Industrial Crops and Products 36 (2012) 485–499

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Industrial Crops and Products

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The development and comparison of bio-thermoset plastics from epoxidized

plant oils
Joo Ran Kim, Suraj Sharma ∗
Department of Textiles, Merchandising and Interiors, University of Georgia, 350 Dawson Hall, Athens, GA 30602, USA

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

Article history: This study investigates the development of thermoset plastics from plant-based oils (e.g., linseed, soy-
Received 4 May 2011 bean, cottonseed, oilseed radish, and peanut oils) using an optimal process of solvent-free epoxidation.
Received in revised form 24 October 2011 The epoxidation of plant oils can be accomplished economically by reacting the double bonds of fatty-
Accepted 26 October 2011
acids with hydrogen peroxide. During the solvent-free process catalyzed by the ion-exchange resin, we
Available online 3 December 2011
observed that the influence of several variables was important: the molar ratio of hydrogen peroxide to
unsaturation, acetic acid to unsaturation, and temperature. The epoxidation of plant oils was determined
Keywords:
from the liquid mixture and the composite matrix by thermal and spectroscopic analyses. Compounds
Epoxidation
Linseed
with a higher double-bond (iodine) value showed higher oxirane oxygen percent and selectivity, and
Soybean a higher hydroxyl value because of a greater possibility of attack by solutions causing side reactions.
Oilseed radish Lower iodine values indicated fewer epoxy groups and selectivity, and a lower hydroxyl value. Benzyl
Cottonseed pyrazinium hexafluoroantimonate (BPH) yielded good thermal curing properties; as little as 1% added
Peanut to the plastics produced light-weight composites. Epoxidized linseed oil promises the highest modulus
DMA and impact resistance due to the largest number of double bonds to contribute more epoxy groups and
BPH the large proportion of linolenic acids to produce epoxy groups rapidly.
FA composition
© 2011 Elsevier B.V. All rights reserved.

1. Introduction or H2 O2 (hydrogen peroxide), and are considered an inexpensive

Thermoset composites from epoxy resins are often used in
high-performance structural applications because they generally
possess excellent properties such as toughness and dimensional
stability (Adachi et al., 2002). These resins are generally used as the
binding agent, offering attractive combinations of strength, ease
of processing, and cost. For example, epoxy resin is used as the
binder in composites reinforced with carbon fibers for aerospace
applications (Williamson, 2001). However, in general these resin
are derived from petroleum based chemicals. Therefore, several
research studies are being undertaken to explore the alternative,
sustainable biopolymers for their use in thermoset applications.
Bio-based materials are finding increased attention due to their
availability on a renewable basis and associated environmental
benefits. Plant oils, which are renewable resources, are found in
abundance and have the potential to replace the petroleum-based
polymers (Can et al., 2006; Zhao et al., 2008). Natural oils from
agricultural resources, such as linseed oil and soybean oil, are
useful in polymer material syntheses. In order to produce a rigid
crosslinked thermoset from plant oils, the triglycerides must be
chemically functionalized by epoxidation with organic peracids
∗ Corresponding author. Tel.: +1 706 542 7353; fax: +1 706 542 4890.
E-mail address: ssharma@uga.edu (S. Sharma).
renewable material for the generation of biobased thermoset epoxy
resins (Boquillon and Fringant, 2000). Many plant oils process have
been studied to develop epoxy functionalized resins into the bio-
based thermoset polymers: soybeans (Zaher et al., 1989), linseed
(Chen et al., 2002), canola (Mungroo et al., 2008), and cottonseed
(Dinda et al., 2008).
In general, four methods are available for epoxidation of oils:
(i) epoxidation with percarboxylic acids by acids or enzymes; (ii)
epoxidation with inorganic and organic peroxides which includes
alkaline and nitrile hydrogen peroxide; (iii) epoxidation with halo-
hydrins; and (iv) epoxidation with molecular oxygen (Guenter
et al., 2003). Epoxidation of oils occurs in three stages: (i) for-
mation of peroxyacetic acid, (ii) reaction of the peroxyacetic acid
and the double bonds, and (iii) side reactions which hydrolyze the
epoxy group, resulting in degradation of the epoxy group as shown
schematically in Fig. 1(A and B) (Rangarajan et al., 1995; Rüsch gen
Klaas and Warwel, 1999). Main epoxidation reaction by transfer-
ring oxygen from percarboxylic acid is always present with side
reactions. During ring opening reaction, the side reactions are pos-
sible due to percarboxylic acid which also plays role to produce
epoxy groups, water, and hydrogen peroxide.
Catalytic processes are characterized by three phases: an acidic
solid catalyst phase, an aqueous phase which shows peracetic acid,
and the organic phase which contains epoxy groups (Campanella
and Baltanás, 2004). Diluting the organic third phase with a

0926-6690/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.indcrop.2011.10.036
486 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499

Fig. 1. (A) Epoxidation, (B) side reactions (Rangarajan et al., 1995; Rüsch gen Klaas and Warwel, 1999), and (C) reaction between epoxy group and BPH (Kim et al., 2004).

solvent decreases the rate of side reaction that opens the epoxy ring.
Espinoza Pérez et al. (2009) evaluated the effect of the solvent in the
conversion to epoxy groups in plant oils. The solvent decreased the
rate of side reactions that opened the prior formed epoxy groups.
In solvent free process, hydrogen peroxide is extremely attractive
and so it is the reagent used most. Hydrogen peroxide is more sol-
uble in organic solvent than in water, so that the production of
carboxylic acids, one type of side reaction, decreases (Vlček and
Petrović, 2006).
Studies on epoxidation of different vegetable oils reported
different experimental conditions catalyzed by an ion exchange
resin. Significant factors such as molar ratio of acetic acid and
the unsaturation, the concentration of hydrogen peroxide and the
temperature simultaneously affected the percent and rate of oil
converted (Sinadinović-Fišer et al., 2001; Espinoza Pérez et al.,
2009). Low levels of conversion indicated lower epoxy groups with
low side reactions or lower epoxy groups with high side reactions.
High levels of conversion may show higher epoxy groups with
low side reactions or higher epoxy groups with high side reac-
tions. More dilute hydrogen peroxide promotes hydrolysis of the
epoxy groups. Increasing the temperature can reduce the impact
of the other factors; when the temperature decreases, the other
factors become more significant. Hydrogen peroxide provides the
oxidant in the epoxidation process and is usually added in surplus
 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499 487

Table 1
The compositions of linseed, soybean, cottonseed, oilseed radish, and peanut oils.

Common name C:U (p) Fatty acid (%)

a
Linseed Soybean Oilseed radish Cottonseed Peanut Canola

Palmitic 16:0 4.65 10.36 6.13 19.09 9.49 4.3

Stearic 18:0 3.75 4.49 1.90 2.53 2.51 2.0
Oleic 18:1(1) 19.3 21.42 23.87 18.46 54.13 64.0
Linoleic 18:2(9,12) 15.13 53.54 13.46 55.47 23.80 18.4
Linolenic 18:3(9,12,15) 52.67 7.94 5.34 0.28 2.06 7.2
Arachidic 20:0 0.5 0.5 0.68 0.21 3.16 0.6
Gadoleic 20:1 0.12 0.37 8.58 0.12 0.17 1.1
Erucic 22:1(9) 0.09 0.4 31.76 0.16 0.72 NA

C, number of carbons of the fatty-acid chain; U, number of unsaturation; p, position of carbon after which the unsaturation is located.
a
Not tested, values as shown in Table 3 by Espinoza Pérez et al. (2009).

to ensure a complete reaction. It can also take part in degrad-
ing the epoxy groups (Goud et al., 2007). An ion-exchange resin
has been employed widely in epoxidation because it not only
exchanges other ions with materials in the solution without physi-
cal alteration but also reduces the degradation of the epoxy groups
because of its large molecular size, which cannot allow it to go into
the resin after the peracetic acid has been produced (Gunstone,
1996).
Curing agents (hardeners) play an important role in determining
the storage and handling requirements of epoxy formulations. Cur-
ing agents such as amines, anhydrides and dicyandiamide (DDA),
a latent curing agent, have been used as part of epoxy systems in
adhesives, composites, printed circuit boards, and powder coatings
(Güthner and Hammer, 1993). Laliberte et al. (1983) found that
a one-part epoxy system consisting of DGEBA (diglycidyl ether of
bisphenol A) and DDA can be cured at a temperature of 180–200 ◦ C.
During polymerization or the curing reaction, epoxy groups open
due to the active hydrogen of the curing agents, creating a cross-
linked network structure. Curing agents such as anhydrides and
amines are available to cure epoxidized vegetable oils, but these
agents are toxic, require long curing processes at high tempera-
tures, and have low heat resistance. Kim et al. (2004) reported
N-benzyl pyrazinium hexafluoroantimonate (BPH) to cure epoxy
resin systems were effective curing agents for various petroleum-
based epoxy resin systems as shown Fig. 1(C). Park et al. (2004a)
used as little as 1% BPH to cure epoxy resin systems which exhibited
improved thermal-oxidative resistance and mechanical proper-
ties. They also showed that this curing agent did not propagate
a reaction at a lower temperature (50 ◦ C), but created a rapid con-
version at a higher temperature (180 ◦ C), indicating that the agent
was latent at room temperature. Using this latent catalyst would
increase the storage stability and handling of thermosetting epoxy
resins.
The overall objective of this study was to develop environ-
mentally sustainable bio-thermoset plastics and to compare the
properties derived from linseed, soybean, cottonseed, oilseed
radish, and peanut oils according to their different fatty acids.
Moreover, research was to investigate the thermal and ultrasonic
curing of natural, vegetable-based epoxy in order to determine
its plastic forming ability using the least amount of the curing
agent.
2. Materials and methods
2.1. Materials
Several seed oils were purchased for this study: commercial-
grade linseed oil (Azure Farm, Inc., Dufur, OR, USA), cottonseed
oil (Glicks, Inc., Bloomfield, NJ, USA), soybean oil (Bakers & Chefs,
Inc., Bentonville, AR, USA), and peanut oil (Hollywood Inc., Boul-
der, CO, USA). The department of bioengineering at the University
of Georgia, Athens, GA, USA, provided oilseed radish oil. Vikoflex®
(Gravity: 1.03, Oxirane oxygen: 9.18, iodine value: 3) was gifted
from Arkema Inc., Philadelphia, PA, USA. The following chemi-
cals were purchased from Sigma Chemical Co., St. Louis, MO, USA:
Amberlite IR 120H, acetic acid, H2 O2 , BF3 , pyrazine, benzyl bro-
mide, sodium hexafluoroantimonate, toluene, pyridine, n-butyl
alcohol, ethanolic potassium hydroxide solution, phenolphthalein,
and C17:0-heptadecanoic acid (>98% purity). All other materials
used in this study were analytical-grade reagents.
2.2. Epoxidation of oils
Epoxidation of each oil was carried out in a round three-necked
1 l flask equipped with a mechanical stirrer using a flexible Teflon
blade 8 cm in diameter. A thermometer and an addition funnel
were attached in the flask. Epoxidation took place under the fol-
lowing conditions to yield high conversion and selectivity of each
oil (Espinoza Pérez et al., 2009): 1:1 molar ratio of CH3 COOH and
unsaturation, 2:1 of H2 O2 and unsaturation, 30% (w/w) H2 O2 and
25% resin by weight at 60 ◦ C without solvent. Each test used 150 g of
linseed oil, cottonseed oil, soybean oil, oilseed radish oil, or peanut
oil, as the case might be. The flask was placed in an oil bath and first
acetic acid and Amberlite IR 120H resin was added and stirred for
5 h at 500 rpm and 60 ◦ C, with gradual dropwise addition of H2 O2
(2 ml/min). The yellow mixture was filtered through a cheesecloth.
The organic layer captured by the cheesecloth was washed with a
saturated Na2 CO3 solution at 50 ◦ C and then dried using MgSO4 .

Table 2
Properties of oils after epoxidation.

Oil IV0 IVf OOe OOp Hydroxyl value (mg KOH/g) Conversion Selectivity

Linseed 189.41 31.02 8.91 11.07 7.3 0.81 0.97

Soybean 138.48 17.11 6.65 7.95 4.7 0.84 0.96
Radish 105.10 20.30 4.89 7.08 1.2 0.69 0.85
Cottonseed 117.93 8.12 5.52 6.93 1.8 0.80 0.86
Peanut 97.91 10.20 4.27 5.89 1.0 0.81 0.89
a
Canola 112.20 2.8 6.50 6.59 NA 98.5 1.00
a
Not tested, values as shown in treatment 13 in Table 4 by Espinoza Pérez et al. (2009).
488 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499

Fig. 2. The composition of plant oils by gas chromatography (A), linseed oil (B), soybean oil (C), cottonseed (D), oilseed radish (E), peanut oil (*they were redrawn using Excel.
C17:0 as a standard).

2.3. Fatty-acid profile • Starting with 100 mg of oil in the glass tube, 20 mg ml−1
heptadecanoic acid (C17:0) was added as an internal
Before and after epoxidation, each oil was run on a gas chro- standard.
matograph using BF3 methylation following AOCS official method • Next, 2 ml of 0.5 N NaOH in methanol was added and then incu-
996.01, Sec. E (35). bated at 100 ◦ C for 5 min.
 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499 489

• Next, 2 ml of 14% BF3 , 2 ml of hexane, and 2 ml of saturated NaCl
were added.
• The tube was vortexed and then centrifuged at 1000 rpm for
10 min.
• The upper layer was filtered with anhydrous sodium sulfate.
The gas chromatograph (Agilent Technology model 6890,
Wilmington, DE, USA) was equipped with a flame ionization detec-
tor (FID). Separation was achieved with an SP-2560 column (100 m,
0.25 mm i.d., and 0.20 ␮m film).
Injection (1 ␮l) was performed at a split ratio of 5:1. The carrier
gas was helium supplied at a constant pressure, flowing at a rate
of 1.1 ml/min. The injector temperature was 250 ◦ C and the FID set
point was 260 ◦ C.
The sample was held in the oven at 150 ◦ C for 3 min, followed by
an increase to 215 ◦ C at a pace of 10 ◦ C/min, and then held isother-
mally for 40 min. The number of double bonds in a molecule (iodine
value) was determined for linseed, soybean, cottonseed, oilseed
radish, and peanut oils using American Society for Testing and
Materials (ASTM) method D5554.

Fig. 3. The presence of epoxy groups and double bonds by FT-IR (A) epoxidized linseed (EL) and linseed and commercial Vikoflex® , (B) epoxidized soybean (ES) and soybean,
(C) epoxidized cottonseed (EC) and cottonseed, (D) epoxidized oilseed radish (ER) and oilseed radish, (E) epoxidized peanut (EP) and peanut oil.
490 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499

Fig. 3. (continued)

2.4. Oxirane oxygen content and hydroxyl value of epoxidized oils
The oxirane oxygen content and hydroxyl value of the
epoxidized oils were examined with American Oil Chemists’
Society (AOCS) official methods Cd 9-57 and Tx 1a-66, respec-
tively.
2.5. Synthesis of benzyl pyrazinium hexafluoroantimonate (BPH)
• Pyrazine (5.49 g) was added to benzyl bromide (100.00 g) and
stirred for 48 h at 24 ◦ C under nitrogen gas to prevent additional
reaction.
• After filtering, the precipitate was washed with toluene several
times and dried overnight under vacuum.
• Sodium hexafluoroantimonate solution (14.99 g) was added to
the dried benzyl pyrazinium precipitate and stirred for 10 min.
• The white precipitate from the previous step was added to 20 ml
methanol and stirred at 70 ◦ C to dissolve all the precipitate and
then dried for several days to crystallize (Kim et al., 2004).
2.6. Preparation of plastics from epoxidized oils
BPH was dissolved in acetone, added to the epoxidized oils, vor-
texed for 5 min, and degassed for 60 min at room temperature. The
mixture was poured into a Teflon mold, which was held in an oven
at 90 ◦ C for 1 h, and then at 140 ◦ C for 12 h.
2.7. Analytical methods
Fourier Transform Infrared (FT-IR) spectra were recorded with
4 cm−1 resolution on an FT-IR spectrometer (Thermo Scientific,
model Nicolet 6700, Waltham, MA, USA). Data was acquired using
FT-IR software (Thermo Scientific, OMNIC series suite, Waltham,
 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499
Fig. 3. (continued)
MA, USA) which has been applied widely elsewhere for lipids,
because lipids have functional groups with absorption bands
in the infrared region of the electromagnetic spectrum (Flatten
et al., 2005). 1 H nuclear magnetic resonance (NMR) spectra were
obtained on a spectrometer (Varian, Inc., model 300; Palo Alto, CA,
USA) using chloroform (CDCl3 ) as a solvent.
Thermal experiments were conducted using the following
equipment to determine the extent of the resin conversions and
their thermal transitions into a thermoset matrix: the differen-
tial scanning calorimeter (DSC) (Mettler Toledo, Inc., model 821;
Columbus, OH, USA), the thermogravimetric analyzer (TGA) (Met-
tler model 851) and the dynamic mechanical analyzer (DMA)
(Perkin-Elmer, model 8000; Waltham, MA, USA). The results of this
testing helped to optimize the amount of curing hardener added to
the resin. In addition, thermal analyses allow us to determine the
chemical changes that had occurred, such as oxidation and degra-
dation. The curing behaviors of epoxidized oils were analyzed with
the DSC at a heating rate of 10 ◦ C/min under N2 . Tests were per-
formed using the TGA to investigate the thermal degradation of
epoxidized oils from 25 ◦ C to 400 ◦ C at a heating rate of 10 ◦ C/min
under N2 . A scanning electron microscope (SEM) (Carl Zeiss SMT,
Inc., model 1450; Peabody, MA, USA) was used to investigate the
morphology of the bioplastics produced.
Oven-cured specimens were tested on the DMA for their
mechanical performance over a temperature range of −30 ◦ C to
200 ◦ C at a frequency of 1.0 Hz. The heating rate was 2 ◦ C/min and
amplitude was 15 ␮m. A three-point bending test was used to
determine the damping performance of each bioplastic by eval-
uating its storage modulus, loss modulus and glass transition
temperature (O’Donnell et al., 2004).
3. Results and discussion
3.1. Iodine value and oxirane oxygen percent
The iodine value and the oxirane oxygen content are important
characteristics in the epoxidation of oils. The iodine value specifies
491
the unsaturation of the oils, whereas the oxirane oxygen content
shows the presence of epoxy groups in the oils. Table 1 and Fig. 2
show the initial iodine value and composition of peanut oil, oilseed
radish oil, cottonseed oil, soybean oil, and linseed oils. Linseed oil
had the highest iodine value because it contains the highest amount
of ␣-linolenic acid, which has three double bonds in its fatty-acid
chain. Soybean and cottonseed oils, which each have two double
bonds in their fatty-acid chain, showed around 54% and 55% linoleic
acid, respectively.
Conversion of double bonds to epoxy groups was followed by
an HBr titration. Table 2 shows a range of 4.9–8.9% oxirane oxy-
gen (OOe ). Conversion ranged between 69% and 84%. The final
iodine value after epoxidation showed numerous minor peaks;
these peaks were not well resolved over 35 s of retention time
because of the high molecular weight of oxygen in the fatty-acid
chains. The low conversion rates were due to different initial iodine
values and reaction rates for linolenic acids, linoleic acids and oleic
acids (Scala and Wool, 2002). Linseed oil contains more than 50%
linolenic acids in the triglycerides, whereas soybean and cottonseed
oils contain more than 50% linoleic acid.
Oleic, linoleic, and linolenic acids are comparatively complex:
while each is 18 carbon atoms long, they each have a different num-
ber of double bonds and their double bonds appear at different
locations along their fatty-acid chains. In contrast, oilseed radish
oil is relatively simple: it has 32% erucic acid containing one double
bond located at the 13th position along its fatty-acid chain from the
glycerol center.
There are at least two possible explanations for the variation
in epoxidation results among the oils in this study. The first possi-
bility is that the differences arise from steric factors such as that
double bonds relatively distant from the glycerol center of the
fatty-acid chain are more reactive than double bonds near the
glycerol center. The second possibility looks to electronic effects.
Free fatty-acids have a higher reaction rate of epoxidation than the
triglycerides. As the number of double bonds increases, the electron
density also increases, which causes the rate constant to increase
(Gunstone, 1996). In particular, linseed oil, which has a high level
492 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499

of linolenic acids, reported partial epoxidation with side reactions
(Chen et al., 2002; Zong et al., 2005). In contrast, the erucic acids in
oilseed radish oil, containing a mono-double-bond fatty-acid chain
22 hydrocarbons long, showed a low conversion ratio.
The range of selectivity was mostly high, around 0.85–0.97. The
highest selectivity was for linseed oil (around 0.97) due to having
more double bonds. In the hydroxyl value test, epoxidized linseed
oil (EL) and epoxidized soybean oil (ES) showed higher readings (7.3
and 4.7, respectively) than epoxidized cottonseed oil (EC), epoxi-
dized oilseed radish (ER), or epoxidized peanut oil (EP), under 1.8
because EL and ES have more epoxy groups that can be attacked
by solutions in the process. Epoxidation is a simultaneous process
that produces both epoxy and hydroxyl groups from side reactions
with H2 O2 , H2 O, and CH3 COOOH, as shown schematically in Fig. 1.
In this study, the higher initial iodine value contributed to higher
epoxy conversion and also to higher hydroxyl values.
Fatty acid chain composition has a significant effect on the rate
of epoxidation. The double bonds in oleic and linoleic acid were
equally reactive and the double bonds of linolenic acid were about
two times more reactive than oleic and linoleic acids (Scala and
Wool, 2002). Erucic acid (22:1, cis-13-docosoenoic acid) is present
at high levels in seed oils. It can also be oxidized at the 13th atom of

Fig. 4. The partially epoxidized plant oils by 1 H NMR (A) EL, (B) ES, (C) EC, (D) ER, and (E) EP.
 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499 493

Fig. 4. (continued)

carbon from the glycerol center. A hydrocarbon chain, in its most
stable zigzag form, is characterized by dense, tightly packed chains.
Long-chain fatty-acid chains bend slightly more than a medium
fatty-acid chain (Markley and Klare, 1947). Shorter chains spread
on water, but longer chains form a lens, indicating that the oil’s
work of adhesion to water is less than the work of cohesion (Small
et al., 1986). Additionally, short and medium fatty-acid chains are
100 times more water soluble than the long-chain fatty-acids, due
to their small molecular size, so they showed different affinity in
the organic phase of the epoxidation processes (Johnson and Fritz,
1989). The long fatty-acid chain in erucic acid is less soluble than
oleic acid in the organic phase. It may, therefore, induce a weaker
attack by hydrogen peroxide or a stronger attack by peracetic acid
or water, in either case producing less conversion. We are left to
conclude that the different reaction rates among the oils used in
this study were caused by intrinsic properties such as composition
of the oils, since the solubility of external solutions or and other
extrinsic conditions are similar.
494 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499

Fig. 4. (continued)

3.2. The double bonds and epoxy groups characterized by FT-IR,
1 H NMR
The bands displayed by the FT-IR at 3010 cm−1 were attributed
to C–H stretching of C C–H, and the very weak minor bands at
1651.0 cm−1 and 3052.0 cm−1 were due to CH CH stretching. The
intensity of the 3010.0 cm−1 band decreased with the increasing
degree of epoxidation (Chen et al., 2002). A new band appeared
in the spectra of epoxidized oils at 823.0 cm−1 attributed to epoxy
groups. The intensity of this band increased with the increasing
degree of epoxidation. Fig. 3(A) indicates the presence of unsat-
uration in the linseed oil at 3010.0 cm−1 prior to epoxidation.
Epoxidized linseed oil and Vikoflex® linseed oil showed no peak in
this region, but displayed the presence of epoxy groups in the epoxi-
dized linseed and Vikoflex® epoxy resins at 823.8 cm−1 . Epoxidized
soybean, cottonseed, oilseed radish, and peanut oils showed a simi-
lar pattern, but ER and EP showed low intensity of absorbance in the
FT-IR because the percent of oxirane oxygen was low (around 4.9%
and 4.3%, respectively), attributable to fewer epoxy groups than in
other oils such as EL, ES, and EC.
Fig. 4 shows the 1 H NMR spectra of oils with different degrees of
epoxidation. New resonances at ı = 2.97–3.13 ppm were identified
which were attributed to H 2 , H 3 , H 4 , and H 10 for ring formation
of epoxide (Zong et al., 2005; Chen et al., 2003). The intensity of the
resonance at ı = 2.97–3.13 ppm increased with increasing epoxida-
tion, which represents the CH protons attached to the oxygen atoms
of both the epoxy group, whereas the double bonds are indicated
at 5.2–5.5 ppm. The resonance between 3.8 and 4.4 indicated the
glycerol center in the triglycerides (Scala and Wool, 2002; Chen
et al., 2002). 1 H NMR allows the researcher to detect the presence

Fig. 5. TGA thermographs of the as-received natural and after epoxide of linseed, soybean, cottonseed, oilseed radish, and peanut oils. Methods: Thermal scan was carried
on a TGA instrument at a heating rate of 20 ◦ C/min to observe the thermal stability of these functionalized oils.
 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499 495

Fig. 6. The heat flow analysis of epoxidized oils with 1% weight of BPH, the curing agent by DSC, M.P.: melting point.
496 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499
Fig. 7. Three points bending test of bio-thermoset plastics from epoxidized oils by dynamic mechanical analysis.
of hydroxyl groups attached to the triglycerides at 3.8 ppm (Farias
et al., 2010). EL and ES portrayed a high concentration of hydroxyl
groups in the graphs. Table 1 shows higher hydroxyl values for EL
and ES; but EC, ES, and EP have lower hydroxyl values. EL and
ES have a greater number of double bonds and epoxide groups
attacked by H2 O2 , H2 O, and CH3 COOOH. The values in Table 1 are
also due to simultaneous epoxidation and side reactions in the
epoxidation process.
3.3. Thermal characterization of vegetable oil resins and their
thermoset plastics
3.3.1. Thermal stability of oils before and after functionalization
Fig. 5 indicates that as measured by the TGA, the vegetable oils
showed good thermal stability before and after epoxidation. While
most of the oils begin degrading at approximately 400 ◦ C, soybean
and linseed oils start to lose weight from 150 ◦ C onward. After epox-
idation, linseed oil and soybean oils started degrading at higher
temperature than before epoxidation. As shown in Fig. 6(A and B),
linseed and soybean oils lost their thermal stability after reach-
ing their melting point; however, Fig. 6(C–E) shows a straight line
after reaching their melting point. The formation of an epoxy group
increased thermal stability as shown in Fig. 5(B).
In general, the unsaturated fatty-acids have lower melting
points than the saturated fatty-acids. The additional double bonds
depress the melting point for oleic, linoleic, and linolenic to
13–16 ◦ C, −5 ◦ C, and −11 ◦ C, respectively, whereas close inter-
molecular interactions such as longer and saturated fatty-acid
Table 3
Crosslinking density of epoxy resin.
Resin with 1% BPH Tg (K)
EL 327.3
ES 326.3
EC 320.5
ER 300.6
EP 319.3
chains result in relatively high melting points (Markley and Klare,
1947). Linolenic acid, with its three double bonds, has been used
as an agent to increase drying and film-forming properties in prod-
ucts manufactured by the paint, varnish and linoleum industries.
Introducing one or more double bonds into the hydrocarbon chain
of unsaturated fatty-acids results in one or more “bends” in the
molecule. The geometry of the double bond is almost always a cis
configuration in natural fatty-acids. These molecules do not “stack”
very well; the intermolecular interactions are much weaker than
in saturated molecules. As a result, the melting points are much
lower for unsaturated fatty-acids. Fig. 6 shows the melting points
of the oils in this study. Linseed oil, with the highest composition
of three double bonds on fatty-acids, has a melting point of −40 ◦ C.
Soybean oil, cottonseed oil, oilseed radish oil, and peanut oil have
melting points of −20 ◦ C, −8 ◦ C, 4 ◦ C, and 4 ◦ C, respectively. Dou-
ble bonds result in bends in the molecule which makes it harder to
‘pack’ these molecules into a low-energy crystalline morphology.
Cottonseed, oilseed radish, and peanut oils show a stable line after
melting point, but linseed and soybean oils indicated decreasing
heat flow over 150 ◦ C.
3.3.2. The thermal curing of epoxidized oils
We also conducted an isothermal curing study of all epoxi-
dized vegetable oils in the differential scanning calorimeter (DSC)
at an isothermal temperature of 140 ◦ C. The typical thermograph
of isothermal curing from the DSC instrument is comprised of an
initial baseline, an exothermic peak, and a final baseline. When the
initial baseline and final baseline are at the same level, the curing
E (MPa)  (mol/cm3 )
170.1 6.27 × 10−2
161.3 5.92 × 10−2
101.0 3.79 × 10−2
97.4 3.67 × 10−2
68.2 2.73 × 10−2
 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499 497

Fig. 8. The morphology of bioplastics from epoxidized oils with 1% BPH after curing by scanning electron microscopy from (A) EL, (B) ES, (C) EC, (D) ER, and (E) EP.
498 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499
is assumed to be complete. The rate of reaction is proportional to
the evolved rate of heat in DSC analysis. Therefore, the reaction
rate (dt/dc) was determined for different degrees of curing at these
isothermal temperatures. As shown in Fig. 6, these graphs clearly
show the autocatalytic behavior of epoxy curing. In addition, the
exothermic curves consist of an initial shoulder (initiation) and
main exothermic peaks (curing reaction). The polymerization of
a cationic epoxy system leads to a Lewis acid process with two
separate initiation reactions (Boquillon and Fringant, 2000). The
polymerization of a vegetable-oil-based cationic epoxy system sim-
ilarly leads to a Lewis acid process with two separate initiation
reactions (Bailey, 1964):

BPH + Epoxide−→Ph–CH2 –(O+ of epoxide)–SbF−
6
+ pyrazine
(1)
 dynamic mechanical characteristics of a rubbery material.
BPH + R-OH−→Ph–CH2 –OR + pyrazine + H+ SbF−
6
(2)
The two reactions shown in chemical reactions (1) and (2) are
responsible for the initial shoulder of the exothermic curves, indi-
cating the initiation of the curing reaction, and the subsequent main
exothermic peak reflecting the catalytic action of HSbF6 . It was
observed that 1% of BPH was sufficient to cure epoxidized oils fully.
BPH exhibited a sharp endothermic peak at a temperature of 120 ◦ C,
resulting in its dissociation, which activates the epoxy curing reac-
tion. Integrating the thermographs disclosed that the exothermic
heat of curing was 70.55 J/g for EL, 59.34 J/g for ES, 49.28 J/g for EC,
42.81 J/g for ER, and 36.66 J/g for the EP system. These differences
in the heat of curing among the vegetable oils can be attributed
to EL having a larger number of epoxy groups than other oils due
to the greater degree of unsaturation from constituent esterified
linolenic acid, which contains three double bonds. Fig. 6 shows the
DSC thermograph for epoxidized oils during and after isothermal
curing, in the absence of the curing agent. The presence of the epoxy
rings inhibits close packing the fatty-acid chains, preventing the
transition of the liquid state to the grease state (Wool and Sun,
2005).
3.4. The performance of bio-thermoset plastics
After curing using BPH, we conducted DMA analysis using the
thermal three-points bending mode at temperatures ranging from
−30 ◦ C to 200 ◦ C. Dynamic mechanical properties depend on the
properties of component polymers. The glass transition tempera-
ture gives an indication about the density of cross-linked polymers.
A formulation containing a lower percentage of the curing agent
showed a single relaxation located at a lower temperature. That
means that epoxidized oils are partially miscible with the epoxy
resins, decreasing the cross-linking density of the sample (Rebizant
et al., 2003).
Tan ı relates the impact resistance of a material and the ratio of
the loss modulus to the storage modulus. The peaks in tan ı occur in
the region of the glass transition where the material changes from
a rigid state to a more elastic state; the measure is associated with
the movement of small groups and chains of molecules within the
polymer structure. Glass transition temperature (Tg) represents the
single peak of the tan ı attributed to a higher value with increasing
content of iodine value and oxirane oxygen percent. The higher the
tan ı peak value, the greater is the degree of molecular mobility
(Kuzak and Shanmugam, 1999).
Fig. 7 shows the effect of temperature on the dynamic mechan-
ical performance of bioplastics from various epoxidized oils. All
samples exhibited a drop in storage modulus as temperature
increased because they became more mobile and moved into a
wider packing arrangement in rubbery plateau area approaching
Tg . Variation in initial storage modulus contributed to different oils
depended upon the number of epoxy groups that react with BPH.
Higher epoxy groups give tough materials because of more reac-
tions with BPH. Oil-based plastics showed a significant amount
of the modulus above the glass transition region in the rubbery
plateau. The plastic from EP showed the lowest tan ı and storage
modulus values, but lost storage modulus at temperatures below
50 ◦ C. The plastics from EL, ES, and EC indicated similar tan ı over
50 ◦ C, but they showed a different initial storage modulus. The plas-
tic from EL promised the highest modulus due to larger number of
epoxy groups in the triglycerides and fatty-acid chains as evident
from the higher oxirane oxygen number. The plastics from EP and
ER shows lower toughness similar to rubbery materials that it can
be used in the form of elastomeric polyurethane for shoe soles and
insulation (Pothan et al., 2003). We observed that the plastic from
EP, ER and EC lacked integrity and crumbled compared to EL and
ES plastics, which demonstrated good integrity and showed the
DMA analysis provides information about the viscoelasticity,
crosslinking density and thermal stability of polymer networks.
Crosslinking density can be obtained from the following equation
for rubber elasticity in a plateau region of the DMA curve (Park et al.,
2004b).
E
=
˚RT
where E represents the rubber modulus,  the density of network
or crosslinking density (mol/cm3 ), ˚ the front factor (usually equal
to unity), R the gas constant, and T the absolute temperature in the
rubbery region.
Table 3 shows the storage modulus in the rubbery plateau and
the glass transition temperature of the epoxidized oils system-
cured using 1% by weight of BPH. The rubbery storage modulus
resulted in different values across the tested oil-based epoxy resins,
while the glass transition temperatures were similar. This differ-
ence in the heat of curing can be attributed to the higher number
of epoxy groups in epoxidized oils due to the higher degree of
unsaturation from the constituent esterfied linolenic acid, which
contains three double bonds. As seen in Table 3, crosslinking density
increases as epoxy groups are created. Adding the heavier molecule
weight of epoxy groups into oils increases the impact-resistance
property of the epoxy, resulting in tougher composites. The results
showed that the epoxidized oils were superior to the other rubbers
as an impact modifier in both thermal properties and environmen-
tal compatibility (Park et al., 2004a). Overall, this thermal stability
would produce minimum volatiles and consequently less shrinkage
during the thermal molding process.
The morphological microstructures from scanning electron
microscopy were used to examine the fracture properties of all
neat epoxidized resins. Fig. 8 shows the morphologies of bioplas-
tics from studied epoxidized oils. The bioplastics from EL, ES and
EC demonstrated rippled or fiber-like (Miyagawa et al., 2004) frac-
ture morphologies indicating their good toughness characteristics
which may be attributed to higher epoxidation conversion and
selectivity due to presence of more linoleic and linolenic fatty-
acid chains. This phenomenon of toughness is more prominent in
EL than ES and less in EC neat plastics. The bioplastics from EP
and ER exhibited more fragmentations (powdered particles around
surface) on fracture indicating lack of structural integrity which
is also evident from their lower dynamic storage modulus. This
phenomenon indicates lack of unsaturation, especially due to the
fatty-acid chains such as linoleic and linolenic. Uniform distribu-
tion of the matrix was observed very important for toughening,
because it allowed the yielding process to operate throughout the
matrix (Ratna, 2001). Therefore, the neat resin matrix from EL, ES
 J.R. Kim, S. Sharma / Industrial Crops and Products 36 (2012) 485–499
and EC showed more uniform fracture surface, indicating greater
toughness and impact strength than EP and ER bioplastics.
4. Conclusions
In this study, an epoxidation by hydrogen peroxide along with a
catalyst was the most efficient method to epoxidize oils promising
a high conversion percentage. Fatty epoxides can be used directly
as plasticizers to improve the flexibility, elasticity and stability of
polymer subjected to heat. The solvent-free epoxidation process
generally showed suitable oxirane oxygen levels and less oxirane
degradation. In this study, adding 1% of BPH by weight as a cur-
ing agent was sufficient to fully cure epoxidized oils and contribute
light weight and good thermal stability. The chain length of fatty-
acids and the number or locations of double bonds give different
properties to the bio-thermoset plastics in this study. Linseed oil
containing linolenic acids promised the highest modulus and good
impact resistance properties. Shorter hydrocarbon length on fatty-
acid chains and the number of double bonds (a higher iodine value)
enabled higher selectivity and conversion of epoxy groups to con-
fer tougher plastics matrices. Future work may focus on studying
fiber-reinforced composites created by adding crystalline natural
fiber and blends of vegetable oil-based epoxy resins to improve the
strength of composites while providing complete biodegradability
and appropriate quality.
Acknowledgements
Portions of this research were supported by an award
(BSRI1102) from the Bioenergy Systems Research Initiative at the
University of Georgia. We acknowledge Dr. Casimir C. Akoh for
allowing us to use his GC equipment and Dr. Vikram Dhende for
synthesis of BPH.
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