Industrial Crops and Products 49 (2013) 412–418

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Industrial Crops and Products

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Use of tung oil as a reactive toughening agent in

dicyclopentadiene-terminated unsaturated polyester resins
Chengguo Liu a,b,∗ , Wen Lei c , Zhengchun Cai c , Jianqiang Chen c , Lihong Hu a,b ,
Yan Dai a , Yonghong Zhou a,∗∗
a
Institute of Chemical Industry of Forestry Products, Chinese Academy of Forest, Nanjing 210042, PR China
b
Institute of Forest New Technology, CAF, Beijing 100091, PR China
c
College of Science, Nanjing Forestry University, Nanjing 210037, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Unsaturated polyester resin terminated with dicyclopentadiene (DCPD-UPR) was modified by tung oil
Received 25 March 2013 (TO) via intermolecular Diels–Alder reaction occurring at the later stage of melt polycondensation. These
Received in revised form 23 May 2013 TO-modified DCPD-UPR (DCPD-UPR-TO) polymers were characterized by FT-IR, 1 H NMR, and gel per-
Accepted 24 May 2013
meation chromatography. The DCPD-UPR-TO polymers were further blended with styrene comonomer
and cured via free-radical polymerization to give crosslinked thermosetting polymers. Scanning elec-
Keywords:
tron microscopy was employed to produce surface morphology and dynamic mechanical analysis was
Tung oil
conducted to study the thermo-mechanical properties. Thermal and mechanical properties of these bio-
Toughening agent
Unsaturated polyester resin
materials were also investigated and the results show that toughness of them increases obviously as the
Dicyclopentadiene increase of TO content. Compared with the neat DCPD-UPR matrix, the matrix obtained from DCPD-UPR-
Diels–Alder reaction TO with a TO content of 20% has maximum increase of 373% and 875% in impact strength and tensile
failure strain due to the synergistic effects of phase separation and crosslink density. However, the opti-
mum amount of tung oil is 10% because its polymer matrix gives a best stiffness–toughness balance. These
oil-based polymer materials show promise as an alternative to replace petroleum-based materials.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction high-added-value areas. As a result, the flexibility and toughness of

Unsaturated polyester resins (UPRs) are currently the most
widely utilized thermosetting polymer because of its low cost,
ease of handling, and good balance of mechanical, electrical, and
chemical properties. The reinforced composite materials and non-
reinforced materials of UPRs have been broadly employed in
aerospace, automotive, marine, infra-structure, military, sports,
industrial fields, etc. (Mighani, 2012). Dicyclopentadiene (DCPD), a
byproduct from the pyrolysis of petroleum for C5 compounds, has
been employed to synthesize DCPD-modified UPRs (DCPD-UPRs)
since 1980s (Krupka et al., 2008; Pan et al., 2012). The excellent
stiffness, corrosion resistance, and air-drying property, combin-
ing with its economical price, make DCPD-UPRs important in UPR
products. However, the brittle nature of them at ambient temper-
ature limits their application in fiber-reinforced plastics and other
∗ Corresponding author at: Institute of Chemical Industry of Forestry Products,
Chinese Academy of Forest, Nanjing 210042, PR China. Tel.: +86 025 85482520;
fax: +86 025 85482777.
∗∗ Corresponding author. Tel.: +86 025 85482777; fax: +86 025 85482777.
E-mail addresses: liuchengguo@gmail.com (C. Liu), yhzhou777@sina.com
(Y. Zhou).
DCPD-UPRs need to be improved.
In the past several decades, numerous soft materials have been
used to address this obstacle for general UPRs. For example, there
are several reports on the modification of UPRs by blending with
rubbers (Pachpinyo et al., 2006; Ray, 2009), diphenylmethane-4,4 -
diisocyanate (Gunduz et al., 2005) or polyurethane prepolymers
having terminal isocyanate groups (Cherian et al., 2006), etc. Due
to the threats of uncertain petroleum supply in the future and envi-
ronmental pollution, there is a growing trend to incorporate natural
oils (renewable resources), especially their derivates, into UPRs as
impact modifiers. Mehta et al. (2004) employed methyl ester of
soybean oil and epoxidized methyl linseedate (EML) to toughen
UPR, and prepared biocomposites from the modified UPRs. The
notched Izod impact strength of biocomposites from the biobased
UPR blends and hemp fiber mat are enhanced by 90% by comparison
with that of the pure UPR/hemp fiber mat composites. Miyagawa
et al. (2006, 2007) used UPRs containing epoxidized methyl soyate
(EMS) or EML to prepare novel biobased resins. The resulting new
biobased thermosets showed relatively high Izod impact strength.
Haq et al. (2009, 2011) prepared biobased resins by a partial substi-
tution of UPR with EMS or EML, and reinforced them with natural
fibers, nanoclays or layered silicates. Toughness of the biobased
resins was improved by the corporation of EMS or EML. Ghorui et al.

0926-6690/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.indcrop.2013.05.023
 C. Liu et al. / Industrial Crops and Products 49 (2013) 412–418
(2011) used maleated castor oil (MACO) as biomodifier in UPR/fly
ash composites. By the incorporation of 5 wt% MACO, the impact
strength of the UPR matrix increased by 52% without any loss in
modulus. Das et al. (2011) prepared novel biomaterials through
the blending of an unsaturated polyester resin/styrene mix with
tung oil (TO), which offered improved impact strength at a very
low content of TO.
In this study, unmodified TO is utilized to improve the tough-
ness of DCPD-UPRs. Although Das et al. (2011) has reported the
physically blending approach to prepare UPR/TO materials, several
distinct features are demonstrated in this work. First, TO is incor-
porated into UPR via the intermolecular Diels–Alder (D–A) reaction
between double (C C) bonds on polyester chains and TO conju-
gated triene groups (Fig. 1). Second, the D–A reaction occurs at the
later stage of melt polycondensation for polyesters. Third, there is
limited report on the modification of DCPD-UPR by natural oils. The
TO-modified DCPD-UPR (DCPD-UPR-TO) polymers are character-
ized by FT-IR, 1 H NMR, and gel permeation chromatography (GPC).
The structures and properties of the cured DCPD-UPR-TO polymer
matrices are also investigated.
2. Materials and methods
2.1. Materials
Tung oil was a commercial product purchased from Jiangsu
Donghu Bio-energy Plant Plantation (China), which has a yellow
color and a specific gravity of 0.935–0.940 at 25 ◦ C. Diethyl-
ene glycol (DEG), 1,2-propanediol (PG), maleic anhydride (MA),
phthalic anhydride (PA), ethanol, potassium hydroxide (KOH), and
phosphoric acid (H3 PO4 ) were obtained from Shanghai Lingfeng
Chemical Reagent Co. Ltd. (China). Dicyclopentadiene (DCPD) with
a purity of 90% was obtained from Hangzhou Yangli Shihua Co. Ltd.
(China). Hydroquinone (≥98%) and styrene (≥98%) were obtained
from Chengdu Kelong Chemical Reagent Co. Ltd. (China). The initia-
tor benzoyl peroxide (≥98%) and the promoter N,N-dimethylaniline
(≥98%) were obtained from Shanghai Aladdin Chemistry Co. Ltd.
(China). The DEG, PG, and styrene were dried by molecular sieves
at least for 1–2 weeks before use. All the other reagents were used
as received.
2.2. Synthesis of DCPD-UPR
The synthesis of DCPD-UPR was performed in two basic steps, as
partially shown in Fig. 1. First, dicyclopentadiene maleate (DCPD-
MA) was synthesized via hydrolysis: a reaction mixture of MA
(39.2 g, 0.4 mol), DEG (12.7 g, 0.12 mol), deionized water (7.5 g,
0.42 mol), and H3 PO4 (0.3 g), was added into a 250-mL four-neck
flask; the flask was then equipped with mechanical stirrer, ther-
mometer, nitrogen (N2 ) gas inlet, and reflux condensation tube.
The reactor was subsequently heated by oil bath to 70 ◦ C and agi-
tated at this temperature for 30 min until the MA solid completely
melt. Then it was heated to 125–135 ◦ C under N2 atmosphere, and
DCPD liquid (41.1 g, 0.28 mol) was added drop by drop. After this
the reacting mixture maintained at this temperature for 2 h to give
a light and transparent liquid. Second, DCPD-modified unsaturated
polyester resin (DCPD-UPR) was prepared via melt polyconden-
sation: a mixture of DEG (5.3 g, 0.05 mol), PG (25.1 g, 0.33 mol),
PA (29.6 g, 0.2 mol), and hydroquinone (0.02 g) was consecutively
added into the reactor. The reflux condensation device was changed
into to a fractional distillation device. The precondensation was
conducted under N2 atmosphere at 160 ◦ C for 1.5 h. After gradually
heating to 200 ◦ C, the polycondensation lasted for 5 h at this tem-
perature until the acid value (Av ) of the reacting mixture decreased
413
to a set value. The obtained DCPD-UPR polymers were a light trans-
parent liquid at 90 ◦ C.
2.3. Synthesis of TO-modified DCPD-UPR
The synthesis of DCPD-UPR-TO polymers was carried out in
three basic steps, as shown in Fig. 1. The first step is the syn-
thesis of DCPD-MA, which is the same as that in the synthesis of
DCPD-UPR. The second and third steps were similar to the second
step shown in Section 2.2. At the latter stage of melt polyconden-
sation, when the acid value of the reacting mixture decreased to
60–70 mgKOH/g, the reactor was cooled to about 160 ◦ C and a cer-
tain amount (for example, 16.7 g) of tung oil was added in drops.
After this the reactor was heated to 200 ◦ C again and maintained at
this temperature until the acid value decreased to the set value. The
obtained DCPD-UPR-TO polymers were light yellow opaque liquids
at 90 ◦ C.
In our experiments, the contents of TO in the obtained
DCPD-UPR-TO polymers were 5%, 10%, 15%, and 20%, thus the corre-
sponding DCPD-UPR-TO polymers were labeled as DCPD-UPR-TO5,
DCPD-UPR-TO10, DCPD-UPR-TO15, and DCPD-UPR-TO20, respec-
tively. The neat DCPD-UPR can be regarded as the DCPD-UPR-TO
polymer with 0% content of tung oil.
2.4. Curing of DCPD-UPR-TO polymers with styrene
All the obtained neat DCPD-UPR and DCPD-UPR-TO poly-
mer products were blended with styrene (64.2 g, 0.62 mol) and
hydroquinone (0.02 g) at 90 ◦ C for 1 h to give liquid resins. The
as-prepared DCPD-UPR-TO/styrene resins were cured following a
same procedure: blended with the initiator (2 wt% of the resins)
for 20 min and then with the promoter (0.2 wt% of the resins) for
1–2 min, poured into molds, cured at room temperature for 24 h,
and postcured at 60 ◦ C for 3 h. After that the neat DCPD-UPR and
DCPD-UPR-TO polymer matrices were acquired, which could be
used for the following characterization of structure and property.
2.5. Characterization
Reaction procedure of melt polycondensation was monitored by
measuring acid values with 1 h time interval, using KOH/ethanol as
standard solution. The acid value was calculated as (Ghorui et al.,
2011)
56.1 · V · CKOH
Av = (1)
1000 · m
where V, CKOH represents consumed volume and initial concen-
tration of KOH solution, respectively; m is the sample weight.
Viscosity (Vs ) measurements for the DCPD-UPR-TO/styrene
resins were performed on a NDJ-8S rotational viscometer (Shanghai
Changji Dizhi Instrument Corporation, China). The IR spectra
were recorded on a Nicolet iS10 IR spectrometer (Thermo-Fisher
Corporation, USA). The 1 H NMR spectra were recorded on a
Bruker DRX-300 Advance NMR spectrometer (Bruker Corpora-
tion, Germany). The GPC chromatographs were recorded on a
GPC instrument with Styragel HR5E and HR2 (300 mm × 7.8 mm,
Waters Corporation, USA) columns as well as equipped with an
Optilab-rEX refractive index detector (Wyatt Technology Corpora-
tion, USA). HPLC-grade tetrahydrofuran (THF) was used as eluent
and the flow rate of the eluent was 1.0 mL/min.
Tensile and flexural tests of the polymer matrices were evalu-
ated using a SANS7 CMT-4304 universal tester (Shenzhen Xinsansi
Jiliang Instrument Corporation, China). Impact tests of the sam-
ples were performed in a XJJY-5 impact tester (Chengde Xinguo
Instrument Corporation, China). All the above tests followed the
procedure specified in the GB/T 2567-2008 Standard. For accuracy
414 C. Liu et al. / Industrial Crops and Products 49 (2013) 412–418

Fig. 1. Reaction scheme for the modification of DCPD-UPR by TO triglyceride molecule.

at least five specimens were measured and the values were
averaged. Thermogravimetric analysis (TGA) was performed on a
STA 409PC thermogravimetry instrument (Netzsch Corporation,
Germany) at a heating rate of 15 ◦ C/min. Dynamic mechanical anal-
ysis (DMA) was conducted in three-point bending geometry on
a Q800 solids analyzer (TA Corporation, USA). Scanning electron
microscopy (SEM) examinations of the impact-fractured samples
were performed on an S-3400N Scanning Electron Microscope
(HITACHI Corporation, Japan). The surface of the fractured samples
after completion of the impact tests was coated with a gold film
prior to SEM observation.
UPRs, is very weak for the DCPD-UPR, which is attributed to the
termination reaction between DCPD and the hydroxyls on UPR.
After the incorporation of TO into DCPD-UPR, two obvious varia-
tions have been found in the spectrum of DCPD-UPR-TO5. First, the
characteristic features of the TO conjugated triene at 3012, 991,
and 964 cm−1 are not observed. Second, the intensity of the peaks
at around 2963 cm−1 greatly increases relative to that of the C O
peak at around 1730 cm−1 . These changes indicate that the con-
jugated triene on TO molecules has reacted with the unsaturated
double bonds on DCPD-UPR chains.
1 H NMR technique is another important tool employed to inves-

tigate the structure of the obtained DCPD-UPR-TO polymers. The

spectra of DCPD-UPR and DCPD-UPR-TO5 are depicted in Fig. 3.
3. Results and discussion The double peak at 7.5–8.0 ppm is corresponding to the protons on
the benzene structure from phthalic anhydride. It can be taken as a
3.1. Structure of the TO-modified DCPD-UPR polymers

The results of ultimate acid value (Av ), viscosity (Vs ), weight- and
number-average molar masses (Mw and Mn ) as well as polydisper-
sity (PDI) for DCPD-UPR-TO polymers with different TO contents
are shown in Table 1. The Av values are very low and almost the
same (about 20 mgKOH/g), indicating the completion of melt poly-
condensation for all the DCPD-UPR-TO polymers. As the increase of
TO contents, viscosities for the DCPD-UPR-TO/styrene resins grad-
ually increase and reach a maximum value of about 1370 mPa s. The
UPRs with these Vs values are in a range suitable for the application
in fiber reinforced materials.
FT-IR technique was employed first to study the structure of
TO-modified DCPD-UPRs. The FT-IR spectra of DCPD-UPR, TO, and
DCPD-UPR-TO5 are depicted in Fig. 2. In the spectrum of TO, there
are several characteristic peaks: the conjugated triene structure
(3012, 991, and 964 cm−1 ), methyl and methylene groups (2925
and 2854 cm−1 ), and ester carbonyl groups (1744 cm−1 ) (Liu et al.,
2012). In the spectrum of DCPD-UPR, there are also some typical
peaks: methyl and methylene groups (2963 and 2887 cm−1 ), C O
on ester group (1730 cm−1 , strong), and C O (1000–1300 cm−1 ).
The hydroxyl peak at 3000–3500 cm−1 , usually strong for general Fig. 2. FT-IR spectra of (a) DCPD-UPR, (b) TO, and (c) DCPD-UPR-TO5.
 C. Liu et al. / Industrial Crops and Products 49 (2013) 412–418
1
Fig. 3. H NMR spectra of (a) DCPD-UPR and (b) DCPD-UPR-TO5.
reference, because the intensity of this peak should not be altered
throughout the synthesis process of DCPD-UPR-TO polymers. The
peaks at 6.3 ppm and 6.9 ppm represent the maleate and fumarate
vinyl protons from maleic anhydride, respectively. It is found that
the ratios of fumarate to maleate vinyl groups are 4.13 and 1.67 for
DCPD-UPR and DCPD-UPR-TO5 polymers, respectively, indicating
the occurrence of maleate to fumarate (cis to trans) isomerization.
Compared the spectrum of DCPD-UPR with that of DCPD-UPR-
TO5 (Fig. 3(a)), the maleate vinyl protons on the DCPD-UPR-TO5
(Fig. 3(b)) almost maintain constant, while the fumarate vinyl pro-
tons have a great decrease from 0.62 to 0.30. Two important facts
are indicated here: first, the TO conjugated triene only reacts with
the fumarate structure on DCPD-UPRs in the D–A reaction; second,
about 50% of the fumarate vinyl groups have been consumed by the
D–A reaction. In addition, the peaks at 3.0–3.3 ppm demonstrate the
protons at the place where the unsaturated double bond is linking
to the conjugated triene group (Liu et al., 2012). The appearance of
the peak at 0.9 ppm belongs to the terminal methyl protons of TO
fatty acids ( CH3 ).
GPC technique is employed to analyze molar masses of the
obtained DCPD-UPR-TO polymers. The elution chromatographs of
GPC are shown in Fig. 4 and the corresponding results of molar
masses are listed in Table 1. As shown in Fig. 4, the area of elu-
tion time at 11–13 min, which corresponds to the section of high
molar mass, has greatly increased for DCPD-UPR-TO polymers by
the incorporation of TO molecules. This fact is further evidenced by
the change of molar masses for the obtained DCPD-UPR and DCPD-
UPR-TO polymers (Table 1). It is observed that both the weight-
and number-average molar masses (Mw and Mn ) of DCPD-UPR-
TO polymers are larger than those of neat DCPD-UPR. All of these
Table 1
Acid value (Av ), viscosity (Vs ), weight- and number-average molar masses (Mw and Mn ) as well as polydispersity (PDI) for DCPD-UPR-TO polymers with different TO contents.
Samples Av (mgKOH/g) Vs (mPa s)
DCPD-UPR 19.9 840
DCPD-UPR-TO5 16.3 967
DCPD-UPR-TO10 20.3 1370
DCPD-UPR-TO15 22.1 1185
DCPD-UPR-TO20 23.6 1348
415
Fig. 4. GPC elution chromatograms of the DCPD-UPR-TO polymers with different
contents of TO.
indicate the occurrence of the D–A reaction between DCPD-UPR and
TO. Moreover, it is found that the DCPD-UPR-TO polymer almost
reach maximum values of Mw and Mn at a TO content of 10%, after
that the molar masses vary slightly. The reason for this may lie in
that the stoichiometric equilibrium of DCPD-UPR and TO in the D–A
reaction is at a ratio of about 9:1 in weight. In other words, it means
that TO molecules can completely react with DCPD-UPR chains until
the TO content is up to a value of about 10%. When adding more TO
(above 10%) into DCPD-UPR, redundant tung oil molecules are left
in DCPD-UPR-TO polymers, thus leading to smaller molar masses
(especially Mn ) and larger PDI values.
3.2. Structures and properties of the cured DCPD-UPR-TO
matrices
The failure surface morphologies of the matrices obtained from
DCPD-UPR-TO polymers with different TO contents were investi-
gated by SEM. Fig. 5 demonstrates the failure-surface morphologies
after the completion of impact tests. In Fig. 5(a), the failure surface
of the DCPD-UPR matrix is generally flat and featureless. This sug-
gests that the behavior of the matrix is linear elastic, and the crack
propagates in a planar manner under the impact loading. However,
the failure surface of the TO-modified DCPD-UPR matrices become
rougher, which is mainly due to the soft structure provided by the
linked or the unreacted TO triglycerides. It was reported that the
rougher surface was identical for dissipating more energy that was
due to shear deformation during the crack propagation (Miyagawa
et al., 2005). Thus it is expected that the increased roughness here
will lead to a pronounced toughening effect on the brittle DCPD-
UPR matrix. In addition, it is found that the DCPD-UPR-TO matrices
with TO contents from 0 to 10% do not show phase separation, while
the matrices with TO contents above 10% demonstrate obvious
phase separation such as small resin pieces. This phenomenon also
indicates that TO can completely react with DCPD-UPR chains up
to a TO content of about 10%, which is in good agreement with the
Mw (g/mol) Mn (g/mol) PDI
1275 618 2.06
2103 737 2.85
3145 858 3.67
2993 807 3.71
3170 818 3.88
416 C. Liu et al. / Industrial Crops and Products 49 (2013) 412–418

Fig. 5. SEM micrographs of the impact fracture surfaces of the polymer matrices obtained from DCPD-UPR-TO polymers with different TO contents.

GPC analysis. This phase separation phenomenon is also expected
to affect the following properties for the TO-modified DCPD-UPR
biomaterials. It is noteworthy that the true TO weight fraction
in the cured DCPD-UPR-TO10 matrix is about 7.4%. This value is
much higher than that reported by Das et al. (2011), in whose
work through a simple physically blending approach the prepared
UPR/TO matrix showed clear phase separation at a TO content of
about 2%.
DMA was conducted to study thermo-mechanical properties
of the obtained bioplastics. The results are depicted in Fig. 6 and
Table 2. It is seen that the storage moduli of all the DCPD-UPR-TO
bioplastics at 25 ◦ C are lower than that of the neat DCPD-UPR, which
means the dynamic mechanical properties of DCPD-UPR-TO matri-
ces decrease by the addition of TO. This fact is also demonstrated by
the storage modulus in the rubbery region (at 120 ◦ C in this study),
as shown in Table 2. Based on the kinetic theory of rubber elastic-
ity, the experimental crosslink density of all the copolymers (ve ),
namely the average number of crosslinks per unit volume, can be
determined from the rubbery modulus using the following equa-
tion (Lu et al., 2005; Miyagawa et al., 2005; Can et al., 2006; Liu
et al., 2013)
E  = 3e RT (2)
where E represents the storage modulus of the crosslinked copoly-
mer in the rubbery plateau region, R is the gas constant, and T is the
absolute temperature. As shown in Table 2, the crosslink densities
of all the matrices are in the range of 2810–2290 mol/m3 , which
is corresponding to crosslink molar masses of 391–480 g/mol. It is
found that both the storage moduli at 25 ◦ C and 120 ◦ C as well as
the crosslink density decrease as the increase of TO content. This is
mainly because the intermolecular D–A reaction between polyester
and TO reduces the amount of crosslinkable C C bonds in the
polyester chains. Glass transition temperature (Tg ) is determined
from the peak of loss factor (tan ı). It can be seen from Fig. 6(b)

Fig. 6. Dynamic mechanical analysis in (a) storage modulus and (b) damping parameter for the polymer matrices obtained from DCPD-UPR-TO polymers with different TO
contents.
 C. Liu et al. / Industrial Crops and Products 49 (2013) 412–418 417

Table 2
Storage modulus (E ), glass transition temperature (Tg ), crosslink density (e ), effective molar mass between crosslinks (Mc ), 10% and 50% weight loss temperatures (T10 and
T50 ) for neat DCPD-UPR and DCPD-UPR-TO polymer matrices.

Samples E at 25 ◦ C (GPa) E at 120 ◦ C (MPa) Tg (◦ C) e (103 mol/m3 ) Mc (g/mol) T10 (◦ C) T50 (◦ C)

DCPD-UPR 1.53 27.5 79.3 2.81 391 294.5 382.0

DCPD-UPR-TO5 1.26 26.8 61.8 2.73 403 294.5 384.5
DCPD-UPR-TO10 1.24 25.4 65.6 2.59 424 302.0 389.5
DCPD-UPR-TO15 0.802 23.6 60.7 2.40 458 294.5 387.0
DCPD-UPR-TO20 0.490 22.4 53.1 2.29 480 292.0 389.5

unreacted oil or other soluble components in the bulk material. The

Fig. 7. TGA curves of the polymer matrices obtained from DCPD-UPR-TO polymers
with different TO contents.
and Table 2 that Tg for the DCPD-UPR-TO bioplastics drops by the
addition of TO and has a minimum decrease of 13.7 ◦ C for the DCPD-
UPR-TO10 polymer matrix by comparison with that of the neat
DCPD-UPR matrix. It may be caused by a combined effect of phase
separation and crosslink density, because the decrease of crosslink
density will result in the decrease of Tg (Can et al., 2006) and the
boundary of phase separation phenomenon at the TO content of
10% make the DCPD-UPR-TO10 matrix less influenced.
Fig. 7 demonstrates TGA thermograms of the DCPD-UPR-TO
polymer matrices with different TO contents. It is observed that
all the bioplastics are thermally stable in nitrogen gas below 180 ◦ C
and exhibit a three-stage thermal degradation above this tempera-
ture (Andjelkovic et al., 2005). The first stage degradation (about
180–320 ◦ C) is attributed to evaporation and decomposition of
stage 2 (about 320–460 ◦ C) is the fastest and corresponds to degra-
dation and char formation of the crosslinked polymer structure,
while the last stage (>460 ◦ C) corresponds to gradual degradation
of the char residue. Table 2 summarizes the thermal data of these
biobased materials, including 10% and 50% mass loss temperatures
(T10 and T50 ). It is clearly seen that both of the two temperatures
increase to maximum values at the TO content of 10%, which is
mainly caused by the phase separation effect as mentioned above.
Compared with the neat DCPD-UPR matrix, the DCPD-UPR-TO10
matrix has a maximum increase of 7.5 ◦ C in both T10 and T50 . Hence,
the DCPD-UPR-TO10 matrix shows slightly better thermal stability
than the pure DCPD-UPR matrix.
The changes in tensile strength and modulus, flexural strength
and modulus of the matrices obtained from DCPD-UPR-TO poly-
mers with different TO contents are shown in Fig. 8. It is observed
that all these properties decrease as the increase of TO content,
indicating the decrease of stiffness for all the DCPD-UPR-TO poly-
mer matrices. This is mainly because of the decrease of crosslink
density, which was reported that its decrease resulted in the stiff-
ness decrease of a polymer matrix (Mehta et al., 2004; Miyagawa
et al., 2005; Haq et al., 2011; Liu et al., 2013). Interestingly, the
decrease in stiffness seems to have two distinct regions: at a
TO content below 10%, the stiffness of DCPD-UPR-TO biomateri-
als gradually decreases; at a TO content above 10%, the stiffness
decreases rapidly. This phenomenon can be attributed to the phase
separation effect, as shown in the above SEM images. As mentioned
in previous works (Mehta et al., 2004; Miyagawa et al., 2005; Ghorui
et al., 2011; Haq et al., 2011; Liu et al., 2013), the introduction of
a second rubber phase like oil-rich phase would sacrifice the stiff-
ness of a polymer matrix but improve its toughness. Therefore, it
is concluded that the phase separation occurring at the TO content
above 10% results in the rapid decrease of stiffness for the DCPD-
UPR-TO matrices. Compared with the neat DCPD-UPR matrix, the

Fig. 8. Tensile and flexural properties in (a) strength and (b) modulus of the polymer matrices obtained from DCPD-UPR-TO polymers with different TO contents.
418 C. Liu et al. / Industrial Crops and Products 49 (2013) 412–418
Fig. 9. Impact strength and tensile failure strain of the polymer matrices obtained
from DCPD-UPR-TO polymers with different TO contents.
DCPD-UPR-TO10 matrix demonstrates decrease of 5.3% and 18.8%
in tensile and flexural strength, 19.3% and 16% in tensile and flexural
modulus, respectively, which still can be utilized in fiber reinforced
materials.
Fig. 9 shows the changes in impact strength and tensile failure
strain of the DCPD-UPR-TO polymer matrices. It is clearly seen that
all these properties increase as the increase of TO content, indi-
cating the increase of toughness for all the DCPD-UPR-TO polymer
matrices. Similarly to the stiffness shown above, the increase in
toughness can be divided into two distinct regions, which can also
be attributed to the effects of phase separation and crosslink den-
sity. It is known to us that both the occurrence of phase separation
and the decrease of crosslink density will lead to the toughness
improvement of the resulting thermosets (Mehta et al., 2004;
Ghorui et al., 2011; Haq et al., 2011; Liu et al., 2013). Compared
with the neat DCPD-UPR matrix, the DCPD-UPR-TO10 matrix shows
increases of 72.5% and 91.3% in impact strength and tensile fail-
ure strain, while the increases in them for the DCPD-UPR-TO20
matrix are 373% and 875%, respectively. Such large improvement in
toughness is due to the synergistic effects of phase separation and
crosslink density. Hence, the toughness of the DCPD-UPR matrix is
greatly improved by the chemical approach we used to incorporate
TO into DCPD-UPR.
4. Conclusion
In this work novel biobased resins, TO-modified DCPD-UPRs,
have been successfully synthesized via the intermolecular D–A
reaction between double bonds on polyester chains and TO con-
jugated triene. The structure characterization of the obtained
DCPD-UPR-TO polymers by IR, 1 H NMR, and GPC indicates the
occurrence of the D–A reaction. Specially, GPC and SEM analysis
demonstrate that TO molecules can completely react with DCPD-
UPR chains at a TO content up to 10%. By the incorporation of TO
into DCPD-UPR, the thermo-mechanical properties, Tg , and stiffness
of the DCPD-UPR-TO polymer matrices decrease, while the ther-
mal stability (T10 and T50 ) and toughness of them are improved.
The mechanical and thermal properties of the polymer matri-
ces are influenced by the synergistic effects of phase separation
and crosslink density. The mechanism analysis on properties will
benefit to the modification of petroleum-based materials with soft
bioresources. These biomaterials including renewable resources
(e.g. tung oil) are very promising in application of fiber-reinforced
composite materials.
Acknowledgements
The authors are grateful to the financial support from Chi-
nese National Special Fund of International Cooperation Of Science
and Technology (No. 2011DFA32440) and Chinese Academy
of Forest for the Special Fund of Fundamental Research (No.
CAFINT2011C02).
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