc/VER specimen, as well as that of the
novel one-step curing process for adipic acid/VER speci-
men, should elucidated in the work below.
According to Arrhenius equation k ¼ Ae
E=RT
, the
k value is related to the apparent activation energy of the
curing reaction (E) and the pre-exponential factor of the
polymerization reaction (A) at a certain temperature (T).
Various curing peak temperatures of Tp obtained from
the non-isothermal DSC curves at various heating rates are
listed in Table 2.
Various values of E of VER specimen, CaCO3/VER
specimen, PVAc/VER specimen, and adipic acid/VER
 

specimen obtained from ln Tb2 ¼ ln AR E
E  RTP are listed in
P

hindrance of long-chain molecule of unsaturated polyester, Table 3 respectively. In Table 3, the E of adipic acid/VER
the hydrogen bonding between adipic acid and unsaturated specimen is 95 kJ mol-1, higher than those of VER, CaCO3/
polyester of VER was stable than that between polyester VER, and PVAc/VER in the first cross-linking stage of the
and polyester of VER. Therefore, the endothermic peak of two-step curing process. It reveals that the reactivity of the

123
 H. Sheng et al.

Fig. 9 Schematic diagram of CH3 CH3

CH3
adipic acid/VER hydrogen bond
H2C C C O CH2 CH2 CH O C O nCH2 CH CH2 O C C CH2
O OH CH3 OH O

H H
O O
C O C O
CH2 CH2
CH2 CH2
CH2 CH2
CH2 CH2
C O C O
O O
H H
O CH3 O
H2C C C O CH2 CH2 CH O C O nCH2 CH CH2 O C C CH2
CH3 OH CH3 OH CH3

S
S S
S

S S Styrene

S S
Unsaturated polyester
S

S Hydrogen bond
S
Adipic acid
S

VER was decreased for the existence of network structure via

VER hydrogen bonding between adipic acid and VER.
Adipic acid/VER
As shown in Table 3, the reaction orders (n) of one-step
curing and two-step curing of specimens were all 1.
Therefore, the above reaction orders follow the first-order
Heat flow

reaction. The pre-exponential factor of the curing reaction

A was calculated by the formula A ¼ bE expRTðE=RT
2
PÞ
. The
P

calculation results are also listed in Table 3 .

Under the conditions of the first order reaction, the
various values of E in Table 3 and A obtained from
lnA in Table 3 were taken into Arrhenius formula, to
calculate the rate constant of the curing reaction (k) (see
Table 4) at a certain temperature (T) of 80 C. Table 4
40 60 80 100 120 140 160 180 200
shows that the one-step curing reaction rate constant
Temperature/°C
(k) (value of adipic acid/VER specimen) was
Fig. 10 Dynamic DSC curves of VER and adipic acid/VER at 33 9 10-3 s-1, indicating the curing reactivity slowed
heating rate of 2 C min-1 down significantly.

123
Thermodynamics and kinetics of one-step curing process for vinyl ester-unsaturated polyester…

Table 2 Parameters for the non-isothermal DSC of the VER speci- Table 5 Parameters of curing reaction heat (QP), residual of curing
men, the CaCO3/VER specimen, the PVAc/VER specimen and the (QR), total curing reaction heat (QT), and curing degree (a)
adipic acid/VER specimen
Specimen QP/J g-1 QR/J g-1 QT/J g-1 a
Specimen b/C min-1 Exothermic Exothermic
peak 1 peak 2 VER 136 13 149 0.91
Tp/K Tp/K CaCO3/VER 116 16 132 0.88
PVAc/VER 117 17 134 0.87
VER 2.5 358.2 372.2
Adipic acid/VER 99 39 138 0.72
5 371.1 388.2
10 380.2 400.1
20 390.1 416.2
CaCO3/VER 2.5 348.2 372.1 Curing degree of various cured VER specimens
5 359.1 390.2
10 377.2 410.1 QP, QR, QT, and a of VER specimen, CaCO3/VER speci-
20 399.1 433.1 men, PVAc/VER specimen, and adipic acid/VER specimen
PVAc/VER 2.5 370.1 383.1 obtained and calculated from non-isothermal DSC and
5 371.1 401.1 isothermal DSC experiment are listed in Table 5.
10 384.2 419.2 In Table 5, the average value of av, acv, apv, and aav
20 398.0 433.1 were 0.91, 0.88, 0.87, and 0.72, respectively. acv, apv and
Adipic acid/VER 2.5 374.1 – aav were decreased separately by 3, 4, and 21% compared
5 382.1 with av. Due to the lowest a value of adipic acid/VER
10 393.2 specimen, adipic acid performed as excellent anti-shrink-
20 398.2 age among three low-shrinkage additives.
Thermogravimetric analysis was used to analyze the
thermal decomposition of cured VER specimen, cured
CaCO3/VER specimen, cured PVAc/VER specimen, and
cured adipic acid/VER specimen [24, 25]. As temperature
Table 3 Parameters for the curing kinetics of the VER specimen, the
increases to 322–359 C, four cured specimens present the
CaCO3/VER specimen, the PVAc/VER specimen, and the adipic
acid/VER specimen first thermal weightlessness (shown in Fig. 11), attributing
to their low degree of polymerization [26]. The weight-
Specimen Exothermic peak 1 Exothermic peak 2
lessness of cured adipic acid/VER specimen decreases the
E/ lnA/ n E/ lnA/ n most of four cured specimens in first weightlessness
kJ mol-1 s-1 kJ mol-1 s-1 because of the low molecular weight of the cured specimen
VER 70 22 1 52 15 1 formed by the hydrogen bonding between adipic acid and
CaCO3/VER 40 12 1 39 10 1 VER. After the first thermal weightlessness, as temperature
PVAc/VER 73 22 1 50 13 1 increases to 423 C, the second thermal weightlessness
Adipic acid/ 95 29 1 – emerges due to the thermal decomposition of cured spec-
VER imen. Comparing the thermal decomposition in two ther-
mal weightlessness stages, it is obvious that the thermal
decomposition temperature shifts to low temperature
gradually for cured VER specimen (359 C), cured CaCO3/
VER specimen (343 C), cured PVAc/VER specimen
(341 C), and cured adipic acid/VER specimen (322 C).
Table 4 Curing reaction rate constant of the VER specimen, the
CaCO3/VER specimen, the PVAc/VER specimen and the adipic acid/
The thermal decomposition temperature of cured adipic
VER specimen at 80 C acid/VER specimen is the lowest among the four cured
specimens, illustrating that the curing degree of the one-
Specimen Exothermic peak 1 Exothermic peak 2
k 9 103/s-1 k 9 103/s-1 step cured specimen caused by adipic acid was the lowest.
According to article [27, 28], the curing degree of a
VER 109 46 thermosetting resin specimen decreased as its thermal
CaCO3/VER 134 44 decomposition temperature lowered. The TG experimental
PVAc/VER 71 26 result obtained from Fig. 11 shows that the thermal
Adipic acid/VER 33 – decomposition temperature of adipic acid/VER sample (at
322 C) is lowest among four specimens of cured VER

123

100
80
60
Mass loss/%
40
VER
CaCO3/VER
20 PV Ac/VER
Adipic acid/VER
0
50 100 150 200 250 300 350 400 450 500 550 600
Temperature/°C
Fig. 11 Thermogravimetric curves of the cured VER specimen, the
cured CaCO3/VER specimen, the cured PVAc/VER specimen and the
cured adipic acid/VER specimen
specimen, cured CaCO3/VER specimen, cured PVAc/VER
specimen and cured adipic acid/VER specimen. It illus-
trates that the curing degree of cured adipic acid/VER
specimen was the lowest among the four specimens,
resulting in low volume shrinkage of cured adipic acid/
VER specimen.
Unsaturated double bond, which was the functional
groups of VER, performed an incompletely cross-linking
in the curing process, resulting in a low curing degree of
resin. Therefore, the results of thermogravimetric analysis
reconfirmed that the curing degree of the cured adipic
acid/VER specimen was the lowest of four cured speci-
mens. TG experimental results revealed that adipic acid
performed an excellent anti-shrinkage effect in the curing
process of VER.
Conclusions
In this work, the anti-shrinkage effect of adipic acid was
the most significant for VER among three kinds of LSAs.
The volume shrinkage and the flexural strength of cured
adipic acid/VER specimen were 0.33 ± 0.04% and
80 ± 4 MPa with a content of adipic acid being 12 phr.
Adipic acid did not consume during the curing process
and formed a network structure through the hydrogen
bonding between adipic acid and VER to inhibit the cross-
linking of unsaturated polyester and styrene. The average
Gibbs free energy change of adipic acid/VER specimen
was -258 kJ mol-1, the highest among pure VER, CaCO3/
VER, PVAc/VER, and adipic acid/VER, indicating the
lowest polymerization spontaneity of adipic acid/VER.
Traditional two-step polymerization of VER glue changed
to a one-step polymerization with the lowest reaction rate
123
H. Sheng et al.
constant of 33 9 10-3 s-1 at 80 C. The curing degree of
adipic acid/VER was 0.72, the lowest among four speci-
mens. Thermogravimetric experiment result illustrated that
the thermal decomposition temperature of adipic acid/VER
through one-step curing was the lowest among four spec-
imens, indicating the inefficient polymerization with the
lowest curing degree.
Acknowledgements The authors would like to thank Jinling Alian-
cys Resins Co. Ltd., for supplying materials, the foundation of the
Priority Academic Program Development of Jiangsu Higher Educa-
tion Institutions (PAPD 2011-6), and the Open Experimental Foun-
dation of Nanjing Tech University (2017DC086).
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