Bio Based Thermosetting Resins For Futur

POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING
2016, VOL. 55, NO. 17, 1863–1896

http://dx.doi.org/10.1080/03602559.2016.1185624
Bio-Based Thermosetting Resins for Future Generation: A Review

Shrikant K. Bobadea, Nagarjuna Reddy Paluvaib, Smita Mohantya, and S. K. Nayaka
a
Laboratory for Advanced Research in Polymeric Materials (LARPM), Central Institute of Plastics Engineering & Technology (CIPET),
Bhubaneswar, Odisha, India; bDepartment of Bionanotechnology, Hanyang University, Educational Research Industrial Cluster at Ansan
(ERICA), Ansan, Korea
ABSTRACT KEYWORDS
In this review, thermosetting polymers derived from natural resources are highlighted for future Bio-based epoxy; bio-based
generation with greater sustainability for different applications. Recently, agro-based polymer polyurethane; bio-based
products are gained popularity since last two decades due to the depletion of fossil reserves and to thermosetting resin;
properties; synthesis
protect the environment from carbon emissions. This review also designed to explain the various
types of agro-based polymer products derived from cardanol, itaconic acid, tannin, sugar
(isosorbide), and vegetable oils as important starting materials due to their abundant availability,
low price, and unique reactive chemical structure.
GRAPHICAL ABSTRACT
Introduction bio-based thermosetting resin has many advantages such

as low price, universal availability, less hazardous, and
We are familiar about rapid growth and improvement in
mostly preferred by chemical industries as an alternative
living standards of population worldwide[1]. So there is
to conventional material but these materials need not to
an urgent requirement of bio-based thermosetting resins
be biodegradable and should reach the industrial perfor-
due to the uncertainty in terms of price and availability
mance. There is a huge demand for bio-based resins in
of crude oil and also to protect living environment
the chemical industry to maintain sustainability[4,5].
(future generation survival)[2,3]. In addition to this, the
CONTACT Nagarjuna Reddy Paluvai nag1987@gmail.com Post Doctoral Researcher, Hanyang University, ERICA Campus, Engineering Bldg. #5,
Room No: 38-331, Nano-Bio Electronic Materials Processing Lab. (NEMPL), Dept. of Materials Engineering, Ansan, 426-791, Korea.
Color versions of one or more of the figures in this article can be found online on at www.tandfonline.com/lpte.
© 2016 Taylor & Francis
1864 S. K. BOBADE ET AL.
usage for the manufacture of infant bottle or printing

ink. In recent years, the research has concentrated on
using the renewable resource materials to develop the
bio-based thermosetting resins from natural oils[16–18],
cardanol[4,18], wood/lignin[19], itaconic acid (IA)[20,21],
tannins[22,23], sugars[24], lactic acid[25], and so on to con-
tribute toward sustainable development in the polymer
Figure 1. Approximate polyurethane elastomer consumption industry. However, a broad attention is required to
for years (a) 2005 (b) 2012, where AP—Asia pacific, LA—Latin the utilization, efficient chemical transformations, and
America, NA—North America, EMEA—Europe, Mi-East and benefits of bio-based materials. So that bio-based poly-
Africa. mers can play an important role in the green chemistry
industry.
Thermosetting polymers are one of the most widely From last two decades, several researchers[26–28] have
used polymers in several industrial applications which reported their ideas on synthesis and modification of
cannot regain their shape after completion of their reac- natural oil-based polymers since increasing their
tion[2]. Typical examples of thermosetting polymers are demand in production of lubricants, coatings, paints,
epoxies[6–9], polyurethanes[10], unsaturated polyesters biodiesel, and biomedicine. The saturated and unsatu-
(UPEs)[11], vinyl esters[12], and formaldehydes[13]. rated fatty acids are the main components of triglyceride
Among these, global markets of polyol and poly- vegetable oils[29]. These fatty acids have industrial value
urethane are estimated to reach USD 22.6 billion and depending on the chemical modification of the ester
USD 66.4 billion, respectively, by 2018. However, Asia (‒COOR) and carbon double bond (C=C). These fatty
pacific expected to be the fastest growing regional mar- acids can be modified into epoxy[4,18], polyurethane[30],
ket for polyurethane (PU) consumption and production polyamide[31], polyester[32], thiol-ene-containing trigly-
[14,15]
. Figure 1 shows the consumption of polyurethane ceride[33–35], aldehyde- and enone-containing triglycer-
elastomer in 2005 and 2012. Figure 2a shows annual ide[36], maleinized triglyceride[37–40], furan-containing
thermoset consumption in the world (PU, polyur- triglyceride[41], azide-containing triglyceride[42], and
ethanes; UP, unsaturated polyesters; PR, phenolic metathesis of triglyceride[43].
resins; AR, amino resins) and Figure 2b predicts market This paper intended to review the synthesis and
shares for the thermoset application sector (PAC, paint, properties of bio-based thermosetting resins such as
adhesive, cements; AT, automotive and transportation; polyurethane, polyester, and epoxy from cardanol, IA,
BC, building and civil engineering; E, electricity and sugar (isosorbide), tannin, and natural oils, and also
electronics; FB, furniture and bedding-consumer goods; discussed its new challenges and applications.
MI, mechanical and industrial; P, packaging; O, others).
One of the most commercialized epoxy resins, digly- Cardanol-based polymers
cidyl ether of bisphenol A (DGEBA) is synthesized from
the condensation reaction of bisphenol A (BPA) and Bio-based phenols were extracted from cashew nut shell
epichlorohydrin (ECH)[2] in which bisphenol is endo- liquid (CNSL) which is a good natural alternative to pet-
crine disruptor so that some countries banned on its roleum-derived phenols[4,44]. It is abundantly available
in many places of world, in India, Brazil, and tropical
region of Africa. Thus, CNSL can be used as starting
material in polymer industry due to its low cost, abun-
dant availability, and chemically reactive nature. Several
researchers have studied the extraction, chemistry, and
composition of CNSL. It is extracted from cashew nut
using different processes, namely, hot oil process, roast-
ing process[45,46], solvent[47] and supercritical fluid
extraction process[48,49].
The CNSL constitutes four major components with
an unsaturated C15 side chain, namely, cardanol, car-
dol, anacardic acid, and 2-methyl cardol[2] and are
shown in Figure 3. The unsaturated side chains are
Figure 2. (a) Annual thermoset consumption in the world. (b) also different as like saturated ( ),
Market shares for the thermoset application sector. monoene ( ), dine ( )
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 1865
Cardanol-based epoxy polymers

Several types of bio-based epoxy polymers such as
monoepoxidized cardanol, diepoxy cardanol, and epox-
idized novolac prepolymer are derived from cardanol.
The monoepoxidized cardanol[52] is obtained by the
direct reaction between ECH and cardanol, while die-
poxidized cardanol consists of two-step reaction. Devi
et al.[53,54] have reported that cardanol-based epoxidized
novolac prepolymer was synthesized by the reaction of
ECH with cardanol formaldehyde resin. The cardanol
formaldehyde resin was synthesized by methylolation
of cardanol with formaldehyde in the presence of citric
acid.
Enzymatic epoxidation can be used as mild and sim-
ple alternative to produce epoxide-containing cardanol.
Epoxidized cardanol can also be synthesized using
enzymes like lipase, peroxidase in the presence of acetic
acid and continuous addition of H2O2. Kim et al.[55]
reported the synthesis of epoxide-containing polycarda-
Figure 3. Different components of cashew nut shell liquid. nol through two ways using two different enzymes like
lipase and peroxidase. In the first way, synthesis of
and triene ( ). CNSL-based epoxide-containing cardanol from cardanol in the pres-
phenolic resins were used in coating, laminate, and ence of lipase and further it was polymerized using
friction materials industries. peroxidase. In another way, polycardanol from cardanol
The CNSL-based resins show high rigidity and was synthesized using peroxidase and further epoxide-
thermal stability due to the presence of aromatic rings containing polycardanol was synthesized using lipase
on their backbone[50]. Jaillet et al.[51] reported with iso- as shown in Figure 4.
phorone diamine (IPDA) as curing agent, Tg value for At last, cardanol, epoxide-containing cardanol, poly-
cardanol-based resin (NC 514) was found to be 45°C, cardanol and epoxide-containing polycardanol were
while for DGEBA, it was found to be 73°C. cured with phenalkamine at 150°C for different times
Figure 4. Synthesis of epoxide-containing cardanol (2), polycardanol (3), and epoxide-containing polycardanol (4).
on glass slide. Order of pencil scratch hardness follows

cardanol < epoxide-containing cardanol < polycardanol
< epoxide-containing polycardanol. They found that
for cured film of epoxide-containing polycardanol at
150°C for 5 h, hardness (9H) was much higher com-
pared to commercially available alkyd resin (4H) coat-
ing and also film obtained was transparent and having
high gloss surface.
Bio-based vinyl ester polymer from cardanol

Vinyl ester is one of the most important classes of ther-
mosetting polymers which are formed by the addition
reaction between epoxy resin and unsaturated monocar-
boxylic acid. It exhibits outstanding properties that can
be used in various industrial applications such as surface Figure 6. Cardanol-based epoxidized novolac resin.
coating, adhesives, composite, radiation curable inks,
and spherical lens materials. Can et al.[58] reported the preparation of vinyl ester
The cardanol-based novolac resin (shown in Figure 5) resin from DGEBA (Epon 828), CNSL-based difunc-
has been obtained from 1:0.7 mole ratio of cardanol to tional epoxy resin (NC514), and CNSL-based mono-
formaldehyde in the presence of p-toluenesulphonic functional epoxy resin (LITE 2513HP) using
acid (PTSA) as catalyst dissolved in methanol under methacrylic acid (structure are shown in Figure 8).
warm condition[56]. The cardanol-based epoxidized The synthesized monomers from cardanol were used
novolac resin (Figure 6) synthesized by reacting carda- as reactive diluents as well as cross-linker. Reactive dilu-
nol-based novolac resin with excess ECH and 40% ent proportions change from 10 to 50 wt%; the tensile,
sodium hydroxide at 120°C for about 10 h. Synthesis dynamic mechanical analysis (DMA), and thermo gravi-
of cardanol-based novolac epoxy vinyl ester resin metric analysis (TGA) properties were investigated for
(CNEVER) was obtained using 1:0.9 mole ratio of epox- different proportional systems of vinyl ester of
idized novolac resin and methacrylic acid (MA) in the DGEBA/vinyl ester of LITE, vinyl ester of NC514/vinyl
presence of triphenylphosphine (TPP) catalyst (1%) ester of LITE, and vinyl ester of NC514/styrene.
and hydroquinone as inhibitor (200 ppm) at 90°C in The authors found that for DMA analysis of 30 wt%
nitrogen atmosphere for about 5 h[9]. Figure 7 depicts of comonomers’ content, vinyl ester of DGEBA/vinyl
the synthesis of cardanol-based epoxidized novolac
vinyl ester resin (CNEVER).
Garg et al.[57] have studied the physical and chemical
toughening of cardanol-based vinyl ester resin using car-
boxyl-terminated butadiene acrylonitrile (CTBN) ranges
from 0 to 15 wt%. They optimized 10 wt% of CTBN.
They found that impact strength was increased by
213% as compared to cardanol-based vinyl ester for
10 wt% of CTBN (in chemical toughening). It was also
found that CTBN–cardanol-based vinyl ester blend shows
good gloss, impact resistance, and good resistance to
acids. Again initial degradation temperature for 10 wt%
of CTBN shifted to higher temperature (i.e., 477°C).
Figure 5. Structure of cardanol-based novolac resin. Figure 7. Cardanol-based epoxidized novolac vinyl ester resin.
characteristics[59]. It is to be noted that the nature of

polyurethane (i.e., rigid or semirigid) which depends
on the polyol structure (i.e., diol or triol)[57], are dis-
cussed in the next sections. The cardanol-based polyols
show the better thermal stability than the triglyceride
oil-based polyols. The cardanol-based polyol can be
synthesized by ring-opening reaction to give diol or
reaction with diethanolamine to give triol or reaction
of 2-mercaptoethanol with cardanol (Figure 9).
Figure 8. Structure of CNSL-based resin (a) LITE (b) NC514.
Note: CNSL, cashew nut shell liquid.
Bhunia et al.[60] have reported the synthesis of
polyurethane using cardanol-based monomer 4-[(4-
hydroxy-2-pentadecenylphenyl)diazenyl]phenol (HPPDP).
ester of LITE and vinyl ester of NC514/styrene, shows However, synthesized polyurethane-based HPPDP gives
storage modulus values at 30°C, 2,586 and 2,356 MPa, higher thermal stability than the cardanol or monomer.
while Tg values found to be 123 and 99°C, respectively. p-Aminophenol on diazotization gives diazonium
They also found that for vinyl ester of DGEBA/vinyl salt. When 3-pentadecylphenol dissolved in chilled
ester of LITE, as reactive diluents ranges from 10 to solution of KOH in methanol was added dropwise
50 wt%, viscosity decreases from 146,500 to 18,020 cP, in diazonium salt solution gives red dye (yield 80%).
for vinyl ester of NC514/vinyl ester of LITE, viscosity Thus, HPPDP has been synthesized as shown in
decreases from 181,900 to 2,743 cP, and for vinyl ester Figure 10. Further, HPPDP dissolved in dimethylfor-
of NC514/styrene, viscosity decreases from 181,900 to mamide (DMF) as solvent followed by the reaction
21 cP. It was also observed that for 30 wt% of comono- with 1,6-diisocyanatohexane (HDI, hexamethylene dii-
mers, 5% weight loss was obtained at the temperature socyanate) to synthesize polyurethane.
270–300°C. Thus, bio-based vinyl ester resin and bio- Fu et al.[61] have synthesized the polyurethane from
based reactive diluents were used by Can et al.[58] and aromatic cardanol (industrial grade)-based polyol using
studied the viscosities, mechanical as well as thermal thiol-ene coupling (Figure 9). The resulting polyols were
stabilities which are helpful in their application. then polymerized with HDI to produce the correspond-
ing bio-based polyurethane. Thiol-ene chemistry for the
synthesis of cardanol-based polyol can be used to give
Cardanol-based polyurethanes
green, practical, and atom-efficient methodology and
Cardanol-based polyurethane was prepared to improve these renewable materials can become suitable alterna-
the thermal stability, hydrophobic nature, and chemical tive to petroleum-based substances.
Figure 9. Different types of polyols synthesized from cashew nut shell liquid.
cardanol-based polyurethane showed good thermal

and hydrophobic properties which could be useful in
material engineering.
Cardanol-based benzoxazines
Benzoxines are a new type of phenolic resins, which are
widely used in several industrial applications due to
their excellent properties such as low volume shrinkage,
low water absorption, and high dimensional stability[62].
Figure 10. Synthesis procedure for HPPDP. Note: HPPDP, 4-[(4- Cardanol benzoxazine was synthesized by reacting car-
hydroxy-2-pentadecenylphenyl)diazenyl]phenol.
danol with paraformaldehyde in round bottom flask
with the addition of aniline dropwise at 80–90°C till
Cardanol-based polyol and 10-undecylenate- 1 h[63] as shown in Figure 11.
modified polyol were synthesized using thiol-ene Moreover, Sharma et al.[64] synthesized benzoxamine
coupling with controlled time. It was found that after monomer from cardanol. It was encapsulated in poly
50 and 45 h for cardanol-based polyol (CP50) and (styrene) shell using solventless approach and operating
modified cardanol-based polyol (UCP45), respectively, parameter (stirring speed and concentration of encapsu-
show total conversion of C=C bond, hydroxyl function- lating polymer).
ality about 3.3 and also good yield about 78%. Again on A mixture of cardanol, aniline, and paraformalde-
1:1 NCO:OH ratio, they give continuous film. hyde were heated at constant temperature 80°C for 1 h
To synthesize cardanol-based polyols, cardanol, followed by at 90°C for 2 h. Then, water was added to
2-mercaptoethanol, and UV1173 were dissolved in it and red brown oil (benzoxazine cardanol) was
dichloromethane (DCM) in a single-necked flask. The obtained after extraction with chloroform. Further,
reaction mixture was stirred at room temperature using solvent evaporation technique, cardanol-based
through UV light irradiation (365 nm) for 15 h. benzoxazine (Bz-C) encapsulated in polystyrene (PS).
2-Mercaptoethanol was removed by washing with water SEM images of Bz-C encapsulated in PS using solvent
and product was obtained. evaporation technique are perfectly spherical, smooth
The 10-undecylenate-modified cardanol-based polyol surface, and shell wall thickness about 7 � 1 µm. These
was synthesized by dissolving 10-undecenoic acid in can be useful in the field of self-healing.
thionyl chloride in a single-necked flask. Mixture was
refluxed for 1.5 h, thionyl chloride evaporated and dry
DCM was added. 10-Undecenoyl chloride was obtained Miscellaneous cardanol-based polymers
in the form of brown oil. Brown oil was added dropwise Huo et al.[65] reported the curing kinetics of lignin
to the solution composed by cardanol, triethylamine, and and cardanol-based novolac epoxy (LCNE) resin
dry DCM. Finally, 10-undecylenate-modified cardanol in (Figure 12a) with methyl tetrahydrophthalic anhydride
the form of pale brown liquid was obtained as shown in (MeTHPA). LCNE resin was synthesized by reacting
Figure 9. ECH with the mixture of lignin and cardanol (2/3 in
Cardanol-based polyurethane was synthesized in a weight ratio). First, in the presence of catalyst like ter-
three-necked round bottom flask equipped with stirrer, tiary amine, anhydride gives zwitterions. Zwitterions
a condenser, and nitrogen (N2) inlet. Then, calculated react with epoxy group containing LCNE to form alkox-
amounts of cardanol-based polyol, dibutyltin dilaurate ide anion, further alkoxide anion reacts with anhydride
(DBTDL), and DMF were added to the flask and HDI (Figure 12b). Thus during curing process, anionic copo-
in DMF was slowly added to the mixture in 1 h and lymerization takes place and value of Ea influenced by
heated to 75°C for 4 h. Polyurethane film was obtained the propagation of the polymer chain and temperature
on polytetrafluoroethylene plates. of the reaction.
The authors also found that Tg value for poly- Differential scanning colorimetry (DSC) analysis of
urethane synthesized from CP50 and UCP45 were nonisothermal curing reaction between LCNE and
31.6 and 16.1°C, respectively, while loss factor (tandmax) MeTHPA at different heating rates was observed by
value were found to be 0.57 and 0.62, respectively. Huo et al. They observed that increasing the heating
From TGA analysis, it was observed that PU based on rate as 5–20°C/min, the onset temperature (Ti), peak
CP50 and UCP45, the 50% weight loss temperature temperature (Tp), final temperature (Tf), and total heat
was found to be 350 and 364°C. Thus obtained of reaction (ΔH) shifted to higher values. For heating
Figure 11. Cardanol-based epoxide and benzoxazine.
rate (b) as 5, 10, 15, and 20°C/min, Ti value increases as to be 367, 350, 285, 362, and 345°C, respectively. Simi-
40, 50, 60, and 68°C, Tp value increases as 145, 154, 160, larly, for Jeffamine T403 as curing agent, epoxy resin
and 172°C, Tf value increases as 195, 205, 216, and DGEBA (petroleum based), epoxidized cardanol, epox-
238°C, and ΔH value decreases as 89.38, 81.78, 80.87, idized sorbitol show Tg values as 70, 23, and 48°C, while
and 78.36 J/g, respectively. The apparent activation degradation temperature at 30% weight loss were found
energy of LCNE cured with MeTHPA was determined to be 364, 352, and 277°C, respectively. It was also
by Friedman method and calculated to be 51.85 kJ/ observed that Jeffamine T403 cannot be cured with
mol. Thus, curing kinetics of LCNE–MeTHPA system epoxidized isosorbide 100 and epoxidized isosorbide
can be helpful in potential application of LCNE as 102 at room temperature.
new epoxy resin. Darroman et al. also study properties of blend
Darroman et al.[66] studied the cardanol-/sucrose- epoxidized cardanol/epoxy sorbitol (100/0, 75/25, 50/
based epoxy for coating applications. In this study, 50, 25/75, 0/100) and epoxy cardanol/epoxy isosorbide
two types of sucrose epoxy such as sorbitol and isosor- (100/0, 75/25, 50/50, 25/75, 0/100) using different
bide were used and two different amines, i.e., IPDA amines, i.e., IPDA and Jeffamine T403 as curing agent.
and Jeffamine T403, were used as curing agent. Digly- They found that for blend system properties like Tg
cidyl ether of cardanol NC-514 (EEW ¼ 400 g/eq), value, degradation temperature, brightness, and shore
polyglycidyl ether of sorbitol Denacol EX622 [epoxide A hardness enhanced as shown in Tables 1 and 2. Thus,
equivalent weight (EEW) ¼ 188 g/eq], epoxidized iso- mixing of different bio-based epoxy resin can help to
sorbide Denacol GSR100 (EEW ¼ 155 g/eq), epoxi- enhance the properties of coating and can become
dized isosorbide Denacol GSR102 (EEW ¼ 158 g/eq.), important in various applications.
and bisphenol A glycidyl ether (DGEBA) were also
used for experimental purpose in this study. Chemical
structure of diglycidyl ether of isosorbide and polygly- Itaconic acid-based polymer
cidyl ether of sorbitol are shown in Figure 13. These Itaconic acid is a recognized large-scale bio-based
resin blended with curing agent (i.e., IPDA and Jeffa- monomer which can be obtained by bacterial fermen-
mine T403) in 1:1 molar ratio to obtain the maximum tation of some plant (such as corn straw), i.e., carbohy-
cross-linking density of cured resin. drates or through the distillation of citric acid and it
The addition of IPDA as curing agent, epoxy resin can substitute the methacrylic acid in chemical
DGEBA, epoxidized cardanol, epoxidized sorbitol, industry[67,68]. Double bond containing IA has ability
epoxidized isosorbide 100, and epoxidized isosorbide to take part in addition polymerization. IA-based
102 shows Tg values as 121, 41, 82, 109, and 72°C, while polymers are used as plastics, coating, adhesive, and
degradation temperature at 30% weight loss were found elastomeric[69,70]. They are highly demanded in additive,
Bio-based epoxy from itaconic acid

Itaconic acid-based epoxy monomer can be synthesized
by the esterification reaction between ECH and IA.
Ma et al.[74] reported the synthesis of epoxy resin
using IA and ECH, then it was cured with the help of
methylhexahydrophthalic anhydride (MHHPA), and
divinyl benzene (DVB) and acrylated epoxidized soy-
bean oil (AESO) were used as comonomers (Figure 14).
The chemical structure of IA-based epoxy resin was
confirmed by FTIR, 1H-NMR, and ESI-ion trap MS
before curing. They also found that epoxidized IA have
higher epoxy value, i.e., 0.625.
In this study, they cured the epoxidized IA with
MHHPA and ratio of comonomers (DVB or AESO)
was varied as 5, 10, and 20 phr. They found that for neat
epoxidized IA cured with MHHPA, Tg values using
DMA and DSC analyses were found to be 130.4 and
111.2°C, respectively, while for neat DGEBA, Tg values
using DMA and DSC analyses were found to be 125
and 107.8°C, respectively. Also, DVB as comonomers in
epoxidized itaconic acid (EIA) system varying as 5, 10,
and 20 phr, Tg values for DMA analysis increase as
132.6, 139.4, and 142°C, respectively, while for DSC
analysis, Tg values increase as 115.2, 117.2, and 119.5°C,
respectively. Again, AESO as comonomers varying as 5,
10, and 20 phr, Tg values for DMA analysis decrease as
127.4, 126.7 and 122°C, respectively, while Tg values for
DSC analysis decrease as 108.5, 107.7, and 100.1°C,
respectively. They also found that for neat epoxidized
IA cured with MHHPA, degradation temperature at
5% weight loss under N2 atmosphere was found to be
Figure 12. (a) Chemical structure of lignin and cardanol-based 325.9°C, while for neat DGEBA, it was found to be
novolac epoxy resin. (b) Mechanism between LCNE and 353.8°C. Again, degradation temperature (5% weight
anhydride in the presence of catalyst. Note: LCNE, lignin and
cardanol-based novolac epoxy.
loss) for DVB as comonomers in EIA varying as 5, 10,
and 20 phr were found to be 322.9, 331.5, and 336.8°C,
respectively, while it for AESO as comonomers in EIA
detergent, and biologically active derivative like agricul- varying as 5, 10, and 20 phr were found to be 310, 319,
ture and pharmaceutical industries[71,72] and well and 320°C, respectively. It was also observed that with
known as top potential bio-based chemical[73]. the increasing amount of DVB in EIA systems, the net-
work rigidity increases, while increasing the amount of
AESO in EIA system, toughness of system could be main-
tained. For 20 phr of DVB in EIA system, flexural modu-
lus was found to be 3,700 MPa, while 20 phr of AESO in
EIA system, flexural modulus was found to be 2,900 MPa.
Thus, EIA showed the great potential for replacement of
petroleum-based epoxy resin like DGEBA.
Bio-based unsaturated polyester resin synthesis

from itaconic acid
Figure 13. Structure of (a) diglycidyl ether of isosorbide and Dai et al.[75] reported the synthesis of polyester from IA
(b) polyglycidyl ether of sorbitol. and different diols [1,4-butanediol, ethylene glycol (EG),
Table 1. Different properties of blend of epoxy cardanol/epoxy sorbitol in different ratios.

Ratio of epoxy Tg value using Degradation temperature Degradation temperature
cardanol/epoxy Tg value using Jeffamine at 30 wt% loss using at 30 wt% loss using Shore A hardness Shore A hardness for
sorbitol IPDA (°C) T403 (°C) IPDA (°C) Jeffamine T403 (°C) for IPDA Jeffamine T403
100/0 41 23 350 352 86 56
75/25 52 28 312 312 84 84
50/50 60 37 295 294 93 94
25/75 68 40 288 283 97 99
0/100 82 48 285 277 97 99
DGEBA 121 70 367 364 100 97
IPDA, isophorone diamine; DGEBA, diglycidyl ether of bisphenol A.
Table 2. Different properties of blend of epoxy cardanol/epoxy isosorbide100 in different ratios.

Ratio of epoxy Degradation temperature Degradation temperature
cardanol/epoxy Tg value using Tg value using at 30 wt% loss using at 30 wt% loss using
isosorbide IPDA (°C) Jeffamine T403 (°C) IPDA (°C) Jeffamine T403 (°C)
100/0 41 23 350 352
75/25 47 34 350 358
50/50 58 42 349 354
25/75 83 48 356 311
0/100 109 109 362 362
DGEBA 121 70 367 364
IPDA, isophorone diamine; DGEBA, diglycidyl ether of bisphenol A.
1,6-hexanediol (HDO)] by prepolymerization and poly- and HDO, molar ratio was used as 1.2/, while for poly-
condensation (Figure 15). PTSA monohydrate was used ester based on IA/1,4 butanediol/glycerol, the molar
as a catalyst for prepolymerization, while ditin butyl ratio was taken as 1.2/0.9/0.1. Further, AESO used as
dilaurate (DBTL) was used as a catalyst for polyconden- 30% by weight for PIE (polyester of EG), PIB (polyester
sation. Further, it was copolymerized with acrylated using 1,4-butanediol), PIH (polyester using HDO), and
soybean oil (AESO). They confirmed their structure AESO varied from 10 to 50% by weight for PIGB (poly-
with the help of FTIR and 1H-NMR, while thermal ester using glycerol and 1,4-butanediol).
and mechanical properties of thermoset were studied From DSC study, it was found that reactivity
by DSC, tensile testing, and DMA. They also studied increases in the order PIE > PIBG > PIB > PIH. The
coating properties on tinplate and glassplate. For the tensile strength and modulus for AESO-PIBG30 was
synthesis of polyester from IA using EG, 1,4-butanediol, higher compared to AESO-PIE30, PIB30, and PIH30.
It was also found that as the amount of PIBG increases,
Figure 15. Synthesis of bio-based amide using itaconic acid,

Figure 14. Synthesis scheme for epoxidized itaconic acid. diacid, and diamine.
for different diols i.e., 1,4-butanediol, HDO. After this,

waterborne UV-cured coating was prepared using the
synthesized resins. The synthesized coating showed good
properties such as water resistance, solvent resistance,
and hardness.
The T-bend test showed that UV-cured poly
(IA-HDO) was more flexible compared to others, while
it also showed highest adhesion. The UV-cured poly
(IA-EG) showed excellent water resistance.
Bio-based polyamides and polyamidoamine-

epichlorohydrin resin synthesis from itaconic acid
The introduction of diacid to diamine gives the forma-
tion of amide linkage. Wang et al.[77] have reported
synthesis of fully bio-based polyamides using equimo-
lar amount of diacid (IA and sebacic acid) and diamine
Figure 16. Synthesis of unsaturated polyester using itaconic
acid and diol. (1,10-decanediamine and 1,4-butanediamine) and for-
mation of pyrrolidone ring takes place through
Michael addition (as depicted in Figure 15). The
tensile properties also increase. For AESO-PIBG50, the obtained polyamides showed increment in glass tran-
tensile strength and modulus were found to be 16.5 sition temperature, tensile strength, and also trans-
and 510.4 MPa which are 5 and 15 times higher than parent materials.
neat cured AESO, respectively. Glass transition tem- Gui et al.[78] have reported synthesis of bio-based
perature by the analysis of DMA for AESO, AESO- polyamidoamine-ECH resin. For synthesis of IA-based
PIE30, AESO-PIB30, AESOPIH30, and AESOPIBG50 polyamidoamine ECH resin, IA, ECH, and diethylene-
were found to be 32.2, 69.6, 68.8, 66.6, and 76.0°C, triamine (DETA) were taken in 1:1:1 molar ratio. The
respectively. Pristine AESO could not be coated well synthesized resin as adhesive showed improvement in
on the surface of sanded tinplates and glassplate but water resistance on plywood. Synthesis of IA-based
modified AESO systems (AESO-PIP/PIB/PIH/PIBG) polyamidoamine ECH resin is shown in Figure 17.
showed good adhesion as 5B according to ASTM
D3359-09 crosshatch adhesion method.
They have synthesized bio-based polyester from IA,
glycerol, and different diols (i.e., EG, 1,4-butanediol
and HDO) without volatile organic compound emission
as shown in Figure 16. The results showed enhancement
in properties and bio-based content. It should be noted
that not only IA and acrylated soybean oil are natural
resources but also EG, 1,4-butanediol, and HDO could
be produced from natural resources.
Dai et al.[76] synthesized the bio-based UPE using the
IA and various diols, i.e., EG, 1,4-butanediol, HDO,
which found application in waterborne UV-curable
coating. They studied the mechanical, thermal, and
coating properties.
First, the mixture of IA and EG was prepared in molar
ratio of 1.2:1. To this mixture, PTSA monohydrate was
added as a catalyst (0.5 mol%) and 4-methoxyphenol
was as an inhibitor for free radical polymerization. These
are charged into a four-necked round bottom
flask maintaining temperature at 160°C for 2 h for the
prepolymerization. Then, DBTL (1 wt%) was added as Figure 17. Synthesis of itaconic acid-based polyamidoamine
polycondensation catalyst. Similar process was followed epichlorohydrin resin.
Bio-based polysulfones and polynorbornenes of resulting double bond was performed as shown in
using itaconic acid Figure 19a. mCPBA and methyl(trifluoromethyl)diox-
irane (in situ preparation from 1,1,1-trifluroacetone
Winkler et al.[79] reported the synthesis of UPE by direct
and oxone) were used as oxidizing agent. Allylation
polycondensation of dimethyl itaconate with diols and
of gallic acid using allyl bromide gives 80% yield of
further it was modified using thiol and on oxidation
allyl 3,4,5-tris(allyloxy)benzoate and structure was
with meta-chloroperbenzoic acid (mCPBA) gives poly-
confirmed by 1H-NMR and 13C-NMR. Further, epox-
sulfones (Figure 18a). They also reported the synthesis
idation was performed with mCPBA and 77% overall
of polynorbornenes. First, itaconic derivative-based
yield of glycidyl ether of gallic acid was obtained (17%
norbornene (Figure 18b) was synthesized using
yield of triglycidyl ether and 60% yield of tetraglycidyl
dimethyl itaconate and cyclopentadiene through
ether), which are depicted in Figure 19b. Similarly,
Diels–Alder reaction and then on ring-opening metath-
epoxidation was performed with methyl(trifluoro-
esis polymerization in the presence of Hoveyda–Grubbs
methyl)dioxirane and 75% overall yield of glycidyl
second generation catalyst gives polynorbornenes.
ether of gallic acid was obtained (30% yield of trigly-
cidyl ether and 45% yield of tetraglycidyl ether),
Tannin-based polymer which is depicted in Figure 19c. Chemical structure
Tannins are phenolic compounds having high molecu- of all obtained product was confirmed by 1H-NMR
lar weight and classified as condensed and hydrolysable and 13C-NMR.
tannins. Depending on the nature of phenolic car- Further, glycidyl ether derivative of gallic acid
boxylic acid, again hydrolysable tannins classified into (GEGA) composed of different mixtures was cured
gallotannins and ellagitannins. Gallotannins are made with formulated IPDA. Then, thermal stability, swell-
up of gallic ester of glucose, quinic acid, shikimic acid, ing properties, and dynamic mechanical properties of
and quercitol. These types of tannins are found in vari- GEGA/IPDA resin were compared with DGEBA/
ous plants and trees such as chestnut, oak, Tara, and IPDA resin after curing. From TGA study, it was
sumac[80–82]. found that 5 wt% loss temperature under N2 atmos-
phere for GEGA/IPDA epoxy resin was found to be
300°C, while for DGEBA/IPDA epoxy resin, it was
Bio-based epoxy from tannin
found to be 350°C. Similarly, 30 wt% loss temperature
A gallic acid is a phenolic acid encountered in various under N2 atmosphere for GEGA/IPDA epoxy resin
plants, both in its simple form and as a part of gallotan- was found to be 335°C, while for DGEBA/IPDA epoxy
nins. Main challenge for gallic acid is the complete func- resin, it was found to be 365°C. Swelling measurement
tionalization of the phenolic hydroxyl groups. By of network was performed with the help of tetrahydro-
Tomita et al.[83], functionalization of gallic acid with furan (THF) as solvent. Swelling percentage for
ECH results in noncontrolled glycidylation. To over- DGEBA-/IPDA-cured resin was 6%, while for
come this problem, Aouf et al.[84] reported another GEGA/IPDA, it was found to be 4%. DMA study
route to gallic acid glycidation by two-step chemical showed that tand value for GEGA-/IPDA-cured resin
synthesis. Further, glycidylated product was cured with was found about 233°C, while for DGEBA-/IPDA-
commercial IPDA yielding cross-linked network and cured resin, it was found about 160°C. This shows that
compared the thermal properties of resulting thermoset higher cross-linking density of GEGA compared to
with standard DGEBA epoxy polymer. DGEBA resin with IPDA. However, the onset tem-
In the first step, allylation of OH group of gallic perature of storage modulus (E′) decrease for
acid was performed and in second step, epoxidation DGEBA-/IPDA-cured resin was more pronounced at
Figure 18. Structure of (a) polysulphone and (b) polynorbornenes synthesized using itaconic derivative.
Figure 19. (a) Synthesis of allylic gallic acid, (b) synthesis of epoxidized gallic acid using mCPBA, and (c) synthesis of epoxidized
gallic acid using methyl(trifluoromethyl)dioxirane. Note: mCPBA, meta-chloroperbenzoic acid.
70°C which indicates better mechanical properties at

high temperature compared to DGEBA-/IPDA-cured
resin. Thus, natural phenolic compound GEGA
appears as good candidate to improve mechanical
properties by increasing the tand value. Again,
challenges using mCPBA or dioxirane are enhance-
ment in rate of epoxidation, increase conversation
(% yield), elimination of by-product (like meta-
chlorobenzoic acid).
Tannin-based polyurethane
Tannin-based polyurethane is also a different topic.
Thébault et al.[85] have synthesized the isocyanate-free
tannin-based polyurethane. The authors highlighted
that how the temperature and pressure affect the wood
coating. The author demonstrates the interesting perfor-
mance that these polyurethanes degrade between 180
and 200°C due to the ability which they have for wood
finishes.
Liu et al.[86] reported the synthesis of nonisocyanate
polyurethane (NIPU) as coating using gallic acid-based
cyclic carbonate with diamines. Further, NIPUs were
modified with epoxy-functionalized polyhedral oligo-
meric silsesquioxanes (POSS). For synthesis of gallic
acid-based cyclic carbonate, epoxidized gallic acid as
resin, LiBr, EG, and N-methylpyrrolidone were taken Figure 20. Synthesis of gallic acid-based nonisocyanate poly-
in autoclave equipped with a magnetic stirrer. The urethane (NIPU) and NIPU/POSS. Note: POSS, polyhedral oligo-
atmosphere was replaced with carbon dioxide. After meric silsesquioxanes.
this, gallic acid-based cyclic carbonate reacted with vari-
ous diamines such as ethylenediamine (EDA), hexam-
Sugar (isosorbide)-based polymer
ethylene diamine (HMDA), IPDA, and Jeffamine
(D230) to give the high cross-linked NIPU network as Bisphenol A is a xenoestrogen molecule which shows
coating. Then, NIPU were modified with epoxy-functio- feminizing effect in living creatures and widely used
nalized POSS yielding NIPU/POSS network as coating in food packaging, dental composites plastic, and baby
(Figure 20). bottles[2,18]. So, in growing environmental issues, there
From DSC study, it was observed that glass tran- is a necessary of bio-derived substances for replacement
sition temperature (Tg) for NIPU using EDA, HMDA, of BPA. Again, 1,4:3,6-dianhydrohexitol-based sugar
IPDA, and Jeffamine were found to be 41.79, 38.36, have rigid structure, nontoxic nature, and chiral struc-
55.43, and 33.59°C, respectively, while Tg values for ture. So that, they can be used in biomedical, packaging,
20% of POSS-modified NIPU were 48.79, 41.75, and polymer synthesis application[87–91]. Depending on
57.58, and 35.60°C, respectively. TGA study observed stereochemistry, they are of three types, i.e., isosorbide,
that all coatings have good thermal resistance proper- isomannide, and isoiodide. For isosorbide, one hydroxyl
ties and 50% weight loss temperatures of all coatings group is exo and another hydroxyl group is endo. For
were above 330°C. Again, water resistance of NIPU/ isoiodide, both hydroxyl groups are exo, while for
POSS was improved compared to NIPU coating. isomannide both hydroxyl groups are endo[92]. Out of
Water uptake for NIPU using EDA was 36.72%, while these three types of isomer, isosorbide can be produced
for 20% weight of POSS-modified NIPU using EDA at an industrial scale having good reactivity[93,94]. Its
was 14.28%. It was also found that pencil hardness chemical structure has been shown in Figure 21. Isosor-
of NIPU/POSS coatings were enhanced compared to bide is synthesized using starch. First, starch degraded
pristine NIPU coatings. However, impact strength into D-glucose using enzymatic process which on
and flexibility of NIPU/POSS coatings were not hydrogenation gives D-sorbitol. On dehydration, sorbi-
observed to be affected. tol gives isosorbide[3]. The synthesis of isosorbide using
Figure 21. Structure of isosorbide.
starch is depicted in Figure 22. Sugar derivatives like

isomannide and isoiodide are derived from D-mannose
and L-fructose, respectively[95].
Isosorbide is bio-based platform for the synthesis of
bio-based polymers like bio-based epoxy[96], bio-based
polyurethane[97–99], bio-based polyester[100], and poly-
carbonate[101].
Bio-based epoxy from sugar

Synthesis of bio-based epoxy from natural polysacchar-
ide is important to replace the DGEBA. Petrochemical-
based epoxy resin of high thermal stability can be
replaced by sugar-based epoxy monomer, while gluco-
pyranoside- and glucofuranoside-based trifunctional
epoxy components are most promising for high-tech
application. Rapi et al.[102] reported that Tg value for
sugar-based epoxy up to 175°C had been achieved and
thermal degradation starts at around 300°C.
Isosorbide has potential to replace petroleum-based
Figure 23. Synthesis of isosorbide diglycidyl ether.
materials like BPA as green alternatives. Isosorbide are
the most widely available dianhydrohexitol, the
hydroxyl group at C-2 shows exo position, while at C- solution and excess of ECH[103,104](Figure 24). The
5 shows endo position. bis-isosorbide diglycidyl ether can be cured with differ-
Again, isosorbide have remarkable chemical proper- ent hardening agents like aliphatic amine (Jeffamine
ties, attractive price, biodegradable and similar structure T403) and resulting isosorbide epoxy shows greater
to that of BPA but no endocrine-disrupting effect. Iso- enhancement in tensile strength and impact strength
sorbide can be introduced to glycidyl ether or allyl ether as compared to that of DGEBA resin which could be
having similar properties to DGEBA resin. used as coating, adhesives, composite, and biomedical
Diallyl isosorbide ether was synthesized by heating applications.
the isosorbide with allyl bromide in alkali solution.
After this, isosorbide diglycidyl ether was synthesized
by reacting diallyl isosorbide with mCPBA in methylene
chloride (as illustrated in Figure 23).
The bis-isosorbide diglycidyl ether was synthesized
by heating the isosorbide with 50% sodium hydroxide
Figure 22. Synthesis of isosorbide using starch. Figure 24. Synthesis of bis-isosorbide diglycidyl.
Bio-based polyurethane from sugar (isosorbide)

It is important to note that polyurethane based on
isosorbide shows high glass transition temperature.
Isosorbide on reacting with diisocyanate gives poly-
urethane. The Tg values of polyurethane based on isosor-
bide have been highly affected by di-isocyanate. The
polyurethane prepared from di-isocyanate like methylene
diphenyl diisocyanate (MDI) shows the high Tg value
compared to toluene diisocyanate (TDI), HDI[93,105,106].
Isosorbide-based polyol
The isosorbide-based polyols could be synthesized by
ring opening of epoxy group present in isosorbide gly-
cidyl ether with the help of trifluoroacetic acid catalyst Figure 26. (a) Epoxidized isosorbide and (b) isosorbide
as shown in Figure 25[107]. oligomer.
Polyurethane synthesis from isosorbide DA10, and IPDA, Tg values were found to be 8, 0,
Normally, polyurethanes are obtained by the reaction 15, and 59°C respectively while 5% weight loss tem-
between isocyanate and diol. However, these isocya- perature were found at 242, 234, 243, and 255°C,
nates are hazardous for human health related to poly- respectively.
urethane industry. Besse et al.[108] reported the Lee et al.[109] reported the synthesis of polyurethanes
synthesis of isosorbide-based polyurethane using from isosorbide and different diisocyanate using n-
isocyanate-free method. They synthesized bio-based butyltin hydroxide oxide hydrate as a catalyst as shown
isosorbide dicyclocarbonates. Further, polyhydroxy in Figure 27a. The resulting polyurethane has been
urethanes were synthesized using different cyclocarbo- characterized using IR, NMR spectroscopy, and
nate–amine (i.e., Jeffamine D-400, 1,10-diaminode- dynamic viscoelastic analysis (DMA). It was also
cane, diethylenetriamine and isophoronediamine) observed that high Tg values and storage modulus were
and products were characterized by 1H-NMR, FTIR, constant to higher temperature for three component
DSC, and TGA analysis. systems (Figure 27b) as compared to two component
Polyhydroxy urethane was synthesized from isosor- systems.
bide oligomer (Figure 26) using different amines, i.e., Marín et al.[110] prepared the polyurethane with 1,4-
Jeffamine D-400, diethylenetriamine, 1,10-diaminode- butanediol, isosorbide, and di-isosorbide diurethanes as
cane and IPDA. They found that for JEF400, DETA, diols using different diisocyanates (i.e., MDI, HDI).
They found that using MDI, Tg values for polyurethane
based on butanediol, isosorbide, BDIs, and BDIs2
(structures are depicted in Figure 28) were found to
be 93, 183, 120, and 115°C, respectively, while ΔH
values found were 20, 20, 18, and 18°C, respectively.
Again using HDI, Tg values for butanediol, isosorbide,
BDIs, and BDIs2 were found to be 15, 77, 30, and
24°C, while ΔH values were found to be 77, 27, 48,
and 62°C, respectively. For TGA study, using MDI,
onset decomposition temperature for polyurethane
based on butanediol, isosorbide, BDIs, and BDIs2 were
found to be 282, 297, 281, and 283°C, while using
HDI, onset decomposition temperatures were found to
be 300, 296, 300, and 302°C, respectively.
Waterborne polyurethane dispersions are widely
used as protective coating. Li et al.[111] reported the
synthesis of waterborne polyurethane from isosorbide
and dimer fatty acid-based diisocyanate using dimethy-
Figure 25. Isosorbide-based polyol. loprionic acid as internal dispersing agent.
Figure 27. (a) Polyurethane synthesis from isosorbide and one type of di-isocyanate. (b) Polyurethane synthesis from isosorbide and
two different types of diisocyanates.
In recent years, the vegetable oil has been used

in increasing the production of lubricants[143,144],
coating[145,146], paints[147], biodiesel[148–151], bio-
surfactant[152], biocomposite[153], and biomedicine[154].
Out of these, soybean oil, palm oil, linseed oil, and
rapeseed oil share major portion, globally. Palm oil
is largest oil production followed by soybean, rape-
seed, and sunflower oils. Palm oil production is
maximum in Indonesia and Malaysia (∼50%); soy-
bean oil production is maximum in USA, china; castor
oil plant as inexpensive plant found in India, china,
and Brazil. Again, challenge for vegetable oils are their
potential chemical modification which can be useful in
Figure 28. Structure for (a) 1,4-butanediol, (b) isosorbide, and
(c) BDIs2. the field of bio-based blend, bio-based composite, bio-
diesel as engine fuel, photosensitive coating material,
eco-friendly paint, and preparation of polyether poly-
Natural oil-based polymer
ols for polyurethane having molecular weight up to
Commonly, there are large number of edible and 10 kDa.
nonedible oil such as soybean oil[112–114], palm Main component of triglyceride vegetable oils
oil[115,116], linseed oil[117–120], rapeseed oil[121–123], (Figure 29) are saturated and unsaturated fatty acids
grapeseed oil[124], castor oil[32,125,126], corn oil[127], (Figure 30) which in its pure form are also available
canola oil[128–130], cottonseed oil[130], Karajan oil[131], as platform chemicals for polymer synthesis. These fatty
Tung oil[132–135], mustard oil[136], Hemp oil[137,138], sun- acid has industrial value depending on chemical modi-
flower oil[139], Jatropha oil[140], and neem oil[141,142] fication of the ester (‒COOR) and carbon double bond
which are helpful in synthesis of bio-based polymer. (C=C) as shown below.
Table 3. Iodine value for different types of natural oils.

Types Iodine value Examples
Drying oils >130 Linseed oils
Semidrying oils 100 < iodine value <130 Soybean oils
Nondry <100 Palm oils
Figure 29. Structure of triglyceride of oil.

iodine value gives higher cross-linked structure which
leads to better thermal and mechanical properties
These triglycerides (glycerol ester of fatty acid) con- (depicted in Table 3).
tain some chemical reactive groups like C=C, ‒OH,
epoxy, ‒COOR which are formed by different chemical
Epoxidation. Epoxidation is one of the most important
reactions like epoxidation, hydroxylation, acrylation,
functionalization reactions of C=C double bond that can
urethanation, maleinization, thiol-ene reaction, and
be achieved by environmentally friendly procedures
furan-containing triglyceride[33–43,140,155]. These
such as catalyzed chemical oxidation with hydrogen
modified fatty acid is the key concept for the synthesis
peroxide or enzymatic oxidation. Unsaturated fatty acid
of new bio-based sustainable polymer like epoxy
(triglyceride) can be converted into epoxy fatty acid by
resins[156,157], polyurethanes[158,159], polyester[160–162],
conventional epoxidation, catalytic acidic ion-exchange
and polyamides[163].
resin, metal catalyst epoxidation, or using chemoenzy-
Vegetable oil polymers can be obtained by free rad-
matic epoxidation, transition metal complexes, chlori-
ical, cationic, and olefin metathesis polymerization.
nated KU-2�8 cation exchanger, Ti(IV)-grafted silica
These vegetable oil polymers show the wide range of
catalyst[155]. Again, challenge for the epoxidized oils
thermal, physical, and mechanical properties and they
are the synthesis of monomer by efficient, good yield,
are promising materials as alternative to their pet-
rapid, and low-cost epoxidation process.
roleum-based polymeric materials.
Thiol-ene reaction for triglyceride. Shortly, thiol-ene

Chemical modification of triglyceride and addition is the radical addition of thiols to C=C double
triglyceride derivative containing natural oil bond in which any alkene functional group can partici-
pate. It is important to note that thiol-ene reaction is
Chemical modification of fatty acid present in vegetable
the most simple, an efficient method for modification
oil depends on the ester groups (‒COOR) or unsatu-
and polymerization of alkenes. Due to this character-
rated carbon groups (C=C).
istic, it can be used as green procedure for thiol-ene
addition reaction with plant oils and their fatty acid
Modification based on C=C derivatives, which naturally possess double bonds.
The number of C=C is very much important to find Stemmelen et al.[35] synthesized the novel vegetable
some important parameters like physical and chemical oil-based polyamine (i.e., aminated grapeseed oil)
structures. The number of C=C is calculated by iodine using cysteamine chloride by thiol-ene coupling and
value. Depending on these values, vegetable oils are AGSO is used as curing agent for epoxidized linseed
classified into three types. Vegetable oils with higher oil (ELO, Figure 31a and B).
Figure 30. Structure of fatty acid (1) oleic acid, (2) linoleic acid, (3) linolenic acid, (4) erucic acid, (5) petroselinic acid, (6) ricinoleic
acid, (7) vernolic acid, (8) 10-undecenoic acid.
method for the introduction of amine group into

vegetable oil.
Acrylation. Acrylate triglyceride are low viscous, highly

reactive and can be free radically polymerized. Acry-
lated oils were synthesized from epoxidized oils through
the ring opening of the oxirane group using acrylic acid
as the ring-opening agent. Different acrylates like meth-
acrylic acid can also be used as the ring-opening agent
and further modification is possible using methacrylic
anhydride, acetic anhydride, etc.[164,168] Kinetically,
curing behavior of acrylated oils is influence by autoca-
talytic mechanism than by nth order mechanism[140].
Wuzella et al.[120] study synthesis of acrylated ELO
using acrylic acid and ELO. The synthesized resin was
mixed with three different initiators, i.e,. benzophenone,
2,4-diethyl-9H-thioxanthene-9-one, 2-hydroxy-2-methyl-
1-phenyl-propan-1-one photoinitiator, and surface
properties like gloss, scratch resistance, adhesion, and sol-
vent resistance of the coating were studied. Cure charac-
teristics of synthesized resin have been studied with three
different photoinitiators, different light intensities, and
different temperatures using real-time FTIR. It was found
that coating properties are best when they cured slowly. It
was found that such types of coatings have sufficient
cross-link density, polymer chains are flexible for
scratches and they have good adhesion to the wood.
Espinosa et al.[41] give new general and environmen-
tally friendly route to introduce acrylate groups in
unsaturated vegetable oil. First, they are converted into
allylic hydroperoxide which on reduction gives corre-
sponding hydroxylic compound. Hydroxyl-containing
triglyceride on esterification with acryloyl chloride gives
acrylate-containing triglyceride having high toughness
and good transparency.
Ma et al.[165] reported preparation of fully bio-based
thermosetting resin from AESO and rosin acid deriva-
tives which is illustrated in Figure 32. Two types of rosin
derivatives, i.e., divinyl rosin (DR) and trivinyl rosin
(TR), synthesized from rosin acid and DVB were used
as comonomer. Chemical structures of all synthesized
compounds were determined with the help of FTIR,
1
H-NMR, and 13C-NMR. Comonomers’ proportions
were changed as 20, 40, and 60% and cured with
2 wt% (by total weight) of tert-butyl peroxybenzoate.
Figure 31. (a) Amination of grapeseed oil using thiol-ene The mechanical and thermal properties of the resulting
reaction. (b) Curing reaction between epoxidized linseed oil thermosets were investigated by DMA, DSC, and TGA.
and aminated grapeseed oil.
From DSC study, they found that maximum tem-
perature of the cross-linking exotherm (Tmax) for neat
Synthesis of bio-based amine from vegetable oil can AESO, AESO/DVB20, AESO/DR20, AESO/DR40,
be developed through aziridine, hydrazine, and nitrile, AESO/DR60, AESO/TR40, and AESO/TR60 were found
but thiol-ene chemistry gives a direct and efficient to be 121.3, 127.6, 130, 135.2, 140.9, 133, and 136.8°C,
found to be 398.3, 396.9, 397, 398.5, 398.9, 404.1, and

416.1°C, respectively. Thus as compared to DVB, the
rosin-based comonomers show more enhancement in
mechanical and thermal properties of cured AESO. This
study synthesized full bio-based thermosetting resin
using soybean oil and rosin acid derivative which
showed the great potential to replace the petroleum-
based thermosetting resin.
Aldehyde (ketone)- and enone-containing triglyceride.

Aldehyde (ketone)-containing triglyceride. Espinosa
et al.[36] have applied new cross-linking approach to
an aldehyde-containing triglyceride to get quinoline-
containing thermoset in the presence of BF3MEA as
a catalyst. Aldehyde-containing triglycerides are ideal
to produce thermoset with higher cross-linking
degree. Similarly, they synthesized vic-diol-containing
triglyceride from epoxidized high-oleic sunflower
oil. First, epoxidized high-oleic sunflower oil was
dissolved in THF in round bottomed flask. In this sol-
ution, 60% HClO4 added and reaction mixture was
Figure 32. Copolymerization of AESO with comonomers (DVB/ extracted with DCM and product was obtained with
DR/TR). Note: AESO, acrylated epoxidized soybean oil; DVB, 96% yield.
divinyl benzene; DR, divinyl rosin; TR, trivinyl rosin. Synthesis of aldehyde containing triglyceride had
been obtained by adding diol triglyceride and NaOI4
respectively. From DSC study, it was clear that vinyl in round bottomed flask. To this, 9/1 mixture of 1,4-
group containing AESO was more reactive compared dioxane/water was added and diluted with DCM. A pale
to other, while TR showed more reactivity compared brown oily product was obtained. In this way, a trigly-
to DR due to its higher functionality. From DMA study, ceride containing 2.5 aldehyde groups per molecule
they found that Tg values for neat AESO, AESO/DVB20, was obtained with 90% overall yield. Finally, at high
AESO/DR20, AESO/DR40, AESO/DR60, AESO/TR40, temperature, with 4,4-diaminodiphenyl methane
and AESO/TR60 were found to be 34.8, 35.6, 46.5, (DDM) in the presence of BF3MEA, aza-Michael adduct
58.5, 81, 60.6, and 86.3°C, respectively, and storage formed through self aldol condensation, cyclization, and
modulus at 25°C were found to be 169.9, 177.7, 296.9, aromatization reactions (Figure 33a). This product was
496.6, 562.9, 752.2, and 1,205 MPa, respectively. Thus cured with DDM yielding a material with a Tg value
from DMA study, it is clear that hydrogenated phen- of 84°C and improved thermomechanical properties
anthrene ring in DR and TR give more rigid cured resin which can related with its higher quinoline content.
than aromatic ring in DVB. The higher Tg in TR-cured Enone-containing triglyceride. Espinosa et al. synthe-
resin was expected because of the higher functionality of sized enone-containing triglyceride from high-oleic sun-
TR. Similarly, Young’s modulus for above systems were flower oil and cross-linking of enone-containing
found to be 26°C � 0.3 MPa, 48.6°C � 0.8 MPa, triglyceride through an aza-Micheal addition. First, the
45.2 � 0.5 MPa, 65 � 2.5 MPa, 126 � 8.3 MPa, 99.7 � 6.1 enone-containing triglyceride was synthesized through
MPa, and 289.9 � 3 MPa, respectively. It is important to photoperoxidation of high-oleic sunflower oil. For enone
note that rosin-based cured thermosetting resin shows synthesis, high-oleic sunflower oil, TPP, and DCM were
higher tensile toughness as compared to DVB-based taken in photochemical reactor with 400-W high-
cured resin. The extraction analysis for cured thermo- pressure sodium vapor lamp (Figure 33b). Then curing
setting resin was performed with DCM under reflux was performed with DDM. First, DDM and enone-
for 40 h. Soluble percentage for the above system were containing triglyceride were melted and mixed well.
found to be 8.7, 8.5, 7.9, 10.8, 16.6, 10.9, and 12.7%, After this, they introduced in mold and heated at 90°C
respectively. The maximum soluble fraction of DR for 12 h and postcuring at 120°C for 6 h[36,166].
might be due to the low reactivity. From TGA study, Kinetic experiment indicates that unsaturated ketone
it is clear that for extracted resin under N2 atmosphere, reacts much faster than the corresponding epoxide even
50% weight loss temperature for above systems were in the presence of cationic ring-opening catalyst. In
explains the improvement of the thermal and mechanical

properties of these thermoset materials[36,166].
Maleinized triglyceride. Maleated castor oil (MACO)

synthesized using maleic anhydride (MA) and
castor oil in the presence of temperature as shown in
Figure 34a and b). Ghorui et al.[37] synthesized MACO
by adding maleic anhydride and castor oil in 3:1 mole
ratio in 500-ml three-necked round bottom flask and
temperature was maintained at 125°C for 4 h with con-
tinuous stirring. The synthesized MACO then mixed
with UPE resin in different ratio from 5 to 15 wt% and
sonicated for 1 h at room temperature to remove the
air bubbles. Cobalt naphthenate has been used as acceler-
ator and methyl ethyl ketone peroxide (MEKP) as
initiator. MACO–UPE/fly ash composite fabricated using
compression molding with constant wt% of fly ash.
The MACO-based UPE blend prepared ranging from
5 to 15 wt% with an interval of 5 wt%. A 5 wt% MACO
had been given better result compared to 10 and
15 wt%. The impact strength increased by 52% without
any loss in modulus while Tg value also shift to higher
temperature.
Again Ray et al.[40] studied the effect of MACO in
affecting mechanical properties of like impact and
damping. Morphological study of DGEBA/MACO
blend cured with DETA hardner and the resulted
MACO/epoxy blend matrix showed significant
enhancement in impact strength and damping proper-
ties compared to that of epoxy. The impact strength
of MACO/epoxy blend increased by 315% compared
to that of epoxy laminate. The SEM micrographs
showed a good compatibility between epoxy and
MACO. Thus, a new material was synthesized to
achieve greener and more sustainable pathways.
Liu et al.[32] synthesized highly functionalized
MACO, namely, castor oil pentaerythritol glyceride
maleates and fabricate partial bio-based UPE resin.
The properties like cross-link density, Tg, tensile and
Figure 33. (a) Synthesis scheme for aldehyde-containing tri- flexural moduli, and impact strength are found to be
glyceride and its cross-linking with DDM using BF3MEA as a enhanced. Can et al. used different polyols like pentaer-
catalyst. (b) Enone synthesis from high-oleic sunflower oil using ythritol, glycerol, and BPA and found a significant
photoperoxidation. Note: DDM, 4,4-diaminodiphenyl methane. enhancement in Tg, modulus and strength value.
this way, the aza-Micheal addition of DDM to these Furan-containing triglyceride. Gandini et al.[41] synthe-
enone-containing triglycerides was used to produce sized the furan-containing epoxidized triglyceride from
thermosets under mild conditions and temperature linseed oil as shown in Figure 35. This approach is econ-
below 120°C. omically viable and greener in character. For the syn-
Tg value of enone-containing triglyceride is equal to thesis of furan-containing linseed oil, experiment was
16°C due to light cross-linking density and aliphatic nat- performed with excess of 2-furfuryl amine and ELO in
ure of triglyceride content. On heating with DDM, it the presence of zinc catalyst like zinc chloride or zinc
shows Tg value equal to 64°C. It means that it has tougher perchlorate hexahydrate. This mixture was stirred at
material characteristics. Thus, trisubstituted quinoline 80°C and maintained the nitrogen atmosphere. Excess
Figure 34. (a) Synthesis of maleated castor oil. (b) Oligomerization of maleated castor oil.
catalyst and 2-furfuryl amine were removed by dissolv- Metathesis of triglyceride. In metathesis of oils, olefins
ing mixture in methylene chloride. Then the product are converted into new olefins through an exchange of
was analyzed with the help of 1H-NMR and FTIR. alkylidene groups. Grubbs ruthenium catalyst (Cy3P)
2Cl2Ru ¼ CHPh (Figure 36) is an effective catalyst for
metathesis of oils. Various types of polymers can be
prepared using olefin metathesis i.e., ring-opening
metathesis polymerization or acrylic diene metathesis
polymerization[43].
Azide-containing triglyceride. Biswas et al.[42] studied

the formation of epoxides and then the azidization of
the epoxides. Azide is thermally and photochemically
labile which can be easily converted to other functional
groups. For azidization, in round bottom flask, water
with ionic liquid, sodium azide in water and epoxi-
dized soybean oil (ESO), or epoxidized methyl linole-
ate were taken and stirred using stirring bar and
further heated up to 65°C and the extraction was
performed with ethyl acetate. The confirmation of
Figure 35. Furan-containing triglyceride. Figure 36. Grubbs catalyst.

Figure 37. Different modified triglyceride.
product was determined with the help of 1H-NMR and

13
C-NMR. Azidization reaction can apply not only to
methyl linoleate, methyl oleate and soybean oil but
also to methyl soyate (Figure 37).
Modification based on COOR (ester group)

Development of new epoxy monomer from vegetable oil
with better oxirane functionality, better reactivity, and
better performance will help for sustainable and envir-
onmentally friendly product. EGS (glycidyl ester of
epoxidized fatty acid derived from soybean oil), EGL
(glycidyl ester of epoxidized fatty acid derived from lin-
seed oil), and analogous epoxy monomers were synthe-
sized to give better compatibility with DGEBA to reduce
pendant chain (Figure 38), to increase reactivity, and to
control oxirane content. On the basis of ester group, Figure 38. Pendant chain presents in epoxidized soybean oil
(ESO) and its derivative (fatty acid).
epoxidized methyl oleate, epoxidized methyl soyate
(EMS), and epoxidized allyl soyate show lower viscosity
and more reactivity as compared to their corresponding resin such as DGEBA, DGEBF. It is a good luck that
ESO or ELO. Scheme for the synthesis of glycidyl ester epoxide group containing vegetable or nonvegetable oils
of epoxidized fatty acid has been given in Figure 39. shows a reactivity similar to petroleum-based epoxy
Thus, Wang and Schuman[167] synthesized free fatty resin when anhydride are used as curing agent. It is
acid using soybean oil in the presence of alkali and important to note that mechanical properties like ten-
H2SO4. After this, free fatty acid converted into glycidyl sile, impact, flexural, thermal like Tg, and morphological
ester of fatty acid in the presence of epichlorohydrin properties not only depend on resin but also on type of
(EPCH) and NaOH. At last, glycidyl ester of epoxidized curing agent. Thus, many of the literature are concen-
fatty acid is obtained in the presence of mCPBA in trated on partially bio-based epoxies and improvement
CH2Cl2 or in mixture of H2O2 and HCOOH. Similarly, of their initial properties. Anhydride curing agent shows
thiol-ene, acrylation, and so on can be performed using good reactivity and good properties with epoxidized oil
glycidyl ester of fatty acid. compared to amine curing agent.
Gerbase et al.[168] have studied mechanical and thermal
properties of ESO cured with different cyclic acid anhy-
Bio-based epoxy using natural oil
drides like phthalic anhydride (PA), maleic anhydride
We know that among the available natural resources, (MA), succinic anhydride (SA), hexahydrophthalic anhy-
vegetable epoxidized oils are widely used as either plas- dride, and dodecenylsuccinic anhydride (DDS) in the
ticizer or stabilizer for polyvinyl alcohol (PVC) syn- presence of tertiary amines. From the DMA analysis, it
thesis or paints and coating purpose. They have ability was observed that PA- and MA-cured systems showed bet-
to replace the conventional petroleum-based epoxy ter dynamic mechanical properties compared to SA- and
Figure 39. Synthesis of glycidyl ester of epoxidized fatty acid from soybean oil.
DDS-cured systems. Park et al.[169] have studied the effect can be synthesized using 1,3-butadine, cyclopentadiene
of epoxidized castor oil (ESO) in affecting the physico- or dicyclopentadiene through Diels–Alder reaction as
chemical and mechanical properties of the DGEBA/ESO shown in Figure 41. Thus, the synthesized cycloaliphatic
blends initiated by N-benzyl-pyrazinium hexafluoroanti- structure of vegetable oils is expected to improve proper-
monate (BPH) as thermally latent initiator. It was found ties like Tg, tensile strength, and impact strength.
that the fracture toughness and flexural strength of epoxy The conversion of double bond should be limited i.e.,
blend improved tremendously with increasing epoxidized <30%; otherwise, high-viscosity liquid will be obtained.
castor oil (ECO) content. Ratna[170] studied mechanical This viscosity can be decreased using the reactive
and thermal properties of ESO (modified and unmodified) diluents and final conversion increases[173].
cured with amine hardener and modified network with
20 phr showed higher impact strength. Effect of nanoparticles on bio-based triglyceride
systems
Main challenge for vegetable oil-based nanocomposite is
Miscellaneous bio-based epoxy using natural oil proper dispersion of nanoparticles so that intercalation
Pan et al.[171] synthesized bio-based epoxy compound
using epoxidized sucrose ester of fatty acids. Sucrose
ester of fatty acids is the combination of sucrose and
vegetable oil fatty acid as shown in Figure 40. Procter
and Gamble (Cincinnati, Ohio) chemicals gives indus-
trial manufacturing process for sucrose ester of fatty
acids under brand name SEFOSE.
Epoxidation of sucrose esters were performed using
hydrogen peroxide (H2O2) and acetic acid in the pres-
ence of Amberlite 120H. Solvent diethyl ether was
removed by rotovapping. The confirmation of yield
structure was performed with the help of FTIR,
1
H-NMR, and 13C-NMR. Additionally, epoxidized
sucrose ester shows high epoxy functionality, high
density, and compact molecular structure compared to
sucrose ester resin of vegetable oil fatty acid. Epoxidized
sucrose ester fatty acid cured with anhydride materials
showed high hardness and modulus values as compared
to cured ESO materials[171,172].
Most of the thermoset polymers obtained from epox-
idized vegetable oils show rubbery nature which leads to
low Tg values. So, cycloaliphatic structure of vegetable oil Figure 40. Structure of sucrose ester of fatty acid.
Haq et al.[177] studied the bio-based UPE composite

reinforced with layered silicate with varying clay concen-
tration and varying bioresin (i.e., epoxidized soy bean
oil) and study the thermophysical properties like tensile
strength, toughness, Tg value, coefficient of thermal
expansion, and moisture absorption. For the synthesis
of nanocomposite, bioresin i.e., EMS in UPE was varied
from 0 to 20%, in increment of 5%, while nanoclay was
varied from 0 to 1.5 wt% with an increment of 0.5 wt%.
The bio-based UPE composite reinforced with nanoclay
showed the improved toughness with the addition of
EMS and optimized for 10% of EMS.
Chen et al.[178] studied the clay montmorillonite-
reinforced castor oil-based polyurethane/epoxy interpe-
netrating network (IPN) composite. For IPN composite,
first specific amount of castor oil in round bottom flask
at 65°C was thoroughly mixed with specific amount of
TDI. Then, mechanically stirred under dry nitrogen
atmosphere to form urethane prepolymer and then cal-
culated amount of DGEBA and montmorillonite
(MMT) are added. It was found that 3 wt% of MMT
showed best damping properties, while thermal stability
also improved compared to PU. Again, tensile strength
and impact strength also found to be improved. This
Figure 41. Synthesis of epoxy norbornene linseed oil using lin- IPN composite may be applicable in damping structural
seed oil and cyclopentadiene. materials.
Again, Chen et al.[179] studied potassium titanate
whisker-reinforced castor oil-based polyurethane/epoxy
has been achieved. These nanoparticles have ability to IPN composite and found that damping, tensile
improve thermal, electrical, and mechanical properties. strength, and thermal stability were enhanced. Chen
Lligadas et al.[174] studied the nanocomposite from ELO et al.[180] studied the nano-CaCO3-reinforced epoxy
and POSS. In this study, ELO and 3-glycidylpropylhep- resin/ECO composite and found that impact strength
taisobutyl-T8-polyhedral oligomeric silsesquioxane were was enhanced by the addition of ECO and nano-CaCO3.
used and curing was performed using 1% cationic cata- It was also found that propagation cracks were pre-
lyst BPH. The cured bionanocomposite was homo- vented. It was also reported that addition of nano-
geneous and transparent having enhanced glass CaCO3 enhanced the thermal stability of composite
transition temperature and storage modulus. Liu and compared to DGEBA-ECO system.
Erhan[175] prepared nanocomposite from ESO and Cloi-
site 30B as nanoclay using triethylenetetramine as curing
Bio-based polyurethane using natural oil
agent. By adding nanoclay from 5 to 10 wt%, storage
modulus from 2 � 106 to 2.7 � 106 Pa, while Tg value We know that over the past several years, much attention
measured by dynamic mechanical study was found to has been given to the use of variety of oil. To produce
be 20°C. From XRD and TEM analyses, nanocomposite polyurethane, various types of oil-based polyols can be
showed the intercalated structure. reacted with isocyanate and a wide variety of oil-based
Miyagawa et al.[176] studied bio-based nanocompo- polyol leads to a wide variety of polyurethane i.e.,
site from anhydride-cured ELO/epoxy matrix reinforced flexible and rigid foam, ductile plastics[181,184]. Thus,
with organomontmorillonite clay. The dispersion of generally, they are used as flexible foam and rigid foams
nanoclay was performed by sonication technique. The as well as coating, adhesive, sealants, and elastomer.
glass transition temperature and heat deflection tem- They have largest demand in automotive and furniture
perature of bio-based epoxy decreased with the addition industry but nowadays they are entered in coating and
of ELO content while decreased in storage modulus due construction application. General reaction to produce
to higher content of ELO could be regained with the polyurethane from diol and di-isocyanate is shown in
reinforcement of nanoclay. Figure 42.
Epoxidation/oxirane ring opening. Vegetable oils are

typically epoxidized by generating a peracid in situ from
hydrogen peroxide and acetic or formic acid. This
method results in sufficient yields of epoxidized oil
(75–90%) and is used in most commercial process.
Mostly, vegetable oil-based polyols are produced by
epoxy ring opening with proton donors (Figure 43).
The use of alcohols gives the best products as polyol
due to their high functionality. Methanol having low cost,
molecular weight, and boiling point is the preferred alco-
hol and fluoroboric acid is used as acid catalyst. Again,
Figure 42. General scheme for synthesis of polyurethane. alcohols like ethylene and propylene glycol and catalyst,
both acid and base, have also been used while use of diols
gives the very high hydroxyl functionality[181,184].
Different method for the synthesis of polyol from It is important to note that EG gives the primary
natural oil hydroxyl groups in polyol which are three times more
We know that polyurethanes are the most versatile reactive than the secondary hydroxyl groups in poly-
polymers because of the wide range of monomer i.e., urethane production. Some drawback like high viscosity
diols or polyols that can be used for polyurethane syn- is also present while producing the polyols from epoxi-
thesis. From the last several years, there is an increase in dized vegetable oils. The self-catalyzed ring opening of
the attention to use of vegetable oils as feedstocks for ESOs with inorganic acids, hydrochloric or hydro-
polyurethane synthesis, because vegetables oils are low bromic acid proceeds to give high-functionality polyol
cost and available in large quantities. There are various like highly viscous greases. Hydrogenation of ESO in
procedures, for polyol or diol synthesis and also for poly the presence of H2 and Raney nickel gives slightly lower
or di-isocyanates obtained from vegetable oils. hydroxyl functionality, but again greasy nature.
Figure 43. Synthesis of various types of polyols from natural oil.

Lactic acid, also a renewable resource, gives the ring

opening of ESO and hydroxyl-containing lactic acid
leads to polyol with sufficient functionality.
Transesterification/amidation. Another same routes to

synthesize vegetable oil-based polyol included transes-
terification with various polyols or amidation with
diethanolamine of vegetable oils as shown in Figure 43.
The most frequently used polyol is glycerol. But gly-
cerol contains hydrogen atoms on the carbons adjacent
to the hydroxyl bearing carbon (i.e., b-hydrogen). So
glycerol is easily degraded at high temperature to give
unsaturated compounds and water molecules. Due to
this, polyols like trimethylpropane or pentaerythritol
with no b-hydrogen have been used in the place of
glycerol.
Typically, the transesterification reaction is catalyzed
not only by base but also by enzymes like lipases. Figure 44. Synthesis of silicon-containing, fatty acid-based
Enzymes like lipases can target the, 1,3-positions of gly- triols.
cerol backbone to give polyols containing only primary
alcohols. Again, higher molecular weight triols are method i.e., epoxidation/oxirane ring opening and
synthesized by the transesterification of methyl esters hydroformylation/reduction[181,184].
of ricinoleic acid and hydroformylated oleic acid with
trimethylolpropane[181,184].
Miscellaneous. Silicon-containing, fatty acid-based
Hydroformylation/reduction. Hydroformylation/reduction triols have been synthesized for potential flame retard-
of vegetable oils involves the two-step procedure. In ant applications. The triols are synthesized in good
the first step, the vegetable oil is reacted with mixture yields in two steps i.e., first triester is obtained by hydro-
of CO and H2 in the presence of a catalyst to give the silylation of methyl 10-undecenoate with phenyl-tris
aldehyde which is then reduced with H2 in the second (dimethylsiloxy)silane in the presence of platinum.
step to yield hydroxyl groups as depicted in Figure 43. Then, primary hydroxyl groups are obtained by the
Commonly, cobalt or rhodium carbonyl complexes are reduction with lithium aluminium hydride (Figure 44).
used as catalyst. They are modified by tertiary
phosphine/phosphite ligands. Cobalt has the advantage
of being inexpensive, while rhodium has disadvantage
of being expensive but rhodium catalyst give excellent
conversion in presence of Raney nickel in the hydro-
genation step.
The main advantage of this method is the production
of primary hydroxyl groups, which are more reactive
with isocyanate for polyurethane synthesis[181,184].
Ozonolysis/reduction. Ozonolysis is the method in

which ozone (O3) reacts with alkenes in vegetable oils
to break the double bond and form two carbonyl groups
and further it is reduced with Raney nickel to give
corresponding primary alcohol. This carbonyl can also
be treated with sodium borohydride (NaBH4) to give
primary alcohol (Figure 43).
It is the advantage of this method that half of each
fatty chain is removed and reduce plasticization effect.
Again, the resulting polyols have approximately 40%
lower molecular weight compared to the previous Figure 45. Synthesis of vegetable oil-based isocyanate.
N-bromosuccinimide is followed by reaction with

silver isocyanate to give allylic iso-cyanates. About 2.1
isocyanate groups per triglyceride are obtained. Again,
challenge of this procedure is alternative to silver isocya-
nate because of its high cost. In another method, oleic
acid-based linear di-isocyanates including saturated
Figure 46. General scheme for synthesis of bio-based epoxy and unsaturated can be synthesized using the Curtius
and bio-based polyurethane. rearrangement (Figure 45).
Thus, all these methods can be useful for synthesis of
Natural oil-based isocyanate. Vegetable oil-based di- different polyols which further gives polyurethane.
isocyanates are aliphatic in nature, while aromatic di- General scheme for synthesis of bio-based epoxy and
isocyanates are used in industry because aromatic bio-based polyurethane from natural oil is shown in
di-isocyanates are more reactive compared to aliphatic Figure 46.
di-isocyanate and this reactivity is required while
producing the foam. These vegetable oil-based iso-
Miscellaneous polyurethane synthesis from
cyanates are useful in coating application due to their
natural oil
unsaturation.
Industrially, isocyanates are prepared by the phosge- Chaudhari et al.[182] studied synthesis of polyurethane
nation of primary amine but it is difficult to introduce for coating purpose from neem oil polyester amide
primary amine into the vegetable oils. So other which has self-healing anticorrosive properties. First,
method, i.e., allylic bromination of soybean oil with they synthesized neem oil fatty amide from neem oil
Figure 47. (a) Synthesis of neem oil amide. (b) Synthesis of polyesteramide using neem oil fatty amide and polyurethane from
polyesteramide.
using diethanolamine in the presence of base which is excess of isophorone diisocyanate (IPDI) using methyl
depicted in Figure 47a. Polyesteramide was synthesized ethyl ketone (MEK) as a solvent.
from fatty amide using phthalic anhydride. For syn- Allauddin et al.[185] reported the synthesis and
thesis, neem oil fatty amide and phthalic anhydride properties of modified castor oil using alkoxysilane
are dissolved in xylene in the presence of PbO as catalyst and their polyurethane/urea–silica hybrid coating films.
and then heated up to 115°C. Solvent was removed First, castor oil was converted into acid-terminated
using rotary vacuum evaporator. castor oil using SA in the presence of SnCl2 (1 wt%)
Polyesteramide of neem oil on reaction with TDI at as a catalyst. Further, it was converted into alkoxy silane
room temperature gives polyurethane (Figure 47b). castor oil (ASCO) using 3-glycidoxypropyl-trimethoxy-
The structure of polyesteramide has been confirmed silane in the presence of triethylamine as a catalyst
by 1H-NMR and FTIR. (Figure 48). After this, ASCO was reacted with IPDI
Zhang et al.[183] synthesized bio-based polyols from in the presence of 0.01 wt% of DBTL as a catalyst with
ESO and castor oil fatty acid using the solvent-free/ different NCO/OH ratios of 1.2:1, 1.4:1, and 1.6:1 at
catalyst-free method. First, the castor oil was converted around 78–80°C to give prepolymer polyurethane and
into fatty acid by heating with sodium hydroxide solution coded as ASCOPU2, ASCOPU4, and ASCOPU6.
at 80°C and purified with the help of water and then Chemical structures of all synthesized chemicals were
drying over MgSO4. Thus, clear, light yellow castor oil determined with the help of FTIR, 1H-NMR, and
13
fatty acids were obtained. After this, soy–castor oil-based C-NMR.
polyols were synthesized by opening epoxy ring on ESO From DMA study, they found that Tg values for poly-
with the help of castor oil fatty acid at 130–170°C under urethanes coded as ASCOPU2, ASCOPU4, and
dry nitrogen atmosphere. Finally, polyurethane film was ASCOPU6 were found as 29, 57.88, and 69.77°C,
obtained from the reaction of polyol with 5% molar respectively. From TGA study, it was found that onset
degradation temperature and wt% remaining at 550°C
for polymer sample ASCOPU2, ASCOPU4, and
ASCOPU6 were found to be 306.2, 309.3, and 313.9°C
and 1.3, 1.7, and 2.5 wt%, respectively. It was also found
that tensile strength (in N/mm2) for polymer sample
ASCOPU2, ASCOPU4, and ASCOPU6 were found to
be 4.2, 11.3, and 14.1, respectively. Thus, this work
can be useful to prepare hydrolysable silane plant oil
for high-performance coating.
Conclusion
It is important to note that future of living environment
strongly dependent on the fuel. These fuels can be
obtained from living environment achieving the more
green and sustainable pathway. It is important to note
that incorporation of the highly functionalized vegetable
oil or nonvegetable oil with petroleum-based thermoset-
ting resin could be helpful in physical, mechanical, and
thermal properties that were comparable or even better
than the neat petroleum-based thermosetting resin
matrix. Bio-based polymer including thermosetting
resins like epoxy, polyurethane can be synthesized using
renewable resources. So that hazardous and waste prob-
lem can be minimized keeping constant or high perfor-
mance introducing bio-based resin like bio-based epoxy
oligomer and replacing toxic substances like BPA and
ECH. Epoxy hardner such as amine hardner are
harmful and replacement of such type of hardner is
important. Bio-based isosorbide diamine can be used
Figure 48. Synthesis of alkoxy silane castor oil. as hardner. Natural phenols such as quercetin or
phenols extracted from tannin derivatives are also good [13] Pizzi, A.; Mittal, K.L. Handbook of Adhesive Technology
candidates. Again, isosorbide is well known for its non- Revised and Expanded. CRC Press: Boca Raton, FL,
toxicity. However, polyurethane for coating application 2003.
[14] Sonnenschein, M.F. Polyurethanes: Science, Technology,
can be achieved using tannin without isocyanate. Carda- Markets, and Trends, Vol. 11. John Wiley & Sons:
nol-based polymer gives bio-based aromatic building Hoboken, NJ, 2014.
block which is helpful in significant enhancement of [15] Biron, M. Thermoplastics and Thermoplastic
mechanical properties compared to natural oil-based Composites. William Andrew: Norwich, NY, 2012.
polymer. Moreover, these are accessible for chemical [16] Ronda, J.C.; Lligadas, G.; Galià, M.; Cádiz, V. A
renewable approach to thermosetting resins. React.
industry because of their bio-based aromatic
Funct. Polym. 2013, 73(2), 381–395.
characteristics. [17] Tan, S.G.; Ahmad, Z.; Chow, W.S. Interpenetrating
polymer network structured thermosets prepared from
epoxidized soybean oil/diglycidyl ether of bisphenol A.
Funding Polym. Int. 2014, 63(2), 273–279.
[18] Auvergne, R.; Caillol, S.; David, G.; Boutevin, B.;
The authors would like to thank the Department of Chemicals
Pascault, J. Biobased thermosetting epoxy: present
and Petrochemicals, Government of India for the financial
and future. Chem. Rev. 2013, 114(2), 1082–1115.
support.
[19] Floch, A.L.; Jourdes, M.; Teissedre, P. Polysaccharides
and lignin from oak wood used in cooperage: com-
References position, interest, assays: a review. Carbohydr. Res.
2015, 417, 94–102.
[1] Yoko, A.; Canning, D. Infeering the economic standard [20] Petruccioli, M.; Pulci, V.; Federici, F. Itaconic acid
of living and health from cohast height evidence from production by Aspergillus terreus on raw starchy
modern populations in developing countries. Econ. materials. Lett. Appl. Microbiol. 1999, 28(4), 309–312.
Hum. Biol. 2015, 19, 114–128. [21] Corma, A.; Iborra, S.; Velty, A. Chemical routes for the
[2] Paluvai, N.R.; Mohanty, S.; Nayak, S.K. Synthesis and transformation of biomass into chemicals. Chem. Rev.
modifications of epoxy resins and their composites: A 2007, 107(6), 2411–2502.
review. Polym. Plast. Technol. Eng. 2014, 53(16), [22] Ma, W.; Guo, A.; Zhang, Y.; Wang, H.; Liu, Y.; Li, H. A
1723–1758. review on astringency and bitterness perception of
[3] Lligadas, G.; Ronda, J.C.; Galia, M.; Cadiz, V. tannins in wine.A review on astringency and bitterness
Renewable polymeric materials from vegetable oils: a perception of tannins in wine. Trends Food Sci.
perspective. Mater. Today, 2013, 16(9), 337–343. Technol. 2014, 40(1), 6–19.
[4] Voirin, C.; Caillol, S.; Sadavarte, N.V.; Tawade, B.V.; [23] Benyahya, S.; Aouf, C.; Caillol, S.; Boutevin, B.;
Boutevin, B.; Wadgaonkar, P.P. Functionalization of Pascault, J.P.; Fulcrand, H. Functionalized green tea
cardanol: towards biobased polymers and additives. tannins as phenolic prepolymers for bio-based epoxy
Polym. Chem. 2014, 5(9), 3142–3162. resins. Ind. Crops Prod. 2014, 53, 296–307.
[5] Tschan, M.J.-L.; Brulé, E.; Haquette, P.; Thomas, C.M. [24] Fenouillot, F.; Rousseau, A.; Colomines, G.;
Synthesis of biodegradable polymers from renewable Saint-Loup, R.; Pascault, J.-P. Polymers from renewable
resources Polym. Chem. 2012, 3(4), 836–851. 1, 4: 3, 6-dianhydrohexitols (isosorbide, isomannide
[6] Jin, F.L.; Li, X.; Park, S.J. Synthesis and application of and isoidide): A review. Prog. Polym. Sci. 2010, 35
epoxy resins: A review. J. Indust. Eng. Chem. 2015, (5), 578–622.
29, 1–11. [25] Marques, D.S.; Santos, J.M.C.; Ferreira, P.; Correia, T.
[7] Hughes, J.D.H. The carbon fibre/epoxy interface—a R.; Correia, I.J.; Gil, M.H.; Baptista, C.M.S.G. Photocur-
review. Compos. Sci. Technol. 1991, 41(1), 13–45. able bioadhesive based on lactic acid. Mater. Sci. Eng. C
[8] Garg, A.C.; Mai, Y.-W. Failure mechanisms in 2016, 58, 601–609.
toughened epoxy resins—A review. Compos. Sci. [26] Ali, B.; Al-Wabel, N.A.; Shams, S.; Ahamad, A.; Khan,
Technol. 1988, 31(3), 179–223. S.A.; Anwar, F. Essential oils used in aromatherapy: A
[9] Tanaka, Y.; Kakiuchi, H.J. Study of epoxy compounds. systemic review. Asian Pac. J. Trop. Biomed. 2015, 5
Part I. curing reactions of epoxy resin and acid (8), 601–611.
anhydride with amine and alcohol as catalyst. Appl. [27] Safaei-Ghomi, J.; Ebrahimabadi, A.H.; Djafari-Bidgoli,
Polym. Sci. 1963, 7(3), 1063–1081. Z.; Batooli, H. GC/MS analysis and in vitro antioxidant
[10] Chen, T.-K.; Tien, Y.-I.; Wei, K.-H. Synthesis and activity of essential oil and methanol extracts of
characterization of novel segmented polyurethane/clay Thymus caramanicus Jalas and its main constituent
nanocomposites. Polymer 2000, 41(4), 1345–1353. carvacrol. Food Chem. 2009, 115(4), 1524–1528.
[11] Dodiuk, H.; Goodman, S.H. (Eds.) Handbook of [28] Padmini, R.; Krishna, P.V.; Krishna Mohana Rao, G.
Thermoset Plastics. William Andrew: Norwich, NY, Effectiveness of vegetable oil based nanofluids as
2013. potential cutting fluids in turning AISI 1040 steel.
[12] Gryshchuk, O.; Karger-Kocsis, J.; Thomann, R.; Kónya, Tribol. Int. 2016, 94, 490–501.
Z.; Kiricsi, I. Multiwall carbon nanotube modified [29] Sharma, V.; Kundu, P.P. Addition polymers from
vinylester and vinylester–based hybrid resins. Compos. natural oils—A review. Prog. Polym. Sci. 2006, 31
Part A Appl. Sci. Manuf. 2006, 37(9), 1252–1259. (11), 983–1008.
[30] Chattopadhyay, D.K.; Raju, K.V.S.N. Structural engin- [46] Lubi, M.C.; Thachil, E.T. Cashew nut shell liquid
eering of polyurethane coatings for high performance (CNSL)-a versatile monomer for polymer synthesis.
applications. Prog. Polym. Sci. 2007, 32(3), 352–418. Design. Monom. Polym. 2000, 3(2), 123–153.
[31] Martino, L.; Basilissi, L.; Farina, H.; Ortenzi, M.A.; Zini, [47] Phani Kumar, P.; Paramashivappa, R.; Vithayathil, P.J.;
E.; Silvestro, G.D.; Scandola, M. Bio-based polyamide Subba Rao, P.V.; Srinivasa Rao, A.J. Process for
11: Synthesis, rheology and solid-state properties of star isolation of cardanol from technical cashew
structures. Eur. Polym. J. 2014, 59, 69–77. (Anacardium occidentale L.) nut shell liquid Agric.
[32] Liu, C.; Li, J.; Lei, W.; Zhou, Y. Development of Food Chem. 2002, 50(16), 4705–4708.
biobased unsaturated polyester resin containing highly [48] Smith Jr, R.L.; Malaluan, R.M.; Setianto, W.B.;
functionalized castor oil. Ind. Crops Prod. 2014, 52, Inomata, H.; Arai, K. Separation of cashew (Anacar-
329–337. dium occidentale L.) Nut shell liquid with supercritical
[33] Lligadas, G.; Ronda, J.C.; Galiya, M.; Cadiz, V. carbon dioxide. Biores. Technol. 2003, 88(1), 1–7.
Monomers and Polymers from Plant oils via click [49] Setianto, W.B.; Yoshikawa, S.; Smith, R.L.; Inomata, H.;
chemistry reactions. J. Polym. Sci. Part A Polym. Chem. Florusse, L.J.; Peters, C.J. J. Pressure profile separation
2013, 51, 2111–2124. of phenolic liquid compounds from cashew
[34] Turunc, O.; Meier, M.A.R. The thiol-ene (Click) (Anacardium occidentale) shell with supercritical
reaction for the synthesis of Plant oil derived polymers. carbon dioxide and aspects of its phase equilibria.
Eur. J. Lipid Sci. Technol. 2013, 115, 41–45. Supercrit. Fluids 2009, 48(3), 203–210.
[35] Stemmelen, M.; Pessel, F.; Lapinte, V.; Caillol, S.; [50] Menon, A.R.R.; Pillai, C.K.S.; Nando, G.B. Thermal
Habas, J.-P.; Robin, J.-J. A fully biobased epoxy degradation characteristics of natural rubber
resin from vegetable oils: From the synthesis of the vulcanizates modified with phosphorylated cashew
precursors by thiol – ene reaction to the study of the nut shell liquid. Polym. Degrad. Stabil. 1996, 52(3),
final material. J. Polym. Sci. Part A Polym. Chem. 265–271.
2011, 49(11), 2434–2444. [51] Jaillet, F.; Nouailhas, H.; Auvergne, R.; Ratsimihety, A.;
[36] Montero de Espinosa, L.; Ronda, J.C.; Galià, M.; Cádiz, Boutevin, B.; Caillol, S. Synthesis and characterization
V.J. Quinoline – containing networks from enone and of novel vinyl ester prepolymer from cardanol. Eur. J.
aldehyde triglyceride derivatives. Polym. Sci. Part A Lipid Sci. Technol. 2014, 116(7), 928–939.
Polym. Chem. 2010, 48(4), 869–878. [52] Jaillet, F.; Darroman, E.; Ratsimihety, A.; Auvergne, R.;
[37] Ghorui, S.; Bandyopadhyay, N.R.; Ray, D.; Sengupta, S.; Boutevin, B.; Caillol, S. New biobased epoxy materials
Kar, T. Use of maleated castor oil as biomodifier in from cardanol. Eur. J. Lipid Sci. Technol. 2014, 116
unsaturated polyester resin/fly ash composites. Ind. (1), 63–73.
Crops Prod. 2011, 34(1), 893–899. [53] Devi, A.; Srivastava, D. Studies on the blends of
[38] Echeverri, D.A.; Cádiz, V.; Ronda, J.C.; Rios, L.A. cardanol-based epoxidized novolac type phenolic resin
Synthesis of elastomeric networks from maleated and carboxyl-terminated polybutadiene (CTPB), I.
soybean-oil glycerides by thiol-ene coupling. Eur. Mater. Sci. Eng. A 2007, 458(1), 336–347.
Polym. J. 2012, 48(12), 2040–2049. [54] Devi, A.; Srivastava, D. Studies on the blends of
[39] Lu, J.; Khot, S.; Wool, R.P. New sheet molding cardanol-based epoxidized novolac resin and CTPB.
compound resins from soybean oil.I. Synthesis and Eur. Polym. J. 2007, 43(6), 2422–2432.
characterization. Polymer 2005, 46(1), 71–80. [55] Kim, Y.H.; An, E.S.; Park, S.Y.; Song, B.K. J. Enzymatic
[40] Ray, D.; Ghorui, S.; Bandyopadhyay, N.R.; Sengupta, S.; epoxidation and polymerization of cardanol obtained
Kar, T. New materials from maleated castor oil/epoxy from a renewable resource and curing of epoxide-
resin blend reinforced with fly ash. Ind. Eng. Chem. containing polycardanol. Mol. Catal. B Enzym. 2007,
Res. 2012, 51(6), 2603–2608. 45(1), 39–44.
[41] Gandini, A.; Lacerda, T.M.; Carvalho, A.J.F. A [56] Sultania, M.; Rai, J.S.P.; Srivastava, D. Studies on the
straightforward double coupling of furan moieties onto synthesis and curing of epoxidized novolac vinyl ester
epoxidized triglycerides: synthesis of monomers based resin from renewable resource material. Eur. Polym.
on two renewable resources. Green Chem. 2013, 15 J. 2010, 46(10), 2019–2032.
(6), 1514–1519. [57] Sultania Garg, M.; Srivastava, K.; Srivastava, D. Physical
[42] Biswas, A.; Sharma, B.K.; Willett, J.L.; Advaryu, A.; and chemical toughening of cardanol-based vinyl ester
Erhan, S.Z.; Cheng, H.N. J. Azide derivatives of resin using CTBN ; A study on spectral, thermal
soybean oil and fatty esters. Agric. Food Chem. 2008, and morphological characteristics, progress in organic
56(14), 5611–5616. coating. Prog. Org. Coat. 2015, 78, 307–317.
[43] Biermann, U.; Friedt, W.; Lang, S.; Lühs, W.; [58] Can, E.; Kınacı, E.; Palmese, G.R. Preparation and
Machmüller, G.; Metzger, J.O.; gen Klaas, M.R.; characterization of novel vinyl ester formulations
Schaefer, H.J.; Schneider, M.P. New syntheses with oils derived from cardanol. Eur. Polym. J. 2015, 72, 129–147.
and fats as renewable raw materials for the chemical [59] Kathalewar, M.; Sabnis, A.; D’Melo, D. Polyurethane
industry. Angew. Chem. Int. Ed. 2000, 39(13), 2206–2224. coatings prepared from CNSL based polyols: Synthesis,
[44] Kim, J.S. Production, separation and applications of characterization and properties. Prog. Org. Coat. 2014,
phenolic-rich bio-oil—A review. Biores. Technol. 77(3), 616–626.
2015, 178, 90–98. [60] Bhunia, H.P.; Nando, G.B.; Chaki, T.K.; Basak, A.;
[45] Tyman, J.H.P. Synthetic and Natural Phenols, Vol. 52. Lenka, S.; Nayak, P.L. Synthesis and characterization
Elsevier: The Netherlands, 1996. of polymers from cashewnut shell liquid (CNSL), a
renewable resource II. Synthesis of polyurethanes. Eur. [76] Dai, J.; Ma, S.; Liu, X.; Han, L.; Wu, Y.; Dai, X.; Zhu, J.
Polym. J. 1999, 35(8), 1381–1391. Synthesis of bio-based unsaturated polyester resins and
[61] Fu, C.; Liu, J.; Xia, H.; Shen, L. Effect of structure on their application in waterborne UV-curable coatings.
the properties of polyurethanes based on aromatic Prog. Org. Coat. 2015, 78, 49–54.
cardanol-based polyols prepared by thiol-ene coupling. [77] Wang, Z.; Wei, T.; Xue, X.; He, M.; Xue, J.; Song, M.;
Prog. Org. Coat. 2015, 83, 19–25. Wu, S.; Kang, H.; Zhang, L.; Jia, Q. Synthesis of fully
[62] Ghosh, N.N.; Kiskan, B.; Yagci, Y. Polybenzoxazines— bio-based polyamides with tunable properties
new high performance thermosetting resins: synthesis by employing itaconic acid. Polymer 2014, 55(19),
and properties. Prog. Polym. Sci. 2007, 32(11), 4846–4856.
1344–1391. [78] Gui, C.; Wang, G.; Wu, D.; Zhu, J.; Liu, X. Synthesis of
[63] Rao, B.S.; Palanisamy, A. Synthesis of bio based a bio-based polyamidoamine-epichlorohydrin resin
low temperature curable liquid epoxy, benzoxazine and its application for soy-based adhesives. Int. J.
monomer system from cardanol: Thermal and Adhes. Adhes. 2013, 44, 237–242.
viscoelastic properties. Eur. Polym. J. 2013, 49(8), [79] Winkler, M.; Lacerda, T.M.; Mack, F.; Meier, M.A.R.
2365–2376. Renewable polymers from itaconic acid by polyconden-
[64] Sharma, P.; Shukla, S.; Lochab, B.; Kumar, D.; Roy, P.K. sation and ring-opening-metathesis polymerization.
Microencapsulated cardanol derived benzoxazines Macromolecules 2015, 48(5), 1398–1403.
for self-healing applications. Mater. Lett. 2014, 133, [80] Radebe, N.; Rode, K.; Pizzi, A.; Giovando, S.; Pasch, H.
266–268. J. MALDI – TOF – CID for the microstructure
[65] Huo, S.-P.; Wu, G.-M.; Chen, J.; Liu, G.-F.; Kong, elucidation of polymeric hydrolysable tannins. Appl.
Z.-W. Curing kinetics of lignin and cardanol based Polym. Sci. 2013, 128(1), 97–107.
novolac epoxy resin with methyl tetrahydrophthalic [81] Castañeda, D.M.; Pombo, L.M.; Urueña, C.P.;
anhydride Thermochim. Acta 2014, 587, 18–23. Hernandez, J.F.; Fiorentino, S. A gallotannin-rich
[66] Darroman, E.; Durand, N.; Boutevin, B.; Caillol, S. New fraction from Caesalpinia spinosa (Molina) Kuntze
Cardanol/sucrose epoxy blend for biobased coatings. displays cytotoxic activity and raises sensitivity to
Prog. Org. Coat. 2015, 83, 47–54. doxorubicin in a leukemia cell line. BMC Complement.
[67] Willke, T.; Vorlop, K.-D. Biotechnological production Altern. Med. 2012, 12(1), 38.
of itaconic acid. Appl. Microbiol. Biotechnol. 2001, [82] Chambi, F.; Chirinos, R.; Pedreschi, R.; Betalleluz-
56(3–4), 289–295. Pallardel, I.; Debaste, F.; Campos, D. Antioxidant
[68] Okabe, M.; Lies, D.; Kanamasa, S.; Park, E.Y. potential of hydrolyzed polyphenolic extracts from
Biotechnological production of itaconic acid and its tara (Caesalpinia spinosa) pods. Ind. Crops Prod.
biosynthesis in Aspergillus terreus. Appl. Microbiol. 2013, 47, 168–175.
Biotechnol. 2009, 84(4), 597–606. [83] Tomita, H.; Yonezawa, K. From epihalohydrin and
[69] Zhao, C.-L.; Roser, J.; Dersch, R.; Baumstark, R. gallic acid or tannic acid. U.S. Patent 4,540,802, issued
Dispersion resins containing itaconic acid for improv- September 10, 1985.
ing wet abrasion resistance. U.S. Patent 6,790,272, [84] Aouf, C.; Nouailhas, H.; Fache, M.; Caillol, S.; Boutevin,
issued September 14, 2004. B.; Fulcrand, H. Multi-functionalization of gallic acid.
[70] Westerman, I.J.; Laurich, J.B.; Flickinger, M.; Oblak, D. Synthesis of a novel bio-based epoxy resin. Eur. Polym.
Butadiene-itaconic acid-styrene copolymers; polymo- J. 2013, 49(6), 1185–1195.
dal particle size distribution; useful in paper coatings. [85] Thébault, M.; Pizzi, A.; Essawy, H.A.; Barhoum, A.;
U.S. Patent 7,629,410, issued December 8, 2009. Van Assche, G. Isocyanate free condensed
[71] Bagvant, G.; Gole, S.R.; Joshi, V.W.; Soni, S.B. Studies tannin-based polyurethanes. Eur. Polym. J. 2015, 67,
on anti-inflammatory and analgesic activities of 513–526.
itaconic acid systems. part 1: itaconoc acids and [86] Liu, G.; Wu, G.; Chen, J.; Huo, S.; Jin, C.; Kong, Z.
diesters. Ind. J. Pharm. Sci. 1994, 56(3), 80. Synthesis and properties of POSS-containing gallic
[72] Diehl, F.L. Polyelectrolyte builders and detergent acid-based non-isocyanate polyurethanes coatings.
compositions. U.S. Patent No. 3,308,067. 7 March 1967. Polym. Degrad. Stabil. 2015, 121, 247–252.
[73] Werpy, T.; Petersen, G.; Aden, A.; Bozell, J.; Holladay, [87] Kricheldorf, H.R.; Gomourachvili, Z. Polyanhydrides
J.; White, J.; Manheim, A.; Eliot, D.; Lasure, L.; Jones, S. 10. Aliphatic polyesters and poly (ester – anhydride)
Top value added chemicals from biomass. Volume s by polycondensation of silylated aliphatic diols.
1-Results of screening for potential candidates from Macromol. Chem. Phys. 1997, 198(10), 3149–3160.
sugars and synthesis gas. No. DOE/GO-102004–1992. [88] Adelman, D.J.; Charbonneau, L.F.; Ung, S. Heating
Department of Energy Washington DC, 2004. mixture of ethylene glycol and isosorbide, terephthalic
[74] Ma, S.; Liu, X.; Jiang, Y.; Tang, Z.; Zhang, C.; Zhu, J. acid or its alkyl ester under pressure; removal of
Bio-based epoxy resin from itaconic acid and its distillate comprising water or volatile alkanol products;
thermosets cured with anhydride and comonomers. continuing reaction in presence of polycondensation
Green Chem. 2013, 15(1), 245–254. catalyst. U.S. Patent No. 6,656,577. 2 December 2003.
[75] Dai, J.; Ma, S.; Wu, Y.; Han, L.; Zhang, L.; Zhu, J.; Liu, [89] Luzzi, L.A.; Ma, J.K.H. Dimethyl isosorbide in liquid
X. Polyesters derived from itaconic acid for the formulation of aspirin. U.S. Patent No. 4,228,162. 14
properties and bio-based content enhancement of October 1980.
soybean oil-based thermosets. Green Chem. 2015, [90] Marten, W.; Weiss, M.; Haase, W. Treatment of
17(4), 2383–2392. coronary heart disease with isosorbide mononitrate
(‘Elantan’20): a multi-centre study in hospital and [107] Feng, X.; East, A.J.; Hammond, W.; Jaffe, M.
general practice. Curr. Med. Res. Opin. 1984, 9(2), Sugar-based chemicals for environmentally sustainable
96–106. applications. Contemp. Sci. Polym. Mater. 2010, 3–27.
[91] Bidoggia, H. Isosorbide-5-mononitrate and isosorbide [108] Besse, V.; Auvergne, R.; Carlotti, S.; Boutevin, G.;
dinitrate retard in the treatment of coronary heart Otazaghine, B.; Caillol, S.; Pascault, J.-P.; Boutevin, B.
disease: A multi-centre study. Curr. Med. Res. Opin. Synthesis of isosorbide based polyurethanes: An
1987, 10(9), 601–611. isocyanate free method. React. Funct. Polym. 2013,
[92] Stoss, P.; Hemmer, R. 1, 4: 3, 6-Dianhydrohexitols. 73(3), 588–594.
Adv. Carbohydr. Chem. Biochem. 1991, 49, 93–173. [109] Lee, C.H.; Hirotaka Okamoto, T.H.; Kato, M.; Usuki, A.
[93] Feldmann, J.; Koebernick, H.; Richter, K.; Woelk, H. J. Synthesis, characterization, and properties of polyur-
Process for recovering pure crystalline monoanhydro- ethanes containing 1, 4: 3, 6 – dianhydro – D – sorbitol
hexitols and dianhydrohexitols. U.S. Patent 4,564,692, Polym. Sci. Part A Polym. Chem. 2009, 47(22),
issued January 14, 1986. 6025–6031.
[94] Hartmann, L.A. Purification of isosorbide. U.S. Patent [110] Marín, R.; Alla, A.; de Ilarduya, A.M.; Guerra, S.M. J.
3,160,641, issued December 8, 1964. Carbohydrate – based polyurethanes: A comparative
[95] Fletcher Jr, H.G.; Max Goepp Jr, R.J. Hexitol study of polymers made from isosorbide and 1, 4 –
anhydrides. 1 1, 4, 3, 6-dianhydro-L-iditol and the butanediol. Appl. Polym. Sci. 2012, 123(2), 986–994.
structures of isomannide and isosorbide. Am. Chem. [111] Li, Y.; Noordover, B.A.J.; van Benthem, R.A.T.M.;
Soc. 1946, 68(6), 939–941. Koning, C.E. Chain extension of dimer fatty acid-and
[96] Łukaszczyk, J.; Janicki, B.; Kaczmarek, M. Synthesis sugar-based polyurethanes in aqueous dispersions.
and properties of isosorbide based epoxy resin. Eur. Eur. Polym. J. 2014, 52, 12–22.
Polym. J. 2011, 47(8), 1601–1606. [112] Öztürk, C.; Küsefoğlu, S.H. J. New polymers from
[97] Thiem, J.; Lüders, H. Synthesis and properties of plant oil derivatives and styrene – maleic anhydride
polyurethanes derived from diaminodianhydroalditols. copolymers. Appl. Polym. Sci. 2010, 116(1), 355–365.
Die Makromol. Chem. 1986, 187(12), 2775–2785. [113] Gupta, A.P.; Ahmad, S.; Dev, A. Development of novel
[98] Varkey, E.C.; Sreekumar, K.J. Isosorbide based chiral bio-based soybean oil epoxy resins as a function of
polyurethanes: optical and thermal studies. Mater. Sci. hardener stoichiometry. Polym. Plast. Technol. Eng.
2010, 45(7), 1912–1920. 2010, 49(7), 657–661.
[99] Gogolewski, S.; Gorna, K.; Zaczynska, E.; Czarny, A.J. [114] Espana, J.M.; Sánchez-Nacher, L.; Boronat, T.;
Structure—property relations and cytotoxicity of Fombuena, V.; Balart, R.J. Properties of biobased epoxy
isosorbide – based biodegradable polyurethane resins from epoxidized soybean oil (ESBO) cured with
scaffolds for tissue repair and regeneration. Biomed. maleic anhydride (MA). Am. Oil Chem. Soc. 2012, 89
Mater. Res. Part A 2008, 85(2), 456–465. (11), 2067–2075.
[100] Braun, D.; Bergmann, M. 1, 4: 3, 6 – Dianhydrohexite [115] Sarwono, A.; Man, Z.; Azmi Bustam, M.J. Blending of
als Bausteine für Polymere. J. für Praktische Chem./ epoxidised palm oil with epoxy resin: The effect on
Chemiker-Zeitung 1992, 334(4), 298–310. morphology, thermal and mechanical properties.
[101] Betiku, O.; Jenni, M.; Ludescher, K.; Meierdierks, E.; Polym. Environ. 2012, 20(2), 540–549.
Lunt, J.; Schroeder, J. Synthesis and characterization [116] Tan, S.; Chow, W.J. Thermal properties of anhydride-
of isosorbide carbonate: lactide copolymers. Polym. cured bio-based epoxy blends. Therm. Anal. Calorim.
Preprints (American Chemical Society, Division of 2010, 101(3), 1051–1058.
Polymer Chemistry) 2007, 48(2), 802–803. [117] Pfister, D.P.; Larock, R.C. Green composites from a
[102] Rapi, Z.; Szolnoki, B.; Bakó, P.; Niedermann, P.; Toldy, conjugated linseed oil-based resin and wheat
A.; Bodzay, B.; Keglevich, G.; Marosi, G. Synthesis and straw. Compos. Part A Appl. Sci. Manuf. 2010, 41(9),
characterization of biobased epoxy monomers derived 1279–1288.
from d-glucose. Eur. Polym. J. 2015, 67, 375–382. [118] Miyagawa, H.; Mohanty, A.K.; Misra, M.; Drzal, L.T.
[103] Feng, X.; East, A.J.; Hammond, W.B.; Zhang, Y.; Jaffe, Thermo – Physical and Impact Properties of Epoxy
M. Overview of advances in sugar – based polymers. Containing Epoxidized Linseed Oil, 1. Macromol.
Polym. Adv. Technol. 2011, 22(1), 139–150. Mater. Eng. 2004, 289(7), 629–635.
[104] Chrysanthos, M.; Galy, J.; Pascault, J. Preparation and [119] Wuzella, G.; Mahendran, A.R.; Müller, U.;
properties of bio-based epoxy networks derived from Kandelbauer, A.; Teischinger, A.J. Photocrosslinking
isosorbide diglycidyl ether. Polymer 2011, 52 (16), of an acrylated epoxidized linseed oil: kinetics and its
3611–3620. application for optimized wood coatings. Polym.
[105] Cognet-Georjon, E.; Méchin, F.; Pascault, J.-P. New Environ. 2012, 20(4), 1063–1074.
polyurethanes based on diphenylmethane diisocyanate [120] Riaz, U.; Ashraf, S.M.; Sharma, H.O. Mechanical,
and 1, 4: 3, 6 – dianhydrosorbitol, 1. Model kinetic morphological and biodegradation studies of
studies and characterization of the hard segment. microwave processed nanostructured blends of some
Macromol. Chem. Phys. 1995, 196(11), 3733–3751. bio-based oil epoxies with poly (vinyl alcohol). Polym.
[106] Beldi, M.; Medimagh, R.; Chatti, S.; Marque, S.; Prim, Degrad. Stabil. 2011, 96(1), 33–42.
D.; Loupy, A.; Delolme, F. Characterization of cyclic [121] Fridrihsone, A.; Stirna, U.; Lazdiņa, B.; Misāne, M.;
and non-cyclic poly-(ether-urethane) s bio-based sugar Vilsone, D. Characterization of polyurethane networks
diols by a combination of MALDI-TOF and NMR. Eur. structure and properties based on rapeseed oil derived
Polym. J. 2007, 43(8), 3415–3433. polyol Eur. Polym. J. 2013, 49(6), 1204–1214.
[122] Kreye, O.; Tóth, T.; Meier, M.A.R. Copolymers derived [138] Francucci, G.; Cardona, F.; Manthey, N.W. J. Cure
from rapeseed derivatives via ADMET and thiol-ene kinetics of an acrylated epoxidized hemp oil – based
addition. Eur. Polym. J. 2011, 47(9), 1804–1816. bioresin system. Appl. Polym. Sci. 2013, 128(3),
[123] Matthäus, B. Effect of dehulling on the composition 2030–2037.
of antinutritive compounds in various cultivars of [139] de Espinosa, L.M.; Ronda, J.C.; Galià, M.; Cádiz, V.J. A
rapeseed Lipid/Fett 1998, 100(7), 295–301. new route to acrylate oils: Crosslinking and properties
[124] Snežana, S.; Janković, M.; Borota, O. Epoxidation of acrylate triglycerides from high oleic sunflower
of castor oil with peracetic acid formed in situ in the oil. Polym. Sci. Part A Polym. Chem. 2009, 47(4),
presence of an ion exchange resin. Chem. Eng. Process. 1159–1167.
Process Intensif. 2012, 62, 106–113. [140] Khalil, H.P.S.A.; Aprilia, N.A.S.; Bhat, A.H.; Jawaid, M.;
[125] Van der Steen, M.; Bretz, I.; Kabasci, S.; Stevens, C.V. Paridah, M.T.; Rudi, D. A Jatropha biomass as renew-
Synthesis of biobased multivalent cross-linkers from a able materials for biocomposites and its applications.
castor oil-derived C22-acyloin. Ind. Crops Prod. Renew. Sustain. Energy Rev. 2013, 22, 667–685.
2013, 46, 238–245. [141] Chaudhari, A.; Gite, V.; Rajput, S.; Mahulikar, P.;
[126] de Souza, V.H.R.; Silva, S.A.; Ramos, L.P.; Zawadzki, S. Kulkarni, R. Development of eco-friendly polyurethane
F. J. Synthesis and characterization of polyols derived coatings based on neem oil polyetheramide. Ind. Crops
from corn oil by epoxidation and ozonolysis. Am. Oil Prod. 2013, 50, 550–556.
Chem. Soc. 2012, 89(9), 1723–1731. [142] Chaudhari, A.; Pyus, B.; Tatiya, D.; Hedaoo, R.K.;
[127] Madankar, C.S.; Dalai, A.K.; Naik, S.N. Green synthesis Kulkarni, R.D.; Gite, V.V. Polyurethane prepared
of biolubricant base stock from canola oil. Ind. Crops from neem oil polyesteramides for self-healing
Prod. 2013, 44, 139–144. anticorrosive coatings. Ind. Eng. Chem. Res. 2013, 52
[128] Espinoza-Perez, J.D.; Nerenz, B.A.; Haagenson, D.M.; (30), 10189–10197.
Chen, Z.; Ulven, C.A.; Wiesenborn, D.P. Comparison [143] Nagendramma, P.; Kaul, S. Development of
of curing agents for epoxidized vegetable oils ecofriendly/biodegradable lubricants: An overview.
applied to composites. Polym. Compos. 2011, 32(11), Renew. Sustain. Energy Rev. 2012, 16(1), 764–774.
1806–1816. [144] Shashidhara, Y.M.; Jayaram, S.R. Vegetable oils as a
[129] Omonov, T.S.; Curtis, J.M. Biobased epoxy resin from potential cutting fluid—an evolution. Tribol. Int.
canola oil. J. Appl. Polym. Sci. 2014, 131(8), 40142. 2010, 43(5), 1073–1081.
doi:10.1002/APP.40142. [145] de Luca, M.A.; Martinelli, M.; Jacobi, M.M.; Becker,
[130] Dinda, S.; Patwardhan, A.V.; Goud, V.V.; Pradhan, N. P.L.; Ferrão, M.F. J. Ceramer coatings from castor oil
C. Epoxidation of cottonseed oil by aqueous hydrogen or epoxidized castor oil and tetraethoxysilane. Am.
peroxide catalysed by liquid inorganic acids. Biores. Oil Chem. Soc. 2006, 83(2), 147–151.
Technol. 2008, 99(9), 3737–3744. [146] Bechi, D.M.; de Luca, M.A.; Martinelli, M.; Mitidieri, S.
[131] Rahman, M.M.; Netravali, A.N. Green resin from Organic–inorganic coatings based on epoxidized castor
forestry waste residue “Karanja (Pongamia pinnata) oil with APTES/TIP and TEOS/TIP. Prog. Org. Coat.
seed cake” for biobased composite structures. ACS 2013, 76(4), 736–742.
Sustain. Chem. Eng. 2014, 2(10), 2318–2328. [147] İşeri-Çağlar, D.; Baştürk, E.; Oktay, B.; Vezir Kahraman,
[132] Shibata, M.; Teramoto, N.; Nakamura, Y.J. High M. Preparation and evaluation of linseed oil based alkyd
performance bio – based thermosetting resins paints. Prog. Org. Coat. 2014, 77(1), 81–86.
composed of tung oil and bismaleimide. Appl. Polym. [148] Misra, R.D.; Murthy, M.S. Straight vegetable oils usage
Sci. 2011, 119(2), 896–901. in a compression ignition engine—A review. Renew.
[133] Hondred, P.R.; Salat, L.; Mangler, J.; Kessler, M.R. Sustain. Energy Rev. 2010, 14(9), 3005–3013.
Tung oil – based thermosetting polymers for self – [149] Motasemi, F.; Ani, F.N. A review on microwave-
healing applications. J. Appl. Polym. Sci. 2014, 131 assisted production of biodiesel. Renew. Sustain.
(12), 40406. doi:10.1002/APP.40406. Energy Rev. 2012, 16(7), 4719–4733.
[134] Hondred, P.R.; Kessler, M.R. Rare Earth triflate initia- [150] Demirbas, A. Biodiesel for future transportation energy
tors in the cationic polymerization of tung oil – based needs.Energy Sources, Part A Recov. Util. Environ.
thermosetting polymers for self – healing applications. Effects 2010, 32(16), 1490–1508.
Macromol. Mater. Eng. 2014, 299(9), 1062–1069. [151] Parawira, W. Biotechnological production of biodiesel
[135] Liu, C.; Dai, Y.; Wang, C.; Xie, H.; Zhou, Y.; Lin, X.; fuel using biocatalysed transesterification: a review.
Zhang, L. Phase-separation dominating mechanical Crit. Rev. Biotechnol. 2009, 29(2), 82–93.
properties of a novel tung-oil-based thermosetting [152] Xu, Q.; Liu, Z.; Nakajima, M.; Ichikawa, S.; Nakamura,
polymer. Ind. Crops Prod. 2013, 43, 677–683. N.; Roy, P.; Okadome, H.; Shiina, T. Characterization
[136] Kulkarni, R.D.; Deshpande, P.S.; Mahajan, S.U.; of a soybean oil-based biosurfactant and evaluation of
Mahulikar, P.P. Epoxidation of mustard oil and ring its ability to form microbubbles. Biores. Technol.
opening with 2-ethylhexanol for biolubricants with 2010, 101(10), 3711–3717.
enhanced thermo-oxidative and cold flow characteris- [153] Pfister, D.P.; Larock, R.C. Thermophysical properties of
tics. Ind. Crops Prod. 2013, 49, 586–592. conjugated soybean oil/corn stover biocomposites.
[137] Manthey, N.W.; Cardona, F.; Francucci, G.; Biores. Technol. 2010, 101(15), 6200–6206.
Aravinthan, T. Thermo-mechanical properties of [154] Bezwada, R.S.; Hunter, A.W.; McGregor, W.;
acrylated epoxidized hemp oil based biocomposites. J. Shchervinsky, S. Castor oil polymers. U.S. Patent
Compos. Mater. 2014, 48(13), 1611–1622. 5,371,176, issued December 6, 1994.
[155] Patil, H.; Waghmare, J. Catalyst for epoxidation of oils: [170] Ratna, D. Mechanical properties and morphology of
a review. Discovery. 2013, 3(7), 10–14. epoxidized soyabean – oil – modified epoxy resin.
[156] Tan, S.G.; Chow, W.S. Biobased epoxidized vegetable Polym. Int. 2001, 50(2), 179–184.
oils and its greener epoxy blends: A review. Polym. [171] Pan, X.; Sengupta, P.; Webster, D.C. Novel biobased
Plast. Technol. Eng. 2010, 49(15), 1581–1590. epoxy compounds: epoxidized sucrose esters of fatty
[157] De, B.; Gupta, K.; Mandal, M.; Karak, N. Biodegradable acids. Green Chem. 2011, 13(4), 965–975.
hyperbranched epoxy from castor oil-based hyper- [172] Pan, X.; Sengupta, P.; Webster, D.C. High biobased
branched polyester polyol. ACS Sustain. Chem. Eng. content epoxy–anhydride thermosets from epoxidized
2013, 2(3), 445–453. sucrose esters of fatty acids. Biomacromolecules 2011,
[158] Eren, T.; Çolak, S.; Küsefoglu, S.H. J. Simultaneous 12(6), 2416–2428.
interpenetrating polymer networks based on bromoa- [173] Chen, J.; Soucek, M.D.; Simonsick, W.J.; Celikay, R.W.
crylated castor oil polyurethane. Appl. Polym. Sci. Synthesis and photopolymerization of norbornyl epox-
2006, 100(4), 2947–2955. idized linseed oil. Polymer 2002, 43(20), 5379–5389.
[159] Javni, I.; Petrović, Z.S.; Guo, A.; Fuller, R.J. Thermal [174] Lligadas, G.; Ronda, J.C.; Galià, M.; Cádiz, V.
stability of polyurethanes based on vegetable oils. Appl. Bionanocomposites from renewable resources: epoxi-
Polym. Sci. 2000, 77(8), 1723–1734. dized linseed oil-polyhedral oligomeric silsesquioxanes
[160] de Espinosa, L.M.; Ronda, J.C.; Galià, M.; Cádiz, V.; hybrid materials. Biomacromolecules 2006, 7(12),
Meier, M.A.R.J. Fatty acid derived phosphorus – 3521–3526.
containing polyesters via acyclic diene metathesis [175] Liu, Z.; Erhan, S.Z. “Green” composites and nano-
polymerization Polym. Sci. Part A Polym. Chem. composites from soybean oil. Mater. Sci. Eng. A
2009, 47(21), 5760–5771. 2008, 483, 708–711.
[161] de Espinosa, L.M.; Meier, M.A.R.; Ronda, J.C.; Galià, [176] Miyagawa, H.; Misra, M.; Drzal, L.T.; Mohanty, A.K.
M.; Cádiz, V.J. Phosphorus – containing renewable Novel biobased nanocomposites from functionalized
polyester – polyols via ADMET polymerization: vegetable oil and organically-modified layered silicate
Synthesis, Functionalization, and radical crosslinking. clay. Polymer 2005, 46(2), 445–453.
Polym. Sci. Part A Polym. Chem. 2010, 48(7), [177] Haq, M.; Burgueño, R.; Mohanty, A.K.; Misra, M. Bio-
1649–1660. based polymer nanocomposites from UPE/EML blends
[162] Baldy, H.M.; Faler, D.L.; Rardon, D.E.; Terrago, G.M. and nanoclay: Development, experimental characteri-
Low temperature cure waterborne coating com- zation and limits to synergistic performance. Compos.
positions having improved appearance and humidity Part A Appl. Sci. Manuf. 2011, 42(1), 41–49.
resistance and methods for coating substrates.U.S. [178] Chen, S.; Wang, Q.; Wang, T. Damping, thermal, and
Patent 6,281,272, issued August 28, 2001. mechanical properties of montmorillonite modified
[163] Mutlu, H.; Meier, M.A.R. Unsaturated PA X, 20 castor oil-based polyurethane/epoxy graft IPN compo-
from renewable resources via metathesis and catalytic sites. Mater. Chem. Phys. 2011, 130(1), 680–684.
amidation. Macromol. Chem. Phys. 2009, 210(12), [179] Chen, S.; Wang, Q.; Wang, T.; Pei, X. Preparation,
1019–1025. damping and thermal properties of potassium titanate
[164] Adekunle, K.; Åkesson, D.; Skrifvars, M.J. Synthesis of whiskers filled castor oil-based polyurethane/epoxy
reactive soybean oils for use as a biobased thermoset interpenetrating polymer network composites. Mater.
resins in structural natural fiber composites. Appl. Des. 2011, 32(2), 803–807.
Polym. Sci. 2010, 115(6), 3137–3145. [180] Chen, J.L.; Jin, F.L.; Park, S.J. Thermal stability and
[165] Ma, Q.; Liu, X.; Zhang, R.; Zhu, J.; Jiang, Y. Synthesis impact and flexural properties of epoxy resins/
and properties of full bio-based thermosetting resins epoxidized castor oil/nano-CaCO3 ternary systems.
from rosin acid and soybean oil: the role of rosin acid Macromol. Res. 2010, 18(9), 862–867.
derivatives. Green Chem. 2013, 15(5), 1300–1310. [181] Pfister, D.P.; Xia, Y.; Larock, R.C. Recent advances in
[166] de Espinosa, L.M.; Ronda, J.C.; Galià, M.; Cádiz, V.J. A vegetable oil – based polyurethanes. ChemSusChem
new enone – containing triglyceride derivative as 2011, 4(6), 703–717.
precursor of thermosets from renewable resources. [182] Chaudhari, A.B.; Tatiya, P.D.; Hedaoo, R.K.; Kulkarni,
Polym. Sci. Part A Polym. Chem. 2008, 46(20), R.D.; Gite, V.V. Polyurethane prepared from neem oil
6843–6850. polyesteramides for self-healing anticorrosive coatings.
[167] Wang, R.; Schuman, T.P. Vegetable oil-derived epoxy Ind. Eng. Chem. Res. 2013, 52(30), 10189–10197.
monomers and polymer blends: a comparative study [183] Zhang, C.; Madbouly, S.A.; Kessler, M.R. Biobased
with review. Express Polym. Lett. 2013, 7(3), 272–292. polyurethanes prepared from different vegetable oils.
[168] Gerbase, A.E.; Petzhold, C.L.; Costa, A.P.O.J. Dynamic ACS Appl. Mater. Interf. 2015, 7(2), 1226–1233.
mechanical and thermal behavior of epoxy resins based [184] Petrović, Z.S. Polyurethane from vegetable oils. Polym.
on soybean oil. Am. Oil Chem. Soc. 2002, 79(8), 797–802. Rev. 2008, 48(1), 109–155.
[169] Park, S.-J.; Jin, F.-L.; Lee, J.-R. Effect of biodegradable [185] Allauddin, S.; Narayan, R.; Raju, K.V. Synthesis and
epoxidized castor oil on physicochemical and mechan- properties of alkoxysilane castor oil and their poly-
ical properties of epoxy resins. Macromol. Chem. Phys. urethane/urea–silica hybrid coating films. ACS Sustain.
2004, 205(15), 2048–2054. Chem. Eng. 2013, 1(8), 910–918.

Bio Based Thermosetting Resins For Futur

Uploaded by

Copyright:

Available Formats

You might also like

Bio Based Thermosetting Resins For Futur

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Bio Based Thermosetting Resins For Futur

Uploaded by

Copyright:

Available Formats

POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING

2016, VOL. 55, NO. 17, 1863–1896

Bio-Based Thermosetting Resins for Future Generation: A Review

Introduction bio-based thermosetting resin has many advantages such

usage for the manufacture of infant bottle or printing

Cardanol-based epoxy polymers

on glass slide. Order of pencil scratch hardness follows

Bio-based vinyl ester polymer from cardanol

characteristics[59]. It is to be noted that the nature of

cardanol-based polyurethane showed good thermal

Figure 11. Cardanol-based epoxide and benzoxazine.

Bio-based epoxy from itaconic acid

Bio-based unsaturated polyester resin synthesis

Table 1. Different properties of blend of epoxy cardanol/epoxy sorbitol in different ratios.

Table 2. Different properties of blend of epoxy cardanol/epoxy isosorbide100 in different ratios.

Figure 15. Synthesis of bio-based amide using itaconic acid,

for different diols i.e., 1,4-butanediol, HDO. After this,

Bio-based polyamides and polyamidoamine-

70°C which indicates better mechanical properties at

Figure 21. Structure of isosorbide.

starch is depicted in Figure 22. Sugar derivatives like

Bio-based epoxy from sugar

Bio-based polyurethane from sugar (isosorbide)

In recent years, the vegetable oil has been used

Table 3. Iodine value for different types of natural oils.

Figure 29. Structure of triglyceride of oil.

Thiol-ene reaction for triglyceride. Shortly, thiol-ene

method for the introduction of amine group into

Acrylation. Acrylate triglyceride are low viscous, highly

found to be 398.3, 396.9, 397, 398.5, 398.9, 404.1, and

Aldehyde (ketone)- and enone-containing triglyceride.

explains the improvement of the thermal and mechanical

Maleinized triglyceride. Maleated castor oil (MACO)

Azide-containing triglyceride. Biswas et al.[42] studied

Figure 35. Furan-containing triglyceride. Figure 36. Grubbs catalyst.

Figure 37. Different modified triglyceride.

product was determined with the help of 1H-NMR and

Modification based on COOR (ester group)

Haq et al.[177] studied the bio-based UPE composite

Epoxidation/oxirane ring opening. Vegetable oils are

Figure 43. Synthesis of various types of polyols from natural oil.

Lactic acid, also a renewable resource, gives the ring

Transesterification/amidation. Another same routes to

Ozonolysis/reduction. Ozonolysis is the method in

N-bromosuccinimide is followed by reaction with

You might also like