Polymer-Plastics Technology and Materials

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Vegetable oil-based epoxy resins and their

composites with bio-based hardener: a short
review

Rohani Mustapha, Abdul Razak Rahmat, Rohah Abdul Majid & Siti Noor
Hidayah Mustapha

To cite this article: Rohani Mustapha, Abdul Razak Rahmat, Rohah Abdul Majid & Siti
Noor Hidayah Mustapha (2019): Vegetable oil-based epoxy resins and their composites
with bio-based hardener: a short review, Polymer-Plastics Technology and Materials, DOI:
10.1080/25740881.2018.1563119

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Published online: 17 Jan 2019.

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POLYMER-PLASTICS TECHNOLOGY AND MATERIALS
https://doi.org/10.1080/25740881.2018.1563119

Vegetable oil-based epoxy resins and their composites with bio-based hardener:
a short review
Rohani Mustaphaa,b, Abdul Razak Rahmata, Rohah Abdul Majida, and Siti Noor Hidayah Mustaphac
a
Department of Polymer Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, Skudai, Malaysia; bSchool of Ocean
Engineering, Universiti Malaysia Terengganu, Kuala Terengganu, Malaysia; cFaculty of Industrial Sciences & Technology, Universiti Malaysia
Pahang, Kuantan, Malaysia

ABSTRACT ARTICLE HISTORY

Vegetable oil (VO) is the latest alternative found to be one of the ideal candidates for production Received 13 June 2018
of bio-based polymeric units. There are two main methods for producing bio-based epoxy resins Revised 2 November 2018
and composites: the direct synthesis of VO and the blends of epoxy with VO incorporated with Accepted 16 December 2018
natural or synthetic fibers. However, it is more challenging to produce a fully green bio-based KEYWORDS
epoxy composite, as they have relatively low strength that limits their applications. Thus, this Epoxy; vegetable oils;
article is designed to review the present research advances on VO-based epoxy resins and their composites; resins;
composites with bio-based hardener incorporated with fibers or fillers. bio-based hardener

1. Introduction interest in both research and industrial applications

over petroleum-based thermoset polymers due to its
The significant environmental stresses from the manu-
sustainability, cost reductions, competitive properties,
facture and consumption of petroleum-based thermosets
and environment-friendly characteristics. VO, in parti-
have spurred effort to develop bio-based thermoset
cular, has tremendous potential to replace petroleum-
resins as an alternative to replace the existing thermoset
based thermoset resin because of their versatility, avail-
petroleum-based polymer resins such as epoxies, polye-
ability, renewability, and biodegradability properties.[1,2]
ster, and polyurethanes. Bio-based thermoset polymer
VOs consist of various chemical structure and com-
produced from natural resources such as sugars, poly-
position which enable them to be activated for conden-
saccharides, vegetable oils (VOs), lignin, lipids, proteins,
sation polymerization with the addition of curing
and other monomers have received a great deal of
agent, that is, anhydrides or with the addition of latent

CONTACT Abdul Razak Rahmat [email protected] Department of Polymer Engineering, Faculty of Chemical Engineering, Universiti Teknologi
Malaysia, Skudai 81310, Malaysia
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lpte.
© 2019 Taylor & Francis Group, LLC
2 R. MUSTAPHA ET AL.

catalyst.[3] VOs such as linseed, perilla, tung, oiticica, VOs can be cross-linked into epoxy resins by the
and walnut, which have iodine value >150, have long addition of hardener or curing agent such as aliphatic
been used in coating industries. They are drying oils and aromatic amines and anhydrides. The efficiency of
and they can easily cross-link under atmospheric oxy- hardener or curing agents is depending on the type and
gen without being heated.[4,5] Semi-drying oils, that is, structure of cross-linking agents.[20] Most epoxy curing
safflower, sunflower, soybean, rubber seeds, and agents or hardeners such as aliphatic and aromatic
tobacco seeds oil, have iodine value between 100 and amines, polyamides, amidoamines, anhydride, thiols,
150 require heating and they are widely used in acids, and phenols are derived from petroleum
foods.[6] Meanwhile, nondrying oils (castor, cottonseed, resources. The most popular and commonly used cur-
coconut, rapeseed, olive, karanja, ground nut, sesame, ing agent aliphatic (diethylenetriamine and triethylene-
rice bran, and Mesua ferrea) have iodine value <100 tetramine), aromatic-amines (methylenedianiline,
and they normally require long periods of heat treat- MDA), and cycloaliphatic (isophoronediamine) are
ment at high temperature before drying.[7] The cross- well known to be toxic and cause adverse effects mainly
linking between the VOs with epoxy resin has toward human health and the environment.[21] For
a significant effect on the thermophysical properties of example, MDA amine is carcinogenic, mutagenic, and
the VO-based resin. reprotoxic chemical in animals and possibly human
These distinctive properties enable VOs to meet the beings.[21,22] Their use is very harmful and the contin-
quality and technological requirements. The triglycerides ued reliance on this material should be avoided.
with high fatty acid esters with unsaturated fraction such Therefore, the recent advances in studies focused on
as linoleic acid (C18:3) have better properties than VO to use bio-based hardener from renewable resources to
with lower degree of unsaturation such as linoleic acid create fully bio-based epoxy resin systems.
(C18:2), oleic acid (C18:1), and with saturated fraction In this paper, we aim to provide a general review of
such as stearic acid (18:0) and palmitic acid (C16:0). selected trends in the development of VO-based epoxy
Therefore, VOs such as linseed oil and soybean oil were resins and their composites with bio-based hardener.
found to have better properties than other VOs as they Previous reviews, which have done on bio-based epoxy
have high content of unsaturated triglyceride, which is resin from renewable resources, were mainly focused
more than 50%. This makes them ideal to use as starting on the synthesis, preparation, and use of epoxy resin
monomers for the preparation of bio-based polymers. from renewable resources with typical amine hardener.
Despite these optimistic prospects of VO, which so Thus, in this article, we will provide a review of litera-
far has been reported as the most interesting option to ture on the properties of VO-based epoxy resins and
produce bio-based resin, one important concern arises: their composites with different bio-based hardener. We
their reactivity in order to synthesize the desired resin. also provide an overview of some effective methods of
This is because VOs are not reactive, though they con- improving the mechanical and thermal properties of
tain unsaturation and ester bonds. Moreover, they lack VO-based epoxy resins and their composites.
aromatic or cycloaliphatic structure which causes
a reduction in stiffness and strength of the resin.
2. VO epoxy-based resin with bio-based
Thus, the direct synthesis of polymer resin from VO
hardener
is more challenging and thus satisfactory results have
not yet reached because they have relatively low Epoxidation of VOs is a great potential feedstock for
strength as compared to petroleum-based epoxy resins the production of VO-based epoxy resins. The oxirane
that limit their applications.[2,8,9] ring produced through epoxidation process as an end
Currently, there is a growing trend of blending the group of triglycerides makes them more reactive to be
VOs with petroleum-based polymer resin with the pre- converted into any other useful polymerizable
sence of appropriate hardeners or curing agents in order functionalities.[23] Several studies have reported on the
to produce properties that are sophisticated in today’s direct synthesis of epoxy resin from various types of
market. For instance, many researchers reported on the epoxidized VO such as epoxidized soybean oil
blending of VOs with epoxy resin.[9–14] They found that (ESO),[2,13,15,24] epoxidized hemp oil,[19] epoxidized lin-
inclusion of VO into polymer resin shows a positive seed oil (ELO),[16,17,25] epoxidized karanja oil,[26] epox-
impact in improving the brittleness and low fracture idized castor oil,[18] epoxidized cottonseed oil,[27]
toughness nature of the resulting polymer epoxy system. epoxidized canola oil,[28,29] and many more.
The most common reported VOs that have been used Nevertheless, VO-based epoxy resins do not offer
for the preparation of bio-based polymer resins are satisfactory properties. For example, most of them
soybean,[2,15] linseed,[16,17] castor,[18] and hemp.[19] have a very low glass transition temperature (Tg)
 POLYMER-PLASTICS TECHNOLOGY AND MATERIALS 3

which probably resulted from the decreasing cross- from GSO and a commercially available curing agent,
linking network of epoxy by partially unreacted epox- Priamine. The thermomechanical behavior of all ELO-
idized VOs and fatty acid chains.[30] This limits their based epoxy resin was characterized. Based on the
applications to low strength requirement applications results from DSC and dynamic rheological analysis,
such as nonstructural, coating, and additives.[31] they concluded that ELO-based epoxy resin with ami-
Moreover, the internal oxirane rings of VO-based nated fatty amide (AFA) system was better than other
resin are less reactive than petroleum-based epoxies. commercialized fatty amides, that is, Priamine. The
Therefore, the mechanical performances of VO-based ELO–AFA bio-based resins exhibited higher glass tran-
resins are low as compared to a petroleum-based epoxy sition temperature (Tg) of −9°C compared to −31 and
resin. −38°C for the ELO–Priamine and ELO–AGSO bio-
Few studies have reported on the preparation of based resins, respectively. The similar trend was also
VO–epoxy resin using bio-based hardener. The devel- observed for shear storage modulus at 30°C. Results
opment of VO-based epoxy resin by using bio-based indicated 25, 4.2, and 1.6 MPa for ELO–AFA, ELO–
hardener will allow fully bio-based epoxy networks. AGSO, and ELO–Priamine bio-based resins,
Based on previous studies, there are fewer researches respectively.
regarding bio-based epoxy resin from VO with bio- Takahashi et al.[2] have conducted the investigation
based hardener than bio-based epoxy resin with petro- on the thermal, mechanical, and biodegradability of
chemical-based hardener. This is possibly due to its ESO cured with a terpene-based acid anhydride
inferior mechanical, that is, strength and stiffness and (ESO–TPAn), ESO cured with a hexahydrophthalic
thermal properties. anhydride (ESO–HPAn), ESO cured with
For example, Stemmelen et al.[30] have synthesized a maleinated linseed oil (ESO–LOAn), and ESO cured
fully bio-based epoxy resin derived from ELO and with a thermally latent cationic polymerization catalyst
cured with bio-based epoxy hardener from grapeseed (ESO–CPI). The results based on DSC thermogram
oil (GSO) prepared using cysteamine chloride (CAHC) revealed that ESO–TPA has a higher glass transition
by thiol–ene coupling (TEC) (Figure 1). The thermal temperature (Tg) than those of ESO–HPAn, ESO–
cross-linking reaction between polyamine grapeseed oil LOAn, and ESO–CPI (67.2 as compared to 59.0, −41,
(aminated grapeseed oil [AGSO]) and ELO was investi- and 10°C, respectively). A possible reason is the fact
gated. The cured AGSO–ELO resins showed very low Tg that the cyclohexene moiety of TPAn is substituted by
which is below 0°C (−38°C) as compared with the a bulky isobutenyl group and two methyl groups. ESO–
methyl tetrahydrophthalic anhydride (MTHPA)-cured TPA also has better tensile strength and modulus than
ELO (Tg = 109°C). This indicates that, in terms of those of ESO–LOAn and ESO–CPI.
mechanical properties, it was proven that the VO-based Ding et al.[31] prepared epoxy thermosets resins
epoxy resins could not lead to high Tg materials. The low from ELO with employment of different chain length
Tg indicated poor cross-linking density due to the much of dicarboxylic acids (DCAs) from C6 to C18 and bio--
higher molecular flexibility of the AGSO curing agent derived C36 diacid Pripol 1009F as curing agent. They
compared to MTHPA. found that increasing chain length of DCAs has
The other study performed by the same author decreased the mechanical properties and increased the
focused on synthesizing bio-based epoxy resin from thermal stability of the resulted resins. Adipic acid (C6):
ELO and various fatty amides and diamides.[32] The the shorter chain diacid, was found to have superior
bio-based ELO-based epoxy resins were cured using mechanical properties than other DCAs but exhibited
three types of curing agent: AGSO, aminated fatty poor thermal stability. The Tg of ELO bio-based resin
amide (AFA) curing agent, which was also derived was significantly decreased from 7.0 to −15.1°C for

Figure 1. The amination reaction of GSO using CAHC by UV initiated thiol–ene coupling.
4 R. MUSTAPHA ET AL.

DCA chain length of C6–C36. The decrease in Tg was Ma and Webster[34] prepared fully bio-based epoxy
due to the decrease in cross-link density. The cross-link resin using epoxidized sucrose soyate (ESS) with water
density was higher for shorter cross-linkers, C6, due to soluble natural acids, oxalic acid, malonic acid, tartaric
less flexibility and tighter cross-linked networks. This acid, CA, malic acid, and glutaric acid as cross-linking
phenomenon, in line with results of mechanical proper- agents without the use of extra catalyst or toxic com-
ties of the obtained bio-based resins, proved that adipic pounds except for water. The mechanical and thermal
acid C6 has the best tensile strength of 8.8 MPa and properties as well as the reactivity of the natural acids
Young’s modulus of 22 MPa. However, the thermal toward ESS and the curing process of ESS–carboxylic
resistance as determined by thermogravimetric analysis acid bioresins were studied. They found that cured
(TGA) shows that at temperature of 5% weight loss, ESS–carboxylic acid bioresins exhibited excellent ther-
resin cured with bio-derived C36 diacid Pripol 1009F mal and mechanical properties, which are also degrad-
had highest thermal stability (368.8°C), whereas adipic able. The dynamic mechanical analysis (DMA) test
acid C6 had the lowest at 347.4°C due to more bonds to results proved that the glass transition temperature
absorb and dissipate energy for internal reordering. (Tg) (based on peak of tanδ) is in the 90°C range
Kadam et al.[26] have synthesized bio-based epoxy and the initial degradation temperatures in the
resin from karanja oil using epoxidation method in the 240–250°C range.
presence of H2O2 and acetic acid. The prepared epox- Darroman et al.[35] prepared bio-based epoxy hard-
idized oil was then reacted with two bio-based acids: ener from cardanol which functionalized by TEC with
citric acid (CA) and tartaric acid (TAR). It was found cysteamine. These bio-based resins have demonstrated
that the thermal stability of bio-based CA–epoxy resin thermal and mechanical properties that are comparable
and bio-based TAR–epoxy resin was comparable with to commercial epoxy hardeners, which was obtained by
petroleum-based epoxy resin with degradation tem- Mannich reaction using phenolic compounds with for-
peratures at 5% weight loss from TGA analyses of 280 maldehyde or toxic amines. From the TGA analysis
and 295°C, higher than that of the comparable diglyci- under nitrogen atmosphere at 10% onset degradation,
dyl ether of bisphenol A (DGEBA) resins (125°C). The the resin cured with commercially available cardanol-
DSC thermogram results revealed that bio-based CA– based amine agents and new cardanol-based amines
epoxy resin has higher Tg (112.70°C) as compared with degraded at temperature about 325 and 328°C, respec-
bio-based TAR–epoxy resin (108.64°C). The biodegrad- tively. This result shows that commercially available
ability analysis revealed that bio-based tartaric acid– cardanol-based amine agents have faster weight loss
epoxy resin was degraded 95% in 259 days as compared than new cardanol-based amines. DSC results show
with bio-based CA–epoxy resin, degraded 82% in that the Tg for commercial and new cardanol-based
69 days. No degradation was observed for petroleum- amine agent is varied with the values of 30 and 19°C,
based epoxy resin under similar conditions. respectively. This is because commercial cardanol-
Shibata and Nakai[33] have explored tannic acid (TA) based amine is less functionalized compared to new
as a curing agent with ESO for bio-based epoxy resins: cardanol-based amine agent.
glycerol polyglycidyl ether (GPE) and sorbitol polygly- Table 1 summarizes the thermal and mechanical
cidyl ether (SPE). In their study, they varied the properties of various types of VO/epoxy resins with
amount of TA in epoxy (GPE/SPE)/hydroxyl ratio of bio-based hardener. It can be concluded that properties
1/0.8, 1/1.2, and 1/1/4. They found that the tanδ peak of VO-based epoxy resin are depending on VO com-
temperature and Tg measured by thermomechanical position, ring-opening agent, degree of epoxidation of
analysis increased with increasing amount of TA. The VO, and types of epoxy resin used. The higher func-
most balanced mechanical and thermal properties were tionality of the vegetable, the higher cross-linking den-
observed for GPE/TA and SPE/TA resins with epoxy/ sity, glass transition temperature (Tg), and tensile
hydroxyl stoichiometry ratio of 1/1 which were cured at strength of the VO-based epoxy resin.
160°C for 3 h and 160°C for 2 h, respectively. The SPE/
TA resin exhibits higher glass transition temperature
(Tg) between 63 and 79°C as compared to GPE/TA 3. VO-based epoxy resin with bio-based
resin (between 65 and 95°C). This can be explained hardener blends
due to greater epoxy functionality of SPE than GPE.
The tensile strength for both types of resin shows the As mentioned previously, the direct synthesis of epoxy
optimum value in agreement with the epoxy/hydroxyl resins generally shows low physical and chemical prop-
stoichiometry (1/1) with ~36 and ~60 MPa for GPE/TA erties that inevitably limit their use in the marketplace.
and SPE/TA, respectively. This is because the Tg for polymer must be higher than
 POLYMER-PLASTICS TECHNOLOGY AND MATERIALS 5

Table 1. Thermal and mechanical properties of various types of vegetable oil–epoxy-based resin with bio-based hardener.
Properties
Tensile Tensile (TGA) Degradation
Hardener, initiator and strength modulus temperatures (Td)
Epoxy resin accelerators Tg (°C) (MPa) (MPa) Impact strength (°C) References
ELO Polyamine issued from Tg (based on peak of – – – – [30]

grapeseed oil (AGSO) loss modulus): −38

ELO ● AGSO Tg (based on peak of – – – – [32]

● AFA loss modulus):

● Priamine 1075 ● −38
● −9
● −31

Epoxidized soybean TPAn Tg (based on DSC <22 <800 – – [2]

oil thermograms): 59–67

ELO DCAs from C6 to C18 −15.1–7 1.1–8.8 4.7–22 – Td 5% (TGA in N2): [31]

diacids and a cyclic diacid, 347.4–368.8

Pripol 1009
Epoxidized karanja oil ● CA Tg (based on DSC CA: 10.60, CA: 2.65, – Td 5% (TGA in N2): [26]

● Tartaric acid (TAR) thermograms): TA: 4.50 TA: 2.58 280–295

109–112.7
Epoxidized soybean Tannic acid (TA) 63°C < Tg (based on 23–60 1400–2400 – – [33]

oil tanδ peaks) < 90°C

ESS Water-soluble natural Tg (based on tanδ – – Reversed impact In the 240–250°C [34]

acids (oxalic acid, malonic peaks): 17–96 (in·lb): 6 to >168 range

acid, tartaric acid, citric
acid, malic acid, and
glutaric acid)
Epoxidized cardanol ● Commercial cardanol- Tg (based on DSC – – – Td 10% (TGA in N2): [35]

NC-514 based amine thermograms): 19–30 280–295

● New cardanol-based
amines (cardanol
cysteamine)

ELO: Epoxidized linseed oil; AGSO: aminated grapeseed oil; AFA: aminated fatty acid; TPAn: terpene-based anhydrides; DCA: dicarboxylic acid; CA: citric acid;
ESS: epoxidized sucrose soyate.

its intended work environment in order to serve as less reactive oxirane rings in the triglyceride as compared
a useful polymer. Therefore, several authors reported to petroleum-based epoxy resin. A further increase in the
on the blends of petroleum-based epoxy resins with VO concentration inevitably contributes to higher stress
epoxidized VOs. The partial replacement of high viscos- concentration point, which decreased the strength prop-
ity of petroleum-based epoxy resin with functionalized erties of the bio-based resin.
VO may produce materials with acceptable properties Several studies have reported a comparison on
and a low overall cost with improved processability.[36] mechanical and thermal properties of epoxy resin cured
Blending of VOs with epoxy resin, particularly with bio-based hardener and commercial petroleum-
DGEBA, has been intensively reported by Refs. [37–40]. based hardener. For example, Ref. [43] reported the
A critical review of bio-based epoxy resin and hardeners is synthesis of two bio-based epoxy curing agents using
also presented by Baroncini et al.[6] and Ding and rosin derivative, maleopimaric acid (MPA) and maleopi-
Matharu.[41] In general, incorporation of VO in epoxy marate. They compared the curing behavior of these
resin leads to increase in the toughness properties of the curing agents with commercial amine curing agents in
resulting bio-based resin system.[8,10,38] The higher order to investigate thermal and mechanical properties of
amount of VO can result in higher impact energy absorp- the cured epoxy resin. They found that epoxies cured
tion in bio-based resins. This could be due to a long, with rosin-based curing agents demonstrated higher Tg
flexible, and resilient network structure exhibited by the and modulus but slightly reduced the thermal stability
VO which has increased the mobility of resulted resins, compared with commercial curing agents.
thus contributing to higher resistance to crack initiation Wang et al.[44] reported the synthesis of rosin-based
and propagation.[42] However, the addition of epoxidized imidoamine type (RMIA) and studied curing behavior
VO decreased the tensile and flexural properties of the of epoxy resin. They compare the curing behavior of
bio-based resin. This reduction is related to a weak inter- rosin curing agent which was obtained by reaction of
phase interaction between VO and epoxy networks due to MPA with diamine (MPA–ED) and MPA with the
6 R. MUSTAPHA ET AL.

commercial aromatic amine curing agent diaminodi- of ESO in the sample also increased the enthalpy of
phenylmethane (DDM). The results showed that the reaction, maximum exothermic temperature as well as
epoxy cured with RMIA exhibited higher Tg and simi- the activation energy of the system.
lar moduli than that of MPA but slightly lower degra-
dation temperature compared with epoxy cured with
4. Fiber-reinforced VO–epoxy-based
DDM, which revealed the importance of the structure
composites with bio-based hardener
of curing agents.
Chang et al.[45] investigated the properties of two VO-based epoxy resins may be reinforced with natural
types of bio-based curing agents derived from terpene, or synthetic fibers and thus produce partially or fully
namely, terpene maleic anhydride (TMA) and MPA. green composites. Synthetic fibers such as glass, carbon,
They also compared these bio-based curing agents with Kevlar, and boron fibers are traditionally being used as
petroleum-based curing agent methyl nadic nhydride reinforcements and fillers in polymer composites. This
(MNA) in order to study the mechanical and thermal is due to their role as reinforcing materials in order to
properties of the cured isosorbide epoxy system. The improve the performance of the composites. However,
results showed that MPA cured isosorbide epoxy resin synthetic fibers are resistant to biodegradation and they
has higher Tg and better or comparable thermal and are derived from petrochemical products, that is, not
mechanical properties than that of MNA cured an iso- sustainable and not eco-friendly products. Continuous
sorbide epoxy system. reliance on these materials may pose environmental
Although the incorporation of bio-based hardener problems and cause depletion of fossil fuel resources.
has improved the Tg and modulus of epoxy resin, the Therefore, recent years have witnessed a huge interest
addition of VO generally leads to a low cross-link in developing another type of reinforcement with nat-
density upon poor miscibility of VO and epoxy resin. ural origin as an alternative to replace traditional syn-
Studies on the mechanical and thermal properties of thetic fibers in polymer composite systems.
various matrix compositions cured with petrochemical Natural fibers are interesting reinforcing materials
anhydrides or with three different types of bio- because they have advantages which include their com-
hardeners (1, 2, 3) in the presence of imidazole as an paratively low cost, nontoxic, acceptable tensile
accelerator have been conducted by Bledzki et al.[12] In strength, and their possible biodegradability.[46,47] In
their study, woven jute and glass fiber fabrics were used addition, in terms of producing fully green composites,
as reinforcement for the bio-based composites. The it is imperative to use natural fibers as reinforcement in
results obtained from DSC showed that the Tg and bio-based resins in which both fiber and matrix are
enthalpy of curing reaction of epoxy system cured derived from natural resources. Different types of nat-
with petrochemical hardener or bio-hardener were ural fibers might result in different properties. For
decreased by increasing the epoxidized plant oil content example, the bast fibers are commonly used as reinfor-
in epoxy system. The higher bio-content matrix (epox- cement in composite applications because it has high
idized plant oil + bio-hardener 2) shows the lower Tg of tensile strength as compared to other plant fibers. The
50° as compared to the petrochemical matrix (DGEBA– properties of natural fibers are strongly dependent on
epoxy + anhydride) which is 120°C. However, the the part of the origin of the plant, the quality of the
charpy impact results proved that the increasing of harvest, age and body of the plant from which they are
epoxidized plant oil content improved the impact extracted, the extraction techniques, environmental
strength of the epoxy system. The impact strength of conditions of the site, and soil condition.
bio-based resin with bio-hardener 3 was 20–30% higher There are few reports on natural fiber-reinforced bio-
than that of resin with anhydride hardener. based epoxy composites with bio-based hardener so far.
Roudsari et al.[13] have conducted the investigation Shibata et al.[48] reported biocomposites produced by
on the kinetics of the reaction of DGEBA-based epoxy ESO, tannic acid (TA), and microfibrillated cellulose
resin containing different amounts of ESO (10, 20, and (MFC). The compression molding was used to fabricate
30 wt%). The prepared resins were cured with sebacic the biocomposites. Varying contents from 5 to 11 wt%
acid as a bio-based hardener. They used nonisothermal of untreated MFC was mixed with an ethanol solution
differential scanning calorimetry (DSC) and model-free with ESO and TA. Biocomposites with the incorporation
isoconversional method to study the curing kinetic data of MCC yielded biocomposites with tensile strength and
and determine the activation energy of the reactions. tensile modulus that are much higher than the control
They found that the enthalpy of reaction, as well as the ESO–TA. The ESO–TA composites at 9 wt% MCC
activation energy of reaction of bio-based hardener, loading depicted the highest tensile strength up to 72%
was higher than that of amine hardener. The addition (26.3 MPa) higher than that of control ESO–TA. The
 POLYMER-PLASTICS TECHNOLOGY AND MATERIALS 7

tensile modulus of biocomposites were found to reach E-modulus of around 60 and 7400 MPa were measured
1.33 GPa at 11 wt% MCC loading. The glass transition for all composites regardless of the bio-content, respec-
temperature was also improved to 61°C for ESO–TA tively. The impact strength increased with increasing
composites with 9 wt% MCC loading. amount of the epoxidized VO. The DSC test showed
Takahashi et al.[2] fabricated composites from ESO that the Tg of the composites decreased with increasing
cured with a TPAn, HPAn, LOAn, and thermally latent epoxidized plant oil content in epoxy system cured with
CPI. The ESO and curing agents were blended using petrochemical hardener or bio-hardener. Tables 2 and 3
a weight ratio of 1:1 and cured at temperature of 150°C. present the summary of thermal and mechanical proper-
The lyocell fibers were used as reinforcement. The fiber ties of various types of VO/epoxy resins and VO/epoxy
content was varied at 25, 50, and 75 wt%. The produced composites with bio-based hardener, respectively.
composites showed that mechanical properties of ESO–
TPAn composites were better than those other compo-
sites. The tensile strength of ESO–TPAn/lyocell compo- 5. Approaches to improve properties of VO
sites increased systematically with increasing fiber content epoxy-based resins and their composites
in the composites. They found an increment in tensile Three approaches may be used to improve the perfor-
strength and tensile modulus for composites at 75 wt% mance of VO–epoxy-based resins and their composites:
lyocell fiber loading were over threefold (65 MPa and modify the VOs, treatment of fibers as well as add
2.3 GPa) higher compared to those of neat ESO–TPAn a filler or additives.
resin.
Bledzki et al.[12] used epoxidized VO-based epoxy
reinforced with jute fibers to produce bio-based compo- 5.1. Chemical and physical modifications of VO
sites by resin transfer molding. The VO-based epoxy
composites contain epoxidized VO with three types of The most common way to modify the VOs is by functio-
bio-based hardener: 1, 2, and 3, as well as petrochemical nalizing the reactive sites in triglycerides, that is, double
anhydrides as curing agents. Depending on the epoxi- bond, ester groups, and allylic carbon into polymerizable
dized VO content, tensile strength as well as the monomer via epoxidation, acrylation, maleinization,

Table 2. Thermal and mechanical properties of various types of vegetable oil/epoxy resin blends with bio-based hardener.
Properties
Tensile Tensile Impact TGA) Degradation
Epoxy Hardener, initiator, strength modulus strength (J/ temperatures (Td) (°
resin Vegetable oils and accelerators Tg (°C) (MPa) (MPa) m) C) References
DGEBA Epoxidized plant oil ● Bio-hardeners Tg (based on DSC 14–58 900–2300 – Td 1% (TGA in N2): [12]

(10, 20, and 30 wt%) (1, 2, 3) thermograms): 127–244

● Imidazole as 50–120
an accelerator

DGEBA ESO (10, 20, and Sebacic acid Tg (based on DSC – – – – [13]

30 wt%) thermograms):
<−5–20
DGEBA: Diglycidyl ether of bisphenol A; ESO: Epoxidized soybean oil.

Table 3. Thermal and mechanical properties of various types of vegetable oil/epoxy composites with bio-based hardener.
Properties
Hardener, Tensile Tensile Impact (TGA) Degradation
initiator and strength modulus strength temperatures (Td) (°
Epoxy resin accelerators Fiber/Particle Tg (°C) (MPa) (MPa) (J/m) C) References
DGEBA ● Bio-hardeners Jute fiber (25 wt – 60 7400 <8–12 – [12]

(1, 2, 3) %)
● Imidazole as
an
accelerator

Epoxidized soybean TPAn Lyocell fibers (25, – <65 <2300 – – [2]

oil 50, and 75 wt%)

Epoxidized soybean TA MFC (5–11 wt%) Tg (based on 15–26 460–1330 – – [48]

oil tanδ peaks):

58–61
DGEBA: Diglycidyl ether of bisphenol A; TPAn: terpene-based anhydrides; TA: tannic acid; MFC: microfibrillated cellulose.
8 R. MUSTAPHA ET AL.

amidation, and glycerolysis reactions. Among these mod- epoxidized oil by in situ peracid method is shown in
ification methods, epoxidation was found to be the most Figure 3. The efficiency synthesis of EVOs is depend-
common, simple, and commercially important reaction ing on the origin, types, and amount of double bonds
to functionalize VOs since the oxirane rings produced of VOs, concentration of the hydrogen peroxide, reac-
have high reactivity to be readily transformed into desired tion temperature as well as types and concentration of
polymerizable functionalities.[23,49,50] catalyst added.[1,52–56]
As acknowledged in the literature, epoxidation of There are many researchers who have conducted
VOs can be done through several processes such as studies focusing on epoxidation of VO in order to
epoxidation with peracids, epoxidation with organic increase the epoxy yield. Methods to optimize the con-
and inorganic acid with a transition catalyst, epoxida- version rate of epoxidation were comprehensively
tion with halohydrin, and epoxidation via molecular reported by Tan and Chow.[57] The quality of EVOs is
oxygen.[7] A schematic example of a triglyceride epox- measured by oxirane and iodine value. Better quality of
idation process is shown in Figure 2. Of the four EVO is EVO with higher number of oxirane ring and
methods, the most common is through peracids lower iodine value.[58]
formed in situ by reacting a carboxylic acid with con- As reported by Abdullah and Salimon,[59] the
centrated hydrogen peroxide to produce percarboxylic sequences of reactivity of some peracids and the effec-
acid. Using this method, EVOs can be produced in tiveness of catalyst are m-chloroperbenzoic > performic
large number.[7,52] The general reaction scheme of > perbenzoic > peracetic and sulfuric acid > phosphoric

Figure 2. Epoxidized triglyceride molecule.[51]

Figure 3. Preparation of epoxidized vegetable oil by the in situ peracid method.[4]

 POLYMER-PLASTICS TECHNOLOGY AND MATERIALS 9

acid > nitric acid > hydrochloric acid, respectively. The Other than functionalizing the triglycerides, there
enzymes that will produce high degree of esterification are several methods that may be applied to modify
reported are n-octanol, n-haxanol, and n-butanol. the double bonds of VOs such as hydroxylation of
Campanella et al.[56] have conducted a study on the triglycerides and conversion of triglycerides into
synthesizing of EVOs from VO using performic acid mono/diglycerides or into simple fatty acids. The
and hydrogen peroxide. They determined the optimiza- monoglycerides can be produced from transesterifica-
tion of in epoxidation of fatty acid methyl esters with tion reaction of natural oil triglycerides with glycerol.
performic acid generated in situ by varying the degree According to Can et al.,[70] maleate half esters can be
of mixing, temperature, concentration, and molar ratios attached to the monoglycerides through maleinization
of reactants. They observed that the epoxidation of reaction of these monoglycerides and further copoly-
soybean oil achieved high yield at a temperature of merization with styrene to produce rigid polymer via
40°C when hydrogen peroxide concentration added free-radical polymerization. Previously, Wool’s group
was up to 60 wt%. had synthesized and polymerized soybean oil monogly-
Synthesis of epoxidation cottonseed oil using hydro- ceride maleates (SOMGMA) by maleinized mixtures of
gen peroxide in presence of inorganic catalysts such as soybean oil monoglycerides, Bisphenol-A, and neopen-
sulfuric acid, phosphoric acid, nitric acid, and hydro- tyl glycol copolymerized with styrene to yield rigid
chloric acid was reported by Dinda et al.[50] They found thermoset polymers.[42,70,71] They found that introduc-
that the sulfuric acid was the most effective acid catalyst tion of neopentyl glycol maleates to SOMGMA
used for oxirane compared to other liquid inorganic improved the Tg and modulus of the final polymer,
acids. while introducing bisphenol-A maleates, caused only
Cai et al.[60] studied the kinetics of in situ epoxida- a slight improvement in the Tg and modulus.
tion of soybean oil, corn oil, and sunflower oil by
peroxyacetic acid in the presence of sulfuric acid as
the catalyst at 45, 65, and 75°C. They found that the
5.2. Chemical and physical modifications of fibers
increase in the process temperature increased the rate
of oxirane ring formation and the reaction rate of Cellulose fibers are too hydrophilic, which make them
epoxidation of soybean oil was higher compared to incompatible with nonpolar polymer which, in turn,
corn oil and sunflower oil. lead to low mechanical properties. They also contain
Other than epoxidation, acrylation reaction is various amounts of cellulose, hemicellulose, lignin, pec-
another commonly used method to further modify tin, waxes, and fat. There are several types of chemical
EVO. The presence of reactive sites such as acrylate modifications of natural fibers are used to remove the
and hydroxyl group promotes the easiness of polymer- artificial impurities associated with the fibers in order
izing/copolymerizing via free radicals reaction and pro- to improve the performance of natural fiber in polymer
duce better cross-linking ability.[61–63] The literatures composites, such as mercerization, isocyanate treat-
contain several studies focused on the acrylation of ment, acrylation, latex coating, permanganate treat-
EVO mainly from unsaturated soybean and linseed ment, acetylation, silane treatment, and peroxide
oils.[64–67] This is because these VOs have a greater treatment with various coupling agents and other
number of oxirane rings than other VOs. According chemicals.[72–75]
to Scala and Wool,[68] the reaction of epoxidized VOs Mercerization, which is also known as alkaline treat-
with acrylic acid was found to have first-order depen- ment, is the well-known method of cellulose fiber mod-
dence on the epoxy concentration and second-order ification. The efficiency of alkali treatment depends on
dependence on the acrylic acid concentration. AEVO the type and concentration of the alkali treatment, time
has been utilized in many applications such as for sur- of treatment, and temperature.[76] For example, Bachtiar
face coating and ink production.[69] et al.[72] studied the effect of alkali treatment on the
According to Manthey,[19] AEVO can be further flexural properties of sugar palm fiber-reinforced epoxy
modified such as by reacting with diamines, diacids, composites. It was observed that the treatment of sugar
anhydrides, and isocyanates. This is because after acry- palm fiber at 0.25 M of NaOH for 1 h of soaking time
lation reaction, triglyceride still contains some showed an improvement in properties both as fibers and
unreacted epoxides. In the literatures, the most effective reinforced composites. Saha et al.[77] studied the effect of
method to modify AEVO is by maleinization reaction. alkali treatment at different concentration on lignocellu-
However, this method results in a large increase in losic jute fibers by alkali-steam treatment. They observed
viscosity of resulting oil, which may affect the proces- an improvement of tensile strength of about 50%
sability to produce the resins. (554 ± 188 MPa) for jute fiber treated with 4% NaOH
10 R. MUSTAPHA ET AL.

with 30 min soaking time compared to the untreated the preparation or synthesis method, types of clay,
fibers (370 ± 134 MPa). amount of organic modifier, organic modifier polarity,
Coupling agents are an effective method used to and type of polymer matrix used.[86]
improve the degree of cross-linking in the interface Several studies reported on the improvements in
region and to establish a better bonding. The most properties such as tensile strength, Young’s modulus,
effective coupling agents used in modifying the natural and thermal stability of the nanocomposites with the
fiber polymer matrix interface are silane coupling inclusion of modified MMT.[87–91] Feng et al.[92] stu-
agents. The most extensive applied silane treatments died the effect of modifying a commercial MMT in
in order to improve surface modification of natural epoxy-based nanocomposites. They used two types of
fiber in polymer composites are aminosilanes, mainly clays: modified and unmodified organoclay. From their
3-aminopropyltriethoxysilanes (3-APE). For example, DMA and differential scanning calorimetry (DSC)
Ismail et al.[78] investigated the effects of silane cou- results, they found that storage modulus and thermal
pling agent on tensile and morphological study of rat- stability for modified organoclay composites were
tan powder-filled natural rubber composites. They improved especially at temperature higher than the
found that the silane coupling agent using 3-APE glass transition temperature, Tg, of the matrix. On the
improved the compatibility between the rattan filler other hand, the mechanical properties such as hardness
and the rubber matrix. Xie et al.[79] reported that their and impact resistance of the nanocomposites also
study on the use of coupling agents resulted in an improved with the addition of 1 wt% of nanoclays.
improvement of mechanical properties of the compo- Basara et al.[93] investigated the effects of different
sites due to the increase in the interfacial strength clay types and effects of clay content on the structure
between fiber and matrix. and mechanical properties of epoxy–clay nanocompo-
Acetylation treatment is a well-known esterification sites. In this study, two different types of clay were used:
method causing plasticization of natural fiber and thus natural (Cloisite Na+) and organically modified (Cloisite
making the fibers more hydrophobic.[80,81] Studied 30B). It was observed that the composites with Cloisite
conducted by Bledzki and Gassan[82] showed that the 30B showed better dispersion and less agglomeration
acetylation of kenaf fiber in UPE composites reduced than Cloisite Na+ nanocomposites. X-ray diffraction
the water absorption of the composites by about 50%. results proved that the degree of intercalation for 3 wt
However, this treatment did not contribute to the % Cloisite 30B nanocomposites was higher than 3%
improvement in tensile properties of the composites.[81] Cloisite Na+ nanocomposites. As a result of this, impact
strength of Cloisite 30B nanocomposites was improved
up to 137% with the presence of 0.5 wt% Cloisite 30B
5.3. Addition of filler or additives
compared to the 0.5 wt% Cloisite Na+ nanocomposites
Although the addition of VO in epoxy-based resin (72%). Scanning electron microscope (SEM) images
improved the toughness properties of the resin, it will result also proved that larger agglomerations of nanoclay
reduce or decrease the stiffness performance of resulting present as nanoclay loading was increased.
bio-based epoxy resin. According to Ref. [83], the addi- As mentioned earlier, the epoxies are brittle in nature
tion of small concentration of nanoclays had improved and have relatively poor resistance to crack initiation and
the mechanical properties, that is, toughness and stiffness growth which limit their use in many high performance
and barrier properties of the resin. The complete disper- applications. The toughness of bioresin may also be
sion of nanoclays in polymer matrix will prevent deflect- improved by the employment of additives such as liquid
ing cracks, facilitate good stress transfer to the rubber, plasticizer, inorganic nanofiller, and carbon nano-
reinforcement phase, and thus increase the tensile and tubes and dispersion of thermoplastic components also
toughness properties of polymer resin. However, in gen- will improve the mechanical properties of the composites.
eral, most polymers are hydrophobic and are not compa- Lu and Wool[42] investigated the suitable toughening
tible with hydrophilic montmorillonite (MMT). As stated agent for triglyceride-based thermosetting resins. Three
by Abdullah,[84] the performance of nanoclays in polymer different methods were studied: (1) liquid rubber, (2)
composites can be improved by the employment of mod- plasticizer, and (3) inorganic nanofiller. It was found that
ification of the nanoclays surface such as by amino acids, using epoxidized soybean liquid rubber with maleinated
organic ammonium salts, or teratogenic phosphonium. acrylated epoxidized soybean oil resin can act as plasti-
Table 4 shows lists of current commercial organoclay cizer and shows the best properties compared to the
products with their modifier agents. The addition of clay other methods. The stress intensity factor (K1c) and
in polymer resin may be exfoliated, intercalated, or in energy release rate (G1c) at 15 wt% plasticizer content
tactoid form as shown in Figure 4. This is depending on were increased significantly over twofold and fourfold
 POLYMER-PLASTICS TECHNOLOGY AND MATERIALS 11

Table 4. Types of commercial organoclays.

Producer Clay Modifier agent
Southern clay products (USA) Cloisite 10A Dimethyl, benzyl, hydrogenated tallow, quaternary ammonium
Cloisite 15A Dimethyl, dihydrogenated tallow, quaternary ammonium
Cloisite 20A Dimethyl, dihydrogenated tallow, quaternary ammonium
Cloisite 25A Dimethyl, dihydrogenated tallow, 2-ethylhexyl quaternary ammonium
Cloisite 30B Methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium
Cloisite 93A Methyl, dehydrogenated tallow ammonium
Cloisite Na+ Sodium montmorillonite
Nanocor Inc. (USA)
Nanomer I.28E Octadecyl trimethyl ammonium
Nanomer I.30E Octadecylamine
Laviosa Chimica Mineraria (Italia) Dellite 43B Dimethyl benzyl hydrogenated tallow ammonium
Co-op chemicals, Japan MAE Dimethyl dialkyl (tallow) ammonium
MTE Trioctyl methyl ammonium
MEE Methyl bis-2-hydroxyethyl coco quaternary ammonium
MPE Polyoxy propylene methyl diethyl ammonium
Sud-Chemie (German) Optigel EX0255 Sodium montmorillonite
Nanofil 804 Stearyl diethoxyamine

Figure 4. Schematic illustration of polymer layer silicate nanocomposite.[85]

higher than K1C value of the resulting material, respec- but modestly reduced the modulus and Tg of the result-
tively. Although the employment of nanoclay doubled ing materials.
the G1C value at 5 wt% of clay loading, the fracture
toughness of the thermosetting resins was reduced.
6. Summary
Ratna and Simon[94] synthesized a family of carboxyl
randomized poly(2-ethyl hexyl acrylate) (CRPEHA) Bio-based epoxy composites from renewable resources
using solution polymerization as toughening agent for have received more attention than conventional petro-
epoxy resin. Dioxan, benzoyl peroxide, and thioglycolic leum-based epoxy composites and their use will continue
acid were used as solvent, free radical initiator, and to rise especially in automotive and housing construction
a chain transfer agent, respectively. They found that applications. With increasing ecological concern and
CRPEHA was able to increase the toughness properties environmental awareness, the development of products
12 R. MUSTAPHA ET AL.

that are compatible with the environment has become Funding

increasingly important and necessary. The use of VOs as
This work was supported by the Ministry of Higher
potential feedstock for the polymer industry is now an Education, Malaysia [16h15] and Universiti Teknologi
attractive solution because of their versatility, availability, Malaysia [16h15].
renewability, biodegradability properties as well as their
ability to increase the renewable content of the final
polymer composites product.[1,2] The concern about the Notes on contributors
toxicity typical amine hardener on human health also has Rohani Mustapha is a young academic training scheme staff
prompted researchers to explore bio-based hardener from in the School of Ocean Engineering, Universiti Malaysia
renewable resources, rather than petroleum-derived Terengganu. She has published several research papers and
materials. The most explored bio-hardener reported in conference proceedings on bio-polymer, natural fiber and
bio-composites. She is currently pursuing studies at
literature is bio-based hardener derived from bio-based
Universiti Teknologi Malaysia and conducts research on
polyamines, bio-based rosin, water soluble natural acids bio-based epoxy nanocomposites with bio-based hardener.
(CA, malic acid, tartaric acid and glutaric acid), terpene-
based anhydrides (TPAn), and tannic acid. Dr. Abdul Razak Rahmat is an Associate Professor at
Department of Polymer Engineering, Universiti Technologi
In the case of direct synthesis of epoxy resin from VO Malaysia (UTM). He has published more than 70 journal
with bio-hardener, the resulted bio-based resin exhibited articles and conference papers on polymer and composite.
unsatisfactory results as they have relatively low stiffness He is co-author of recently published technical book by
and strength. The blending of VOs with rigid compo- Elsevier entitled “Polylactic Acid: PLA Biopolymer
nent, that is synthetic epoxy resin, is required to improve Technology and Applications”.
the mechanical properties for real-world applications. Dr. Rohah Abdul Majid is a senior lecturer at Bioprocess and
Both synthetic fibers and natural fibers have been incor- Polymer Engineering Department, Universiti Technologi
porated into epoxy resins to produce composites. Malaysia (UTM). She has published several research papers
Incorporation of fibers as reinforcement can generally and conference proceedings on Journal of Thermoplastic
Composite Materials, Applied Mechanics and Materials,
increase the strength and modulus of the neat bio-based Composites: Part B and Key Engineering Materials.
epoxy matrix. Natural fibers are the most commonly
used reinforcement fiber for bio-based or green polymer Dr. Siti Noor Hidayah Mustapha is a senior lecturer at
Universiti Malaysia Pahang, Malaysia. She was enrolled her
composites. However, they are hydrophilic in nature.
Doctorate degree in Polymer Engineering from Universiti
Therefore, to improve the compatibility between fibers Teknologi Malaysia in year 2016. She has published several
and epoxy matrices, modification of their fiber surface is research papers and conference proceedings on biopolymer
required. Alkali is common and popular method because and biocomposite materials.
it is inexpensive and relatively effective method of
removing lignin and other soluble substances from the
surface of cellulose.[95] References
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