Progress in Polymer Science 33 (2008) 1199–1215

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Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci

Condensation polymers from natural oils

Vinay Sharma, P.P. Kundu ∗
Department of Chemical Technology, Sant Longowal Institute of Engineering and Technology, Sangrur, Punjab 148106, India

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

Article history: Innovative technologies and competitive industrial products are reducing the dependence
Received 23 August 2007 on petrochemicals for the production of polymers. Increasing concerns about the deteri-
Received in revised form 1 June 2008
orating environment caused by conventional polymers have directed worldwide research
Accepted 1 July 2008
toward renewable resources. Vegetable oils are one of the most readily available alterna-
Available online 23 August 2008
tive renewable resources. The functional groups present in natural oils can be activated
for condensation polymerization. Accordingly, various types of useful condensation poly-
Keywords:
Soybean oil mers, such as polyurethanes, polyesters and polyethers, are being produced by this route.
Castor oil The incorporation of natural oils into the polymer chain allows tailoring the properties of
Nahar seed oil polyurethane products, for their widespread applications.
Polyols © 2008 Published by Elsevier Ltd.
Condensation polymers
Polyurethanes
Polyesters

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1199
1.1. Polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1200
1.2. Polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1200
2. Polymers based on soybean oil polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1200
3. Polymers and IPNs based on castor oil polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1205
3.1. Polymers based on castor oil polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1205
3.2. Interpenetrating and semi-interpenetrating networks based on castor oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1209
4. Polymers based on nahar seed oil polyol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1212
5. Other polymers based on oil polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1213
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1214
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1214

1. Introduction (i.e., polyester or polyether polyol) and a chain extender

(usually a low molecular weight diol or diamine). Cur-
Since the synthesis of polyurethanes by Bayer in rently, the majority of polyols (polyether and polyester
1937 [1], their utilization has become ubiquitous. These polyols) is derived from petrochemicals, a resource sub-
polymers are synthesized by reacting three basic compo- ject to depletion. Hence, bio-based materials are receiving
nents: polyisocyanate, polyhydroxyl containing polymer wide attention as the oil crisis and threat of global warming
deepen. The synthesis of bio-based materials from natural
oils affords an alternative route [2–4] to natural oil-based
∗ Corresponding author. addition polymers, which we discussed in an earlier review
E-mail address: ppk23@yahoo.com (P.P. Kundu). [5].

0079-6700/$ – see front matter © 2008 Published by Elsevier Ltd.

doi:10.1016/j.progpolymsci.2008.07.004
1200 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215
Vegetable oils are becoming extremely important as
renewable resources for the preparation of polyols required
for the polyurethane industry. Polyols from natural oils,
such as soybean, castor, and palm oils are increasingly being
viewed by industry as a viable alternative to hydrocarbon-
based feedstocks. These oils are annually renewable, and
are cost-competitive as well as environment friendly.
According to a market summary published by the United
Soybean Board in February 2000, vegetable oil-based
polyurethanes are best suited to three markets namely:
polyurethane foams, polyurethane binders and agricultural
films (the last may not be polyurethanes). Currently, the
total U.S. annual market size is approximately 3000 million
pounds for polyurethane foams and 400 million pounds
for polyurethane binders and fillers. The introduction of
natural oils as polyols into the polyurethane supply chain
can provide an opportunity for polyurethane suppliers and
customers to reduce their dependence on natural gas and
crude oil, whose highly volatile and increasing costs con-
tinue to make it difficult for them to compete.
Vegetable oils are excellent renewable source of raw
materials for the manufacture of polyurethane components
such as polyols. The transformations of the double bonds
of triglycerides of oils to hydroxyls and their application in
polyurethanes have been the subject of many studies [6].
The main technological advantages of these polyurethanes
from vegetable oils are high strength as well as stiffness,
environmental resistance and long life.
1.1. Polyols
Oil-based polyols are often oligomers with a wide dis-
tribution of molecular weights and a considerable degree
of branching, which affect the viscosity and processing
properties of polyurethane foams produced from them.
Precise characterization of the polyol composition and its
properties are very important for understanding synthetic
processes as well as for quality control. Polyols are a compo-
nent in the production of polyurethanes used in appliances,
automotive parts, adhesives, building insulation, furniture,
bedding, footwear and packaging. Although, polyols are
currently produced from petroleum, vegetable oils are also
used extensively for their production. The vegetable oil
molecules must be chemically transformed in order to
obtain hydroxyl moieties. For example, soybean oil does
not contain hydroxyl groups, but it has an average of 4.6
double bonds per molecule. The unsaturated portion of the
oil can be converted to hydroxyl groups.
1.2. Polyurethanes
Polyurethanes (PU) are polymers containing urethane
linkages (–NHCOO–) in the main polymer chain. They can
be classified in the following major groups: (a) flexible
foams, (b) rigid foams, (c) elastomers, (d) fibers, (e) molding
compositions, (f) surface coatings and (g) adhesives.
Depending upon the degree of cross-linking,
polyurethane foams may be flexible or rigid. Polyester
polyols used in the foams are based on industrial waste
streams of polyester and depolymerized PET from scrap
bottles. Flexible foam is based on a flexible aliphatic
polyester polyol (such as adipic polyester resin) and rigid
foam is prepared from aromatic polyester polyol, e.g.
depolymerized PET.
The biggest challenge for the production of PU using
polyols from natural oils is the variation of the unsatura-
tion content among natural oils. If the double bond content
in natural oils is not properly controlled, the nature of the
polyol will be changed, affecting the performance of the
final polyurethane product. Polyurethane foam finds appli-
cation as one of the most effective insulating materials.
Blowing agents are generally used to create a fine cellu-
lar foam structure. Upon dissociation the blowing agent
generates gases, which are trapped within the small cells
(or closed cell) of the foam. This enhances the insulating
properties of the PU foam.
2. Polymers based on soybean oil polyols
Petrovic and co-workers [7] studied polyurethane
foams-based on soybean oil. They prepared both
hydrochlorofluorocarbon (HCFC) and pentane blown
rigid polyurethane (PU) foams from polyols derived from
soybean oil. The effect of process variables on foam prop-
erties was studied by varying the amounts and types of
catalyst, crosslinker, blowing agent, surfactant and water.
The foams prepared from these polyols were found to have
mechanical and insulating properties such as compressive
strength and thermal strength comparable to those of
commercially available polypropylene oxide (PPO)-based
foams. The commercial PU foams derived from PPO-based
triols have the disadvantages of thermal degradation
and thermal oxidation. It was observed that the soybean
polyol derived PU foams were more stable. Comparative
thermo-gravimetric analysis (TGA) of PU foams-based on
PPO triols and soybean polyols in air and in nitrogen N2 is
shown in Fig. 1. In air (Fig. 1b), both the PU samples from
PPO and soy polyol show higher weight loss, compared
with the thermo-gravimetric loss in nitrogen (Fig. 1a).
The weight loss of up to 5% is important as PUs are never
used beyond this weight loss level because of substantial
deterioration in mechanical and other properties. The PUs
from soy polyol were observed to be more stable than
those from PPO-based polyol at around 200 ◦ C, where the
weight loss was less than 5%.
Petrovic and co-workers [8] studied the thermal sta-
bilities of PU-based on various vegetable oils. They used
TGA and Fourier-transform infra-red (FTIR) spectroscopy
for thermal analysis of the polymers. In TGA, PPO-based
PU showed single-stage degradation, while the vegetable
oil-based PUs degraded in two stages. The isothermal (at
250 ◦ C) thermo-gravimetric loss of PPO-PU, SOY-PU and
castor-PU versus time is shown in Fig. 2. The PU from PPO
(arcol, as shown in Fig. 2) was more stable at 250 ◦ C than
the PUs from soy and castor polyol. The degradation pat-
tern with temperature of these three PUs derived from PPO,
castor and soybean oils are shown in Fig. 3. This figure
shows four derivative peaks for oil-based and two peaks
for PPO-based PUs. The temperature for initial degradation
up to 10% by weight was almost the same for all PUs. The
residue at 500 ◦ C appeared to correlate with the amount of
isocyanate in the polymer, except for PPO-based PU. From
 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215
Fig. 1. Thermal behavior of soybean oil polyol based foam versus PPO-based foam: (a) TGA in N2 . (b) TGA in air. Reproduced from Guo et al. [7] with
permission of John Wiley and Sons, Inc.
Fig. 2. Isothermal TGA curve at 250 ◦ C of three polyurethanes in nitrogen.
Reproduced from Javni et al. [8] with permission of John Wiley and Sons,
Inc.
Fig. 3. Derivative TGA curves of PPO-based PU, castor-based PU and
soybean-based PU in air. Reproduced from Javni et al. [8] with permission
of John Wiley and Sons, Inc.
1201
Fig. 3, the PPO-based PU showed the fastest rate of weight
loss and the smallest residue at 300 ◦ C. On the other hand,
at the same temperature the oil-based PUs were thermally
more stable than PPO-based PU. From these studies, Petro-
vic et al. proposed three mechanisms of decomposition of
urethane bonds, as shown in Scheme 1. All three reactions
may proceed simultaneously.
The Petrovic group [9] also studied the structure and
properties of PUs prepared from halogenated as well as
non-halogenated soybean polyols. They determined the
structure and properties of these polymers by spectro-
scopic, chemical and physical methods. In this study, they
modified epoxidized soybean oil (ESBO) with hydrochloric
acid, hydrobromic acid, methanol and hydrogen. The effects
of these modifications on PUs were studied by infra-red
(IR) spectroscopy, nuclear magnetic resonance (NMR), gel
permeation chromatography (GPC) and rheological meth-
ods. The properties of polyols obtained from ESBO are
given in Table 1. From these polyols, four types of polyol
polyurethanes were prepared [10]. The properties of these
polyurethanes followed the same pattern as those of the
polyols. For example, the brominated PU had higher den-
sity, followed by chlorinated, then by methoxylated and,
finally, hydrogenated PUs. For the preparation of PUs, two
types of isocyanates PAPI-2143L (a crude MDI) and Isonate
2143L (a liquid MDI prepolymer containing carbodiimide
Scheme 1. Mechanisms of decomposition of urethane bonds. Reproduced
from Javni et al. [8] with permission of John Wiley and Sons, Inc.
1202 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215

Table 1
Properties of polyols derived from epoxidized soybean oila

Polyol Reagent Yield (%) Hydroxyl no. Equivalent weight Functionality Polyol, Mn Physical state at
(mg KOH/g) (g/equivalent) room temperature

Soy-H2 H2 89 212 265 3.5 938 Grease

Soy-Met CH3 OH 93 199 282 3.7 1053 Liquid
Soy-HClb HCl 94 197 285 3.8 1071 Grease
Soy-HBrb HBr 100 182 308 4.1 1274 Grease
a
Reproduced from Guo and Petrovic [9] with permission of John Wiley and Sons, Inc.
b
All values were calculated on the basis of the analyzed Cl and Br contents and under the assumption that each halogen is accompanied by a hydroxyl
group.

bonds) were used. The PUs from both of these isocyanates
showed comparable thermal stability, mechanical strength
and dielectric properties.
The PU networks from soybean oil had numerous valu-
able properties. These properties solely depended upon the
chemical composition and cross-link density. The NCO/OH
mole ratios (isocyanate index) in the polyol directly affected
the physical and mechanical properties of the resulting
PU networks [11]. NCO/OH molar ratios were varied from
1.05 to 0.4 with the resulting properties shown in Table 2.
With a decrease in the NCO/OH mole ratio, the glass tran-
sition temperature Tg decreased linearly from 64 to −3 ◦ C.
The tensile strength of the networks decreased from 47.3
to 0.3 MPa with a decreasing NCO/OH mole ratio. The
polyurethane networks, prepared with lowering of the
molar ratio of NCO and OH groups, had an increasing
amount of imperfections in the form of dangling chain
ends. Therefore, the properties of the networks deterio-
rated with a decrease in the NCO/OH molar ratio. Petrovic
et al. [12] also studied the properties of vegetable oil-based
PUs through hydroformylation. Hydroformylation is an
aldehyde synthesis process that falls under the general clas-
sification of a Fischer–Tropsch reaction. Hydroformylation,
also known as the oxo synthesis, is an important industrial
process for the production of aldehydes from alkenes. This
chemical reaction entails the addition of a formyl (CHO)
group and a hydrogen atom to a carbon–carbon double
bond.
The double bonds of the soybean oil were first converted
to aldehydes using either rhodium or cobalt as catalyst.
The aldehydes were hydrogenated to alcohols forming a
triglyceride polyol. Polyols from a rhodium-catalyzed reac-
tion (95% conversion) resulted in a rigid polyurethane,
while polyols from a cobalt-catalyzed reaction (67%
conversion) resulted in hard PU rubbers with lower
mechanical strength. The soybean-based polyurethanes
were prepared from aliphatic, cycloaliphatic and aromatic
isocyanates [13]. The isocyanates used in this study were
4,4 -diphenylmethane diisocyanate (MDI), 2,4:2,6-toluene
diisocyanate (TDI), hydrogenated MDI (RMDI), isophorone
diisocyanate (IPDI), hexamethylene diisocyanate (HDI),
Desmodur N-100 and Desmodur N-3300 (triisocyanates
derived from 1,6-hexamethylene diisocyanate), Desmodur
RF-E (a tris (p-isocyanato-phenyl)-thiophosphate) and
Desmodur CB 75N a (trimethylol propane TDI-based pre-
polymer). A higher cross-link density of the PU networks
resulted for triisocyanates than for diisocyanates.
The density, glass transition temperature [measured by
differential scanning calorimetry (DSC), thermal mechan-
ical analysis (TMA) and dynamic mechanical analysis
(DMA)] and the degree of swelling in toluene are
reported in Table 3. In comparison with diisocyanates,
the triisocyanates resulted in better overall properties
such as density, Tg , swelling and mechanical properties.
The triisocyanates RF-E [a tris (p-isocyanato-phenyl)-
thiophosphate-based prepolymer] and CB 75N (a trimethy-
lol propane TDI-based prepolymer) showed flexural moduli
of the order of 2480 and 2040 MPa and tensile strengths of
48 and 65 MPa, respectively.
Petrovic et al. [14,15] also studied the properties of
polyisocyanurate cast resins and foams from soybean
oil-based polyols. Polyisocyanurate cast resins are heat
resistant materials obtained by polycyclotrimerization
of diisocyanates or isocyanate-terminated prepolymers
(Scheme 2). The formation of polyisocyanurate from
the prepolymer took place at higher temperatures com-

Table 2
Molecular weights Mc between crosslinks and concentration e of ENAC for polyurethanes (based on soybean polyol and MDI) withNCO/OH mole ratios
(between 1.05 and 0.4)a

NCO/OH mole ratio Density (g/cm3 ) Degree of swelling (W1 /W0 ) Sol fraction (%) Affine model Phantom model

e (mol/cm3 ) Mc (g/mol) e (mol/cm3 ) Mc (g/mol)

1.05 1.104 1.5199 0.82 2.73 × 10−3 404 4.30 × 10−3 257
1 1.104 1.5528 1.02 2.45 × 10−3 451 3.91 × 10−3 282
0.95 1.104 1.5911 1.29 2.17 × 10−3 509 3.52 × 10−3 313
0.9 1.101 1.6334 1.55 1.92 × 10−3 574 3.17 × 10−3 348
0.8 1.095 1.7299 2.78 1.48 × 10−3 741 2.52 × 10−3 435
0.7 1.088 1.8480 5.20 1.12 × 10−3 981 1.96 × 10−3 556
0.6 1.083 2.0165 8.68 7.65 × 10−4 1415 1.41 × 10−3 769
0.5 1.074 2.350 11.67 4.13 × 10−4 2601 8.09 × 10−4 1372
0.4 1.064 3.060 24.78 1.49 × 10−4 7118 3.19 × 10−4 3333
a
Reproduced from Petrovic et al. [11] with permission of Plenum Publishing Corp.
 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215 1203

Table 3
Density, Tg (measured by DSC, TMA, and DMA), and degree of swelling in toluene of soybean oil-based polyurethanesa

Isocyanate Density (kg/m3 ) Tg by DSC (◦ C) Tg by TMA (◦ C) Tg by DMA (◦ C) Swelling degree (%)

MDI 1104 59 55 74 55
TDI 1104 47 53 62 64
RMDI 1062 50 47 69 75
IPDI 1061 48 48 68 79
HDI 1066 10 15 22 79
N100 1082 26 25 41 52
N3300 1096 25 25 37 59
RFE 1272 NA 64 84 22
CB 75N 1186 93 85 92 12
a
Reproduced from Javni and Petrovic [13] with permission of John Wiley and Sons, Inc.

pared to the reaction temperature for the formation of
polyurethane [14]. As a result, the isocyanate terminated
prepolymers (PU) also reacted with themselves, producing
strong isocyanurate chains (Scheme 2). These cross-links
were stronger than normal bonds in polyurethane. For
example, polyisocyanurate foam from soy polyol (59 MPa)
showed nearly double the stress at break than PPO-based
polyisocyanurate foam (31 MPa). Thus, the resulting poly-
isocyanurate foam was chemically and thermally more
stable (disintegration started above 400 ◦ C). Polyisocyanu-
rates are used in applications where the material is exposed
for an extended period of time at an elevated temperature.
Two polyols (PPO 168 and Soypolyol 173) having the same
hydroxyl number, functionality and molecular weight, but
with significant structural differences, were used. PPO 168
had terminal OH groups, which on reaction with isocyanate
of polyisocyanurate formed polyurethane. Soypolyol 173
had internal hydroxyl groups positioned in the middle of
the fatty chain. Thus, Soypolyol 173 exhibited higher cross-
link density of the polyisocyanurate network than PPO
168. The soybean polyol-based polyisocyanurate showed
a higher Tg (about 30 ◦ C higher) than PPO 168-based poly-
isocyanurates.
All the PU foam samples showed a ␤-transition at about
−30 to −20 ◦ C [15]. The PPO 168-based PUs decomposed
at a higher rate at 235 ◦ C, while the maximum rate of
decomposition for soy polyol-based PUs was 370 ◦ C. The
compression strength (measured at a stress of 10, 20 and
30% strains with applied force parallel to the foam rise of
soy polyol-based PU foams was much higher than for PPO-
based PU foams, as shown in Fig. 4. The PPO-based foams
were semi-rigid at an isocyanate index of 110, but the soy
polyol foams had a higher density at an index of 110 and
showed higher compressive stress.
The thermal and mechanical properties of glass rein-
forced soybean oil-based polyurethane composites were
also studied by Petrovic [16]. PUs in this study were
derived from a soybean oil-based polyol (Soypolyol 204)
and petrochemical polyol (Jeffol G30-650). Although the Tg
of jeffol composites was slightly higher than that of soy
polyol composites, the oxidative, thermal and hydrolytic
stability of the latter was superior to propylene glycol-
based polyurethanes [17–19], suggesting that it could
find increasing applications in the composites area. The
structure–property relationships were further studied by
Petrovic et al. [20]. They prepared two types of soybean
polyols, one from epoxidation of soybean oil, followed
by methanolysis and the other from hydroformylation of
soybean oil, followed by hydrogenation [18,19]. The mech-
anistic paths of these processes are shown in Scheme 3.
The polyol II in Scheme 3 was more reactive than polyol
I, because polyol II contains a primary hydroxyl group
as well as one additional carbon atom in the crosslink-
ing chain after hydroformylation, while polyol I contains
a secondary hydroxyl group and methoxy groups as side
chains.

Fig. 4. Compression stress of soybean-based foams and PPO-based foams.

Scheme 2. Schematic representation of polyisocyanurate structure. Reproduced from Javni et al. [15] with permission of Plenum Publishing
Reproduced from [14] with permission of John Wiley and Sons, Inc. Corporation.
1204 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215

Scheme 3. Schematic representation of methanolysis and hydroformylation of soybean oil. Reproduced from Guo et al. [20] with permission of Springer
Science and Business Media, LLC.

Dunjic and co-workers [21] prepared a series of ure-
thane acrylates derived from soybean fatty acid modified
hyperbranched aliphatic polyesters through a two step
process. The material obtained was used as oligomer in
radiation curable compositions. The UV cured acrylates
exhibited good mechanical and thermal properties. The
tensile strengths of these samples ranged from 15.73 to
72.53 MPa and they showed 5% weight loss at around 300 ◦ C
during thermal degradation. Fan et al. [22] reported soy-
based polyamide resins via condensation polymerization
from different dimer acids and diamines. The polyamide
prepared from 1,4-phenylenediamine showed a rapid
increase in molecular weight above 260 ◦ C. Polyamide from
1,4-phenylenediamine showed higher Tg , melting temper-
ature (Tm ), decomposition temperature and mechanical
strength than aliphatic polyamides. The flexibility of dimer
acid and its macrostructure, such as the contents of
monomer and trimer acids, directly affected the resulting
polymer properties.
Deng et al. [23] reported the synthesis of soy-
based copolyamides with different ␣-amino acids. The
contents of amino acids were varied, keeping the con-
tents of dimer acid and phenylenediamine constant. The
copolyamides thus prepared showed a drastic decrease
in mechanical strength. For instance, Young’s modu-
lus for homopolymer was 2116.0 MPa; and that for
copolymers containing tyrosine, glutamic acid and pheny-
lalanine were 330.8, 242.9 and 183.2 MPa, respectively.
John et al. [24] studied PU foams derived from soybean
oil. The reaction was monitored by FTIR spectroscopy.
The introduction of soybean oil caused an increase in
hydroxyl values and acid values as well as molecular
 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215
Fig. 5. SEM micrographs of (a) soybean polyol foam at 3-php water and
(b) voranol polyol foam at 3-php water. Reproduced from Singh and Bhat-
tacharya [25] with permission of John Wiley and Sons, Inc.
weight, whereas iodine values and fatty acid content
decreased.
Singh and Bhattacharya [25] also studied PU foams
from soybean oil. They studied the viscoelastic changes
and cell opening by using vane geometry in a strain-
controlled rheometer. They identified four stages of
modulus development during the foaming reaction namely,
(i) bubble nucleation and growth, (ii) packing of bubble net-
work/liquid foam, (iii) urea microphase separation and cell
opening, and (iv) final curing. In their study, they further
investigated the effects of temperature, voranol (a synthetic
polyol), water and straining frequency on the properties of
PU foam. A SEM micrograph for soybean oil polyol foam
and voranol polyol foam at 3-php (parts per hundred parts)
water is shown in Fig. 5. The size and shape of the cells was
less uniform for soybean polyol foams compared to syn-
thetic voranol foams (Fig. 5). Soybean polyol-based foams
had more pinhole openings and more partially open cell
structures rather than completely open cells.
Rosch and Mulhaupt [26] synthesized polyester resins
and blends from anhydride-cured epoxidized soybean oil.
The mechanical and thermal properties of the casting resins
were dependent upon the type of anhydride used. At low
epoxy conversions, i.e., using low accelerator content or
less reactive anhydrides such as cycloaliphatic anhydrides,
the crosslinked polyesters were highly flexible. For exam-
ple, norbornene dicarboxylic acid anhydride resulted in
1205
polyester with a Tg of −5 ◦ C, which indicated the rubbery
nature of the polyester. With maleic and phthalic anhy-
drides, stiffer polyesters with flexural moduli in the range of
500–1000 MPa and Tg between 43 and 75 ◦ C were obtained.
Eren et al. [27] polymerized maleinized soybean oil with
different alcohols such as low molecular weight polyols
and long chain diols [glycerol, pentaerythritol, polyethy-
lene glycol (PEG) 160, PEG 400, PEG 600, etc.]. The material
obtained was highly crosslinked and become jellylike in
common solvents like acetone and chloroform.
Mohanty and co-workers [28] evaluated the thermo-
mechanical properties of PU-based on soybean phosphate
ester polyols and polymeric dipenylmethane diisocyanate
(pMDI). The glass transition temperature of the PUs var-
ied from 69 to 82 ◦ C and the values of storage moduli were
between 4 × 108 and 1.3 × 109 Pa. The PU samples were
postcured at 100 and 150 ◦ C. The crosslink density e of
the samples postcured at 100 ◦ C was lower than for those
postcured at 150 ◦ C, despite a longer postcure time. Mon-
teavaro et al. [29] investigated the thermal properties of
soybean oil-based PUs by thermogravimetric analysis. The
TGA was carried out under nitrogen at a heating rate of
10 ◦ C min−1 for dynamic TG, and isothermal measurements
were carried out at 230, 240 and 250 ◦ C. Fig. 6a presents
the rate of weight loss in isothermal measurements at 230,
240 and 250 ◦ C for the PU samples. The curves show an
increase in the rate of weight loss with an increase in tem-
perature. The rate of weight loss was highest in the initial
period (up to approximately 100 min). From Fig. 6a, one can
measure the time for weight loss of 4, 5 and 7% at 230, 240
and 250 ◦ C. Fig. 6b shows the log–log plot of time versus
temperature for 4, 5 and 7% weight loss of PU. The verti-
cal lines in Fig. 6b correspond to iso-conversional (for same
weight loss) plots and the plots along the temperature axis
correspond to isothermal lines. If the PU had followed the
same decomposition pattern at different temperatures, the
isothermal lines would be expected to be parallel. Instead,
they are not parallel, indicating different decomposition
processes at different temperatures.
Pechar et al. [30] synthesized PU networks from soybean
oil polyol, petroleum-based polyols and their blends. The
soybean polyols were prepared by air oxidation of raw soy-
bean oil and hydroxylation of epoxidized soybean oil. The
Tg of the PU samples ranged from −21 to +83 ◦ C and was
linearly related with the hydroxyl numbers (55–237 mg
KOH/g) of the soybean oil polyols. Quintero et al. [31]
developed the vegetable oil macro-monomer (VOMM)
technology for application to aqueous coatings. This would
help to reduce the volatile organic content in waterborne
coatings. They used soybean acrylated macro-monomer
(SAM) as a copolymerizable hydrophobe for miniemulsion
polymerization. This system allowed an improvement in
flow and smoothing of the coated film before crosslinking
and cessation of flow.
3. Polymers and IPNs based on castor oil polyols
3.1. Polymers based on castor oil polyols
The use of castor oil in the polyurethane industry adds
value to the crop. Bao et al. [32] studied the effect of the
1206 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215

Scheme 4. Preparation of modified castor oil polyurethane dispersions. Reproduced from Bao et al. [32] with permission of Iran Polymer and Petrochemical
Institute.
 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215
Fig. 6. (a) Isothermal TG curves for PU04 (from toluenediisocyanate and
soy polyol with NCO/OH ratio 0.80) at 230, 240 and 250 ◦ C in nitro-
gen (b) Variation of degradation time (isothermal) with temperature
(dynamic TGA) in nitrogen to achieve the same conversion level at three
temperatures (isothermal and isoconversion lines) for PU04. Reproduced
from Monteavaro et al. [29] with permission of Associacao Brasileira de
Polimeros.
NCO/OH mole ratio on the structure and properties of aque-
ous PU from modified castor oil (MCO). The synthesis of the
PU from modified castor oil (MCPU) is shown in Scheme 4
where acid-ended modified castor oil used for the produc-
tion of PU-polyamide forms salts with a triamine, leading
to the formation of a water-soluble polymer. A three step
degradation was observed for all the PU-polyamide sam-
ples. In the first stage, a weight loss of less than 5% occurred
at about 210–240 ◦ C. In the second stage, a rapid weight loss
started at 250 ◦ C and continued up to 360 ◦ C.
Barrett et al. [33] studied the crystallization kinet-
ics of poly ethylene terephthalate (PET) from a mixture
containing naturally functionalized triglyceride oil. The
crystallization of PET was dependent on several factors such
as plasticization due to the presence of the triglyceride oil,
nucleation from added agents, bond interchange reactions
and the formation of a crosslinked triglyceride oil network.
The identification of such factors allowed some control
over microstructure of these products and similar blends
and semi-IPNs. The Avrami analysis supported the effec-
1207
Fig. 7. Avrami plots for castor oil, sodium benzoate and related PET
compositions during isothermal crystallization from the melt at 220 ◦ C.
Reproduced from Barrett et al. [33] with the permission of John Wiley and
Sons, Inc.
tiveness of castor oil. Avrami plots for castor oil, sodium
benzoate and related PET compositions during isothermal
crystallization from the melt at 220 ◦ C are shown in Fig. 7.
In the presence of castor oil, a high curvature appeared in
the Avrami plot for the crystallization of PET. This showed
a smooth transition from the primary to secondary crys-
tallization. The sodium benzoate blends displayed a rapid
transition from primary to secondary crystallization. The
mixture of castor oil and sodium benzoate showed a grad-
ual transition.
Kansara et al. [34] statistically studied the reaction
kinetics of castor oil (CO)-based polyol and TDI. They used
a second-order rate expression for the equimolar reaction
between polyol and TDI. For a specific case, a moles of both
of the reactants are present at the start of the reaction and
at a specific instant t, x moles of the reactants are reacted.
Then, one can find from the bimolecular rate expression
that the quantity x/a(a − x) is directly proportional to the
time t. Thus, plots of x/a(a − x) versus time were linear.
They studied the reactivity of ortho and para—NCO groups
in TDI with varying temperature, catalyst ratio and polyol
chain length of. The prepolymers R60 and R92 were polyols-
based on castor oil. The hydroxyl value, equivalent weight
and Brookfield viscosity (cP) of R60 and R92 were reported
to be 5, 220, 620 and 6, 190, 700, respectively. R60 and R92
showed higher conversion compared with the parent castor
oil at all temperatures and catalyst concentrations.
Kansara and co-workers [35] also studied castor oil-
based polyurethane adhesives. They used two teak wood
pieces and applied the adhesive solution to a thickness of
0.1 mm and joined the pieces together under a load of 2.5 kg
for 12 h. These samples were found to have 10 times more
lap shear strength as compared with commercially avail-
able wood adhesives. The adhesive films were also tested
for thermal stability and chemical resistance.
Yeganeh and Mehdizadeh [36] investigated millable
PU elastomers from castor oil-based polyols. Millable PU
elastomers (MPE) are a special type of synthetic rub-
ber. MPEs can serve the rubber industry as they can be
1208 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215

Each sample has NCO/OH mole ratio 1.0. Quantities in parentheses are in g. PHC-I, PHC-II and PHC-III contain castor oil, polyethylene glycol, polyethylene terephthalate and zinc acetate. The curing agent is
mixed, extruded, calendared, and compression or injec-

Dielectric strength
tion molded in conventional rubber processing equipments
[37]. The MPEs were prepared by the reaction of difunc-
tional castor oil and TDI dimer in an inert atmosphere. The

(V/mil)a
synthesis of difunctional castor as reported by Yeganeh and

2159
2117
1926
Mehdizadeh [36] is as follows. In a three-necked, round-
bottomed flask equipped with a stirrer, dropping funnel

Q factor
and thermometer, dried castor oil (100 g) was added. The

121.95
44.24
35.33
temperature was brought to 100 ◦ C, followed by dropwise
addition of phenyl isocyanate (8.33 g) under stirring. The
reaction was continued for 2 h, before cooling.

Dielectric constant
These MPEs showed two-step degradations, one at
270 ◦ C and the second one at 380 ◦ C. The mechanical prop-
erties of these MPE were dependant on the contents of
castor oil and the chain extenders. On comparison with

toluene diisocyanateand trimethylol propane dissolved in a minimum amount of dimethyl formamide and N-methyl aniline. Sample thickness: 17 mil (0.017 in.).
(60 Hz)
a commercially available elastomer (Urepan 600), these

5.00
5.45
5.10
MPEs exhibited comparable tensile strength, compression
set, resilience and slightly inferior abrasion resistance and
elongation at break.

Dissipation factor
Novel PU insulating coatings from glycolyzed PET
(GPET) and castor oil were also investigated by Yeganeh
and Shamekhi [38]. First, they synthesized polyhydroxy

(60 Hz)

0.0082
0.0226
0.0283
compounds from different compositions of CO and GPET.
Several types of reactions can occur during the prepara-
tion of polyhydroxy compounds (PHC). So, proper analysis
such as measurement of hydroxyl values and acid val-

Char (%)@600
ues was carried out to ascertain the transesterification
as the major reaction. The thermal and electrical prop-
erties of the PUs obtained from the PHCs are shown in

(o C)

8.0
3.8
8.7
Table 4. The Tg of the samples ranged from 47 to 61 ◦ C. The
tensile strength was between 19 and 47 MPa and the elon- T 50% (◦ C)
gation was 8–24%. It was observed that with a decrease

Reproduced from Yeganeh and Shamekhi [38] with permission of John Wiley and Sons, Inc. [38].
in the hydroxyl value of PHC, the crosslink density also 345
326
320
decreased. Yeganeh and Hojati-Talemi [39] also studied
biodegradable PU networks obtained from the PHCs of
T 10% (◦ C)

castor oil and PEG. The PU networks obtained were char-

acterized by their physical, mechanical and viscoelastic
262
267
272

properties. The stress–strain curves for the castor oil PUs

(CPU) are shown in Fig. 8. Fig. 8 shows a smooth transition in
Tg (◦ C)

stress–strain behavior for CPU1 and CPU2 samples similar

to that in lightly crosslinked amorphous rubber. However,
61
57
47

the stress–strain behavior of CPU3 and CPU4 was different:

these showed a yield point due to presence of a crystalline
Pu4[PHC-II(1.01) + curing agent (1.3) + DMF(0.86) + xylene(2.59)]
Pu1[PHC-I(0.99) + curing agent (1.3) + DMF(0.86) + xylene(2.57)]

Pu7[PHC-III(1.1) + curing agent (1.3) + DMF(0.9) + xylene(2.7)]

phase.
Because of the higher crystallinity of CPU4, it showed
higher initial modulus and tensile strength and lower
elongation at break. The tensile strength of these
CPUs ranged from 0.66 to 2.51 MPa. The Tg of the
samples was below room temperature (between −2.0
and 5.1 ◦ C).
Preparation of PU nanoparticles by miniemulsion
Thermal and electrical propertiesa

polymerization from castor oil polyol was reported by

Zanetti-Ramos et al. [40]. The PU particle size measured
by dynamic light scattering ranged from 200 to 300 nm.
Ogunniyi et al. [41] reported the preparation and proper-
ties of PU foams from the reaction of TDI with a mixture
of castor oil polyol and polyether polyol. The introduc-
tion of castor oil polyol in the formulation of PU foams
increased the tensile strength from 3.33 to 138.89 kN/m2
Sampleb
Table 4

and compression set from 5.2 to 49.25% with increasing oil

a

content.
 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215
Fig. 8. Stress–strain curves for CPU 1–4. CPU1 containing100% epoxy mod-
ified PU prepolymer-based on castor oil (EPU1) and 0% epoxy modified
PU-based on polyethylene glycol (EPU2), CPU2 containing 90% EPU1 and
10% EPU2, CPU3 containing 70% EPU1 and 30% EPU2 and CPU4 contain-
ing 50% EPU1 and 50% EPU2. Reproduced from Yeganeh and Hojati-Talemi
[39] with permission of Elsevier Ltd.
3.2. Interpenetrating and semi-interpenetrating
networks based on castor oil
Polymer systems comprising of two or more networks,
which are at least partially interlaced on a molecu-
lar scale, but not covalently bonded to each other, are
called interpenetrating polymer networks (IPN). These
polymer networks cannot be separated unless chemical
bonds are broken. Polymer systems comprising one poly-
mer network and another of linear or branched polymer,
characterized by the penetration on a molecular scale
of the linear or branched macromolecules in the poly-
mer networks, are called semi-interpenetrating networks.
Semi-interpenetrating polymer networks are distinguished
from interpenetrating polymer networks because the con-
stituent linear or branched polymers could, in principle, be
separated from the constituent polymer network(s) with-
out breaking chemical bonds. When they can be separated,
they are called polymer blends.
Attempts have been made to synthesize interpenetrat-
ing polymer networks (IPN) and a series of cross-linked
copolymers and IPNs from epoxidized vegetable oils and
maleinized tung oil [42]. Cross-linked copolymers were
synthesized by mixing epoxidized vegetable oils and
adduct of tung oil with maleic anhydride in different
proportions. The IPNs were tested by dynamic mechan-
ical spectroscopy (DMS) to investigate compatibility and
damping properties. The IPNs formed by triglycerides were
found to increase the toughness and fracture resistance
in conventional thermoset polymers. There are reports of
development of IPNs consisting of cross-linked polystyrene
and epoxidized linseed oil elastomers [43]. IPNs from cross-
linked polystyrene and castor oil elastomers have also
been reported [44–46]. Suthar and co-workers [47–50]
prepared IPNs from polyurethanes-based on castor oil
with other vinyl monomers. They found that the IPNs
1209
formed were tougher than the corresponding homopoly-
mers.
Patel and Suthar [51] synthesized liquid pre-
polyurethanes from castor oil and TDI under different
conditions and with varying NCO/OH ratios. Then, the
pre-polyurethane was reacted with poly (ethyl acrylate) to
obtain IPNs. These IPNs were characterized by chemical,
mechanical and thermal methods. The glass transition
temperature of these IPNs ranged from 38 to 41 ◦ C. The
chemical resistance of the IPNs was studied in different
reagents: 25% H2 SO4 , 15% HCl, 5% HNO3 , 5% NaOH, 25%
acetic acid, 5% H2 O2 , 40% NaCl, methylethyl ketone, dis-
tilled water, carbon tetrachloride and toluene for seven
7 days. The IPNs were stable in all the media except
methylethyl ketone, carbon tetrachloride and toluene.
The IPNs were stable up to 300 ◦ C with 7–9% weight loss;
54–57% weight loss was observed around 400 ◦ C and
decomposition was complete beyond 550 ◦ C. Mechanical
properties of these IPNs are given in Table 5.
Suthar and Patel [52] studied IPNs from castor oil-
based PU and poly (methyl acrylate). The castor oil was
reacted with 4,4 -diphenylmethanediisocyante to obtain
pre-polyurethane, which was further reacted with methyl
acrylate monomer and ethylene glycol dimethacrylate as
a crosslinker. These IPNs showed low chemical resis-
tance towards CCl4 , methylethyl ketone and toluene. They
showed high light transmittance (49–81%). These poly-
mers were stable up to 300 ◦ C, lost 45% weight rapidly at
around 450 ◦ C and decomposed completely beyond 600 ◦ C.
The tensile strength of these polymers was between 0.43
and 1.87 mN/m2 and they had elongations in the range of
84–102%.
Suthar et al. [53] also studied the IPNs from castor
oil-based polyesters and poly (methyl methacrylate). The
polyesters were synthesized from castor oil and dibasic
acids such as malonic, succinic, glutaric, adipic, suberic and
sebacic acids. These IPNs showed two glass transitions cor-
responding to their individual component networks. The
first Tg was in the range of −76 to −70 ◦ C and the second was
between 25 and 34 ◦ C. The tensile strength was between
140 and 280 kPa and Young’s modulus was 730–1200 kPa.
These polymers were stable upto 300 ◦ C showing only
2–4% weight loss, whereas they showed 50% weight loss
at around 400 ◦ C. The samples decomposed completely
beyond 500 ◦ C.
Suthar et al. [54] synthesized three series of IPNs-
based on PU from castor oil and TDI with polystyrene,
poly (methyl methacrylate) and poly (n-butyl methacry-
late). They studied the effects of structural variables such
as composition, type of vinyl monomer and the effect of
interaction of phases on the dielectric properties. These
IPNs were characterized in terms of the variation of dielec-
tric permittivity E , dissipation factor E and tan ı versus
temperature. The dielectric relaxation studies showed that
these IPNs behaved like homogeneous materials. Sperling
and co-workers [55,56] reported the preparation of inter-
penetrating networks from castor oil-based polyurethanes
and styrene monomer. The resulting IPNs were char-
acterized by electron microscopy, modulus-temperature
measurements and stress–strain analysis. The interpen-
etrating networks (IPN) showed stress–strain behavior
1210 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215
Table 5
Mechanical properties of IPNsa
Sampleb , c Tensile strength (mN/m2 )
IPN-1 (PPU-25 + EA-75) 3.41
IPN-2 (PPU-35 + EA-65) 3.66
IPN-3 (PPU-45 + EA-55) 2.85
IPN-4 (PPU-25 + EA-75) 3.37
IPN-5 (PPU-35 + EA-65) 7.10
IPN-6 (PPU-45 + EA-55) 6.38
IPN-7 (PPU-25 + EA-75) 9.38
IPN-8 (PPU-35 + EA-65) 10.60
IPN-9 (PPU-45 + EA-55) 8.67
PEAd 62.30
a
Reproduced from Patel and Suthar [51] with permission of John Wiley and Sons, Inc.
b
Contents of pre-polyurethane (PPU) and ethyl acrylate (EA) are given in parenthesis.
c
NCO/OH molar ration for IPNs 1–3 is 1.6, for IPNs 4–6 is 1.8 and for IPNs 7–9 is 2.0.
d
PEA is the homopolymer of ethyl acrylate.
similar to reinforced elastomers. The properties of the IPN
showed a dependence on the NCO/OH ratio in the castor oil-
based PU and the content of polystyrene. At a fixed NCO/OH
ratio of 0.75, with a decrease in the polystyrene content
in the IPN from 53 to 50%, the IPNs exhibited an increase
in elongation from 130 to 140% and in tensile stress from
1000 to 2500 psi. For a fixed 50% content of polystyrene,
a decrease in elongation (from 140 to 130%) and in tensile
stress (from 2500 to 1200 psi) was observed for an increase
in the NCO/OH ratio from 0.75 to 0.85. The decrease in
polystyrene content and NCO/OH ratio caused a decrease
in the amount of stiff material in the IPN, leading to an
increase in elongation. The decrease in stiff material was
expected to cause a decrease in tensile stress; but con-
trary to expectation, the tensile stress increased with a
decrease in stiffer material. This phenomenon has not been
explained [56], but may possibly be due to synchronization
of the phases.
Prashantha et al. [57] studied IPNs-based on
polyol modified castor oil polyurethane and poly (2-
hydroxyethylmethacrylate). They investigated mechanical
and thermal properties of the IPNs such as tensile strength,
elongation, hardness, Tg and degradation. The tensile
strength ranged from 27 to 38 MPa and elongation at break
was between 58 and 120%. All the IPNs showed about 2–4%
decomposition at 200 ◦ C, about 10% at 300 ◦ C and about
40% at 400 ◦ C. There was a rapid weight loss from 40 to
90% in temperature ranges of 400–500 ◦ C.
Sanmathi et al. [58] synthesized and characterized IPNs
from modified castor oil-based polyurethane and poly (2-
ethoxyethyl methacrylate). The preparation of these IPNs
is shown in Scheme 5. The triglyceride of castor oil was
exchanged with glycerol, followed by reaction with a diiso-
cyanate to form castor-based PU (GC-PU). 2-Ethoxyethyl
methacrylate was subsequently polymerized in the pres-
ence of GC-PU to prepare the IPNs. The presence of
H-bonding between poly (2-ethoxyethyl methacrylate) and
castor PU (GC-PU) is also shown in Scheme 5. The incor-
poration of poly (2-ethoxyethyl methacrylate) in GC-PU
during the formation of IPN caused an increase in tensile
strength and decrease in elongation, when compared with
the individual components of GC-PU and (2-ethoxyethyl
methacrylate). These IPNs exhibited Young’s modulus of
the order of 2.9–84 mN/m2 .
Young’s modulus (mN/m2 ) Elongation @ break (%) Hardness shore A
1.64 194 79
2.17 182 83
1.90 188 95
3.67 148 81
3.01 225 73
2.99 200 80
4.67 183 86
4.13 186 87
3.84 178 79
2500 16 92
Kansara et al. [59,60] also studied the sorption and
diffusion behavior of IPNs-based on PU and unsaturated
polyester (UPE). The PU was prepared from castor oil polyol.
The sorption behavior of these IPNs was studied with
changes in crosslink density, NCO/OH mole ratio, composi-
tion of the constituents and hydroxyl value. Chlorobenzene
was used to study the swelling behavior of the IPNs. Sorp-
tion was inversely related to the NCO/OH mole ratio. The
crosslink density ranged from 5 to 27 × 104 mol/g for dif-
ferent IPNs, as calculated by the Flory–Rehner equation
[61]. An increase in diffusion coefficient was observed with
an increase in the NCO/OH molar ratio and the content of
unsaturated polyester.
Xie and co-workers [62] studied the damping behav-
ior of grafted interpenetrating networks. They prepared
IPNs from castor oil, toluene diisocyanate, monohydroxy
terminated acrylic prepolymer and acrylic monomer in the
presence of dibutyltin dilaurate and redox initiators. The
dynamic mechanical properties of the IPNs were observed
to exhibit high damping properties over a wide range of
temperature.
Xie and Guo [63] studied adhesives made from IPNs for
bonding with rusted iron without pretreatment. They pre-
pared two types of room-temperature curable IPNs: one
from castor oil-based PU and vinyl or acrylic polymer and
the other from castor oil PU, unsaturated polyester and vinyl
or acrylic polymer. The lap shear strength of joints between
rusted iron plates and IPNs (adhesives) ranged from 1.51 to
8 MPa.
Nayak and co-workers [64–68] also synthesized and
characterized castor oil-based interpenetrating networks.
First, they prepared polyurethanes from castor oil and hex-
amethylene diisocyanate by varying the NCO/OH ratio and
then prepared IPNs by reacting polyurethanes with various
acrylates such as hydroxyethyl methacrylate and cardanyl
methacrylate by using benzoylperoxide as initiator and
ethylene glycol dimethacrylate as crosslinker. Infra-red IR
spectroscopy, NMR spectroscopy, TGA, etc. were employed
to study the properties of resulting IPNs.
Cunha et al. [69] employed a statistical method to
accurately evaluate the properties of castor oil-based semi-
interpenetrating polymer networks (sIPN). They used a
23 factorial experimental design for optimization of the
properties. The semi-interpenetrating polymer networks
 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215 1211

Scheme 5. Preparation of GC-PU/poly (2-EOEMA) IPNs. Reproduced from Sanmathi et al. [58] with permission of John Wiley and Sons, Inc.

(sIPNs) were prepared from castor oil polyol, toluene diiso- to study the properties of the sIPNs. They showed differ-
cyanate and methyl methacrylate. The properties of these ent swelling properties for different samples. The sample
sIPNs depended upon the ratio of the contents and the containing maximum methyl methacrylate exhibited low
mole ratio NCO/OH. Various techniques were employed swelling. Mechanical properties were also largely influ-
1212 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215
enced by the methyl methacrylate content. For instance,
the sIPN containing 20% MMA showed 22.6% swelling and
1.48 MPa elastic modulus, whereas the sIPN containing 60%
MMA showed 17.4% swelling and 6.49 MPa elastic modulus.
4. Polymers based on nahar seed oil polyol
Nahar (Mesua ferrea L.) seed oil contains mainly triglyc-
erides of linoleic, oleic, palmitic and stearic acids [70]. Karak
and co-workers [71–74] studied polyester, polyesteramide,
polyurethane and polyurethane amide resins from nahar
seed oil [71–74]. They prepared polyester resins from
nahar seed oil monoglycerides and phthalic and or maleic
anhydrides [71]. Nahar seed oil was first converted into
monoglycerides by alcoholysis and then the resins were
prepared by reacting monoglycerides with phthalic and
or maleic anhydrides. The alcoholysis and polycondensa-
tion reaction of the oil with acid anhydride is shown in
Scheme 6. An increase in the maleic anhydride content in
the resin decreased the curing time. Resin with 50% maleic
anhydride took 7 h for complete curing, whereas resin with
75% maleic anhydride took 6 h. The polyester films were
highly resistant to dilute HCl (10%), aqueous NaCl salt solu-
tion (10%) and distilled water.
Polyesteramide resins from nahar oil were also studied
by Karak and Mahapatra [72]. The oil was first converted
Scheme 6. Alcoholysis and poly-condensation reaction of oil with acid anhydride. Reproduced from Dutta et al. [71] with permission of Elsevier B.V.
into methyl ester, and then reacted with diethanol amide
to form diethanol amide of fatty acids. The fatty acids amide
was then reacted with dibasic acid or their derivatives. The
hardness of the resins was tested as pencil hardness.
The pencil hardness test is used to test coatings for their
hardness and resistance to scratches and wear. The princi-
ple of operation uses a pressure applied to allow the pencil
lead to just crush and therefore, repeatable results for the
hardness of the coating can be obtained. These pencils,
when pressed for a specified number of times on the coat-
ing, will also allow a wear factor to be determined. This
wear factor is related to the hardness of the pencil used.
Pencils of different grades are used in the test, ranging from
9H to 9B. [H signifies hardness and as one goes to a lower
H number, the lead becomes softer, and grades HB to 9B
designate increasing softness (B = blackness).]
The pencil hardness of the cured resins as reported by
Karak and Mahapatra [72] ranged from HB to 2H. The cured
resin had a gloss between 81 and 85 at 60◦ and had 100%
adhesion. Karak and Dutta [73] studied the effect of the
NCO/OH ratio on the properties of nahar seed oil modified
PU resins. The resins were prepared by varying NCO/OH
molar ratio from 0.8 to 2.0. The coating properties such
as pencil hardness, gloss, adhesion was studied. The hard-
ness of the resins ranged from HB to 3H, the gloss at a 60◦
angle was from 109 to 117% and the adhesive strength was
 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215 1213

125–336 kN/m. These properties were found to increase

with increasing NCO/OH ratio from 0.8 to 2.0. The PU resin
with equal proportions of NCO and OH showed three degra-
dation stages at temperatures of 295, 375 and 490 ◦ C. The
degradation temperatures were observed to decrease with
increasing NCO/OH ratio. Resin with a NCO/OH ratio of 1.5
showed two-stage degradation at 290 and 390 ◦ C and the
resin with a NCO/OH ratio of 2 showed a single-stage degra-
dation at 320 ◦ C.
Karak and Dutta [74] synthesized poly (urethane amide)
resins from nahar seed oil and TDI in the presence of dibutyl
tin dilaurate (DBTDL) as catalyst. The coating performance
of these resins was tested by measuring gloss, pencil hard-
ness, adhesion and chemical resistance. The gloss at a 45◦
angle ranged from 66 to 70 and the pencil hardness ranged
from HB to 2H. Chemical resistance was studied for 10 days
insolutions of NaOH, HCl, NaCl, ethyl alcohol and in dis-
tilled water. The cured PU amide resin showed average to
excellent chemical resistance.

5. Other polymers based on oil polyols

There are many vegetable oils other than soybean, cas-

tor and nahar that can be used in the synthesis of polyols
for PUs, such as rapeseed oil, palm oil, canola oil, linseed
oil, olive oil, sunflower oil, safflower oil, etc. Rapeseed
oil methyl esters have been synthesized by the reaction
of rapeseed oil and methanol at a temperature range of
60–70 ◦ C with sodium hydroxide as a catalyst. They have
been produced on an industrial scale for use as biodiesel
fuel [75].
Hu et al. [76] prepared rigid polyurethane foam from
rapeseed oil polyol. They first converted the oil into polyol
by hydroxylation, followed by alcoholysis. The alcoholysis
of the hydroxylated rapeseed oil was required because of
its low hydroxyl value (ca. 100 mg KOH/g), which is not
suitable for the preparation of rigid polyurethanes. The
polyol thus prepared was compared with a commercially
available polyester polyol, Daltolac P744. The experimental
data indicate that the compression strength of the PU foam
made from rapeseed oil polyol is lower than that of Dalto-
lac P744-based foam. The other properties of the rapeseed
oil polyol foam are similar to those of commercial foam,
Daltolac P744.
Chian and Gan [77] reported the development of
rigid PU foams from palm oil. Their PU foams exhib-
ited high compression strength (1–35 MPa) and densities
(200–300 kg/m3 ). Desai and co-workers [78] reported PU
adhesive from argemone oil and castor oil for wood bond-
ing applications. The best performing adhesive (argemine
oil-based) was compared with various commercially avail-
able adhesives such as Dunlop adhesive, Fevicol and
Araldite. The average lap shear strength of PU adhe-
sive was 63.1 × 105 N/m2 , while the highest strength for
the commercially available adhesives was observed to be
28.3 × 105 N/m2 for araldite.
Ahmad et al. [79] synthesized polyesteramide from
Pongamia glabra oil for biologically safe anticorrosive coat-
ings. The oil was first converted to N,N-bis(2-hydroxyethyl)
P. glabra fatty amine (HEPGA) and then HEPGA was con-
verted into polyesteramide (PGPEA) by reaction with
Fig. 9. Glass transition behavior for several vernonia-sebacic polyester
network/PET semi-IPN compositions. First heat data, the materials as syn-
thesized (A) and second heat data, recorded after cooling rapidly from
300 ◦ C. Reproduced from Barrett et al. [81] with permission of John Wiley
and Sons, Inc.
phthalic acid. The PGPEA coatings showed 10% weight loss
up to 275 ◦ C, 50% weight loss up to 370 ◦ C and 78% weight
loss up to 400 ◦ C. Almost all of the physico-mechanical
properties such as scratch hardness (3.5 kg), gloss (up to
90% at a 60◦ angle) and adhesion strength (100%) were
superior to those of polyesteramides obtained from other
seed oils. Ahmad et al. [80] also studied ambient cured
PU modified epoxy coatings from linseed oil. The linseed
oil was first hydroxylated and then linseed oil PU was
prepared. The linseed oil PU obtained by 10% loading of
TDI showed the best physico-mechanical and anticorrosive
properties.
Barrett et al. [81] synthesized semi-IPNs from vernonia
oil–sebacic acid polyester network (VOSA) and PET. The
semi-IPN containing 50% PET and 50% VOSA was observed
to be over 15 times tougher than PET and over 50 times
tougher than the neat vernonia oil elastomer. The semi-
IPN with 50% PET showed better properties than the other
semi-IPNs, e.g. the tensile strength for the semi-IPN with
50% PET was 6030 MPa and the modulus was 25.8 MPa. The
derivative plots for the first and the second heating scans
in DSC heat flow around the Tg region are shown in Fig. 9.
1214 V. Sharma, P.P. Kundu / Progress in Polymer Science 33 (2008) 1199–1215
All the semi-IPNs showed two glass transitions in the first
scan, which transformed into a single transition in the sec-
ond scan after rapid cooling from 300 ◦ C. Thus the materials
were multiphase as prepared, but after heating to above the
melting point of the PET and cooling, they became nearly
single phase or microheterogeneous.
6. Conclusions
Waste plastic materials are the major concerns of envi-
ronmentalists. Thus, renewable resources are now greatly
favored for the production of polymers. The wide range
of mechanical properties and the ability for easy machin-
ing and forming cause the plastic foams and elastomers to
find wide industrial and consumer applications. In partic-
ular, urethane foams and elastomers have been found to
be well suited for many applications. The vegetable oils
provide a large variety of options for the preparation of
polyurethanes. All the vegetable oils are triglycerides of
fatty acids and most contain unsaturated groups. Only a few
oils contain other groups such as hydroxyl in castor oil, saf-
flower oil and lesquerella oil, and oxirane group in vernonia
oil. Soybean and linseed oils are also used in the prepa-
ration of polyurethanes by converting them into epoxies
or by hydroformylation. The incorporation of oils in the
polyurethanes provides a great opportunity to tailor the
properties of polyurethane products.
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