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Pernick Faculty of Engineering, Shenkar College of Engineering and Design, Ramat-Gan, Israel
O U T L I N E
Polymers from Renewable Sources
Determination of Bio-Based Content in
Polymers
Raw Materials for Renewable Sources
Polymers
Polymers from Renewable
Sources
In the past few decades concern about the environ-
ment, climate changes, and limited fossil resources
has led to an intensive research of alternatives to
fossil-based polymers. From a historical point of
view, the first polymers used by mankind were from
renewable sources, bio-based polymers, long before
the birth of synthetic polymers. Celluloid, a bio-
based man-made polymer was invented in the 1860s,
and since then, many other bio-based polymers have
been developed. However, the development of the
crude oil industry in the 20th century transformed the
world of polymers, leading to the use of synthetic
polymers as a replacement for bio-based polymers.
The increasing use of synthetic polymers as a result
of the growing human population and standard of liv-
ing in the next decades will result in higher demands
on oil production and will contribute to a possible
depletion of crude oil before the end of the 21st cen-
tury. It is estimated that by 2015 the worldwide
annual production of plastics is very likely to reach
300 million tons (14
18% are thermosets), which
will require large amounts of petroleum and will
result in the emissions of hundreds of millions of tons
of CO2 to the atmosphere [1]. A return to bio-based
polymers will reduce the dependency of the polymers
and plastics industry on petroleum, thus creating
more sustainable alternatives.
Handbook of Thermoset Plastics. DOI: http://dx.doi.org/10.1016/B978-1-4557-3107-7.00015-4
2014 Elsevier Inc. All rights reserved.
15 Biobased Thermosets
Ana Dotan
577 Thermoset from Renewable Sources 594
References 615
578
579
Bio-based polymers are derived from renewable
resources such as plant and animal mass from CO2
recently fixed via photosynthesis [2]. Bio-based poly-
mers can be natural or synthetic. Natural bio-based
polymers are polymers synthesized by living organ-
isms such as animals, plants, algae, and microorgan-
isms. The most abundant bio-based polymers in
nature are polysaccharides [3]. Cellulose and starch
are natural polymers based on polysaccharides, and
are abundant in nature. Proteins and bacterial polyhy-
droxyalkanoates are also natural bio-based polymers
[4]. Bio-based polymers are not necessarily sustain-
able; this depends on a variety of issues, including
the source material, production process, and how the
material is managed at the end of its useful life. Sus-
tainable produced bio-based polymers are those
grown without genetically modified organisms
(GMOs), hazardous pesticides, certified as sustain-
able for the soil and ecosystems, and compostable.
Sustainability also depends on the reduction of
impacts to occupational and public health as well as
the environment throughout their life cycles [2]. Bio-
based materials are important candidates for sustain-
able development since they present the potential to
reduce greenhouse emissions by sequestering CO2, to
reduce raw material costs, and to create opportunities
for growth and employment in agriculture [5].
Life cycle assessment (LCA) is the most widely
applied and accepted method to quantitatively assess
the environmental impact of a given material
577
578
throughout its life cycle; its principles and frame-
work are described in ISO 14040 [6]. Usually the
impact categories considered in LCA are global
warming, acidification of soil, ozone layer depletion,
aquatic eutrophication, respiratory organics, respira-
tory inorganics, land occupation, non-renewable
energy, and aquatic ecotoxicity [7]. Additional envi-
ronmental indicators are resource depletion and
human toxicity [5].
Global warming impact is measured by the
amount of CO2 that is liberated from the material
throughout its life cycle. CO2 is the principal anthro-
pogenic gas that is thought to affect the Earths radia-
tive balance. For this reason it is believed that there
is a close correlation between CO2 and the change of
the Earths temperature [8]. The CO2 footprint of a
material is assessed by the carbon emissions conse-
quent on the creation of a unit mass of material,
including those associated with transport, generation
of the electric power used by the plant, and that of
feedstocks and hydrocarbon fuels. The CO2 footprint,
which is measured in units of kg of CO2/kg material,
is the sum of all contributions per unit mass of mate-
rial. Renewable resource polymers have a low CO2
footprint since plants grow by absorbing CO2 from
the atmosphere and thus sequester carbon [9].
Determination of Bio-Based
Content in Polymers
Bio-based polymers can be made totally or par-
tially from renewable source raw materials, pro-
duced from photosynthesis and CO2. In order to
determine the bio-based content of the polymer, the
new carbon content must be measured. A renew-
able source is replenished by natural processes at a
rate comparable to its exploitation rate. The carbon
content of such polymers is derived from the so-
called short carbon cycle within an expected time
frame between 1 to 10 years. Most industrial poly-
mers and plastics are presently produced from fossil
resources that are non-renewable as they cannot be
replenished at a rate comparable to the exploitation
rate. Fossil resources have a long carbon cycle,
with an expected time frame to convert biomass to
petroleum, gas, and coal of greater than 106 years
[10]. The accepted measure of bio-based content is
the level of 14C isotope in the feedstock (basically,
HANDBOOK OF THERMOSET PLASTICS
carbon dating), because ancient petroleum has lost
its 14C through radioactive decay whereas feedstock
derived from recently living organisms have a 14C
content related to the current equilibrium concen-
tration in the atmosphere.
ASTM D6866-11 has developed a protocol to
quantify the bio-based content in materials by com-
paring the 14C/12C ratio to that of a standard speci-
men typical of living organisms [11]. CEN/TS
16137 is the equivalent European for the ASTM
standard test [3]. ASTM D6866-11 is the Standard
Test Methods for Determining the Bio-based
Content of Solid, Liquid, and Gaseous Samples
Using Radiocarbon Analysis. It defines bio-based
content as the amount of bio-based carbon in the
material or product as a percent of the weight
(mass) of the total organic carbon in the product.
This standard utilizes two methods to quantify the
bio-based content of a given product: (a) Accelera-
tor Mass Spectrometry (AMS) along with Isotope
Ratio Mass Spectrometry (IRMS); or (b) Liquid
Scintillation Counters (LSC) using sample carbon
that has been converted to benzene. Those methods
directly discriminate between product carbon result-
ing from new carbon input and that derived from
fossil-based input. A measurement of the 14C/12C
ratio is determined relative to the modern carbon-
based oxalic acid radiocarbon Standard Reference
Material (SRM) 4990c (referred to as HOxII), as
the oxalic acid standard is 100% bio-based. The
percent new carbon can be slightly greater than
100% due to the continuing (but diminishing)
effects of the 1950s nuclear testing programs.
Because all sample 14C activities are referenced to
a pre-bomb standard, all modern carbon values
must be multiplied by 0.95 to correct for the bomb
carbon and to subsequently obtain the true bio-
based content of the sample [11].
CEN/TS 16137 specifies the calculation method
for the determination of bio-based carbon content
in monomers, polymers, plastics materials and pro-
ducts using the 14C method based on three test
methods: (a) Proportional scintillation-counter
method (PSM); (b) Beta-ionization (BI); and
(c) Accelerator mass spectrometry (AMS). The ana-
lytical test methods specified in this Technical
Specification are compatible with those described
in ASTM D6866-11. The bio-based carbon content
is expressed by a fraction of sample mass, as a frac-
tion of the total carbon content, or as a fraction of
15: BIOBASED THERMOSETS
the total organic carbon content. This calculation
method is applicable to any polymers containing
organic carbon, including bio-composites [3].
Calculation of percentage of bio-based content
according to CN/TS 16137:2011 is based on the
calculation of carbon content as a fraction of the
total organic carbon content (TOC) expressed as a
percentage, using Equation (15.1):
XB ;TOC 5 XB =XTOC (15.1)
Here, XB 5 is the bio-based carbon content by
mass, expressed as a percentage; and XTOC 5 is the
total organic carbon content, expressed as a per-
centage, of the sample.
Raw Materials for Renewable
Sources Polymers
Natural Oils
Natural oils, which can be derived from both
plant and animal sources, are considered to be one
of the most important classes of renewable sources
because of the wide variety of possibilities for
chemical transformations, worldwide availability,
and relatively low price [12]. Vegetable oils, fish
oils, and oils from algae can be transformed in raw
materials for polymers. Vegetable oils are inexpen-
sive and offer different degrees of unsaturation
while fish oils have a high degree of unsaturation
[13]. Plant oil is a type of lipid, stored in an organ-
elle in the form of triglycerides, during the oilseed
development. Lipids may be defined as
1
H2C O
O 5
HC O
O
H2C O
2 3
Figure 15.1 A triglyceride molecule (from top to bottom: saturated palmitic acid and unsaturated oleic acid and
alpha-linolenic acid), glycerol linkage (1), ester group (2), -position of ester group (3), double bonds (4),
monoallylic position (5), and bisallylic position (6).
579
hydrophobic or amphiphilic (both hydrophilic and
lipophilic) small molecules. Different plant species
contain lipids with different fatty acid compositions
and distributions. Lipids help form a hydrophobic
biological membrane that separates cells from their
surroundings and keeps chloroplasts, mitochondria,
and cytoplasm apart, thus preventing or regulating
diffusion of chemicals [14].
Plant oil is a mixture of various triglycerides
(also called triacylglycerol). One glycerol is
attached to three different fatty acids to form a tri-
glyceride. Glycerolipid and fatty acids are synthe-
sized in the oilseed simultaneously during seed
development, before forming diacylglycerol and
subsequently triacylglycerols. Triglycerides are
composed of three fatty acids joined at a glycerol
juncture, as can be seen in Figure 15.1. Fatty acids
account for approximately 95% of the total weight
of triglycerides and their content and chemistry are
characteristics of each plant oil and geographical
conditions [15]. The most common oils contain
fatty acids that vary from 14 to 22 carbons in
length with 0 to 3 double bonds per fatty acid.
Fatty acids derived from nature have even an num-
ber of carbons due to their biosynthesis (acetyl
coenzyme A, two carbon carrier). Some of the fatty
acids may have additional functional groups like
hydroxyl (castor oil), epoxide (vernonia oil), or
ketone (licania oil), as well as triple bonds [14,16].
Although fatty acid pattern varies between crops,
growth conditions, seasons, and purification meth-
ods, each of the triglyceride oils has a unique fatty
acid distribution, as can be seen in Table 15.1 [17].
Hydrolysis of vegetable oils provides about 15 dif-
ferent fatty acids (some of them can be seen in
9 12 15
4 6
Table 15.1 Fatty Acid Composition of Different Plant Oils [14,16]

Fatty Acid Composition (X:Y, where X is the number of carbon atoms and Y is the number of double bonds) %
Palmitic Stearic Oleic Linoleic Linolenic Gadoleic Erucic Ricinoleic
Oil 16:0 18:0 18:1 18:2 18:3 20:1 22:1 18:1
Linseed 5.5 3.5 19.1 15.3 56.6



Soybean 11 4 23.4 53.2 7.8



Palm 44.4 4.1 39.3 10 0.4



Rapeseed 3 1 13.2 13.2 9 9 49.2

Castor 1.5 0.5 5 4 0.5

87.5
Sunflower 6 4 42 47 1



15: BIOBASED THERMOSETS 581

Table 15.1). Triglyceride oils have been used

extensively to produce coatings, inks, plasticizers,
lubricants, and agrochemicals.
The stereochemistry of the double bonds, the O2
degree of unsaturation, and the length of the carbon
chain are important parameters affecting physical
and chemical properties. The degree of unsaturation
can be expressed by the iodine value (the amount of
iodine in grams that can react with double bonds
present in 100 grams of sample). According to iodine O OH

value, oils can be divided into three categories:

(1) drying oils (iodine value above 130, e.g. linseed
oil), (2) semi-drying oils (iodine value between 90
and 130, e.g. sunflower or soybean oil), and (3) non-
drying oils (iodine value below 90, e.g. palm kernel
oil) [17]. Triglycerides contain active sites amenable
to chemical reaction: the double bond, the allylic car-
bons, the ester group, and the carbons alpha to the
ester group. These active sites can be used to intro-
duce polymerizable groups on the triglyceride using
similar techniques applied in the synthesis of
petrochemical-based polymers. The key step is to
reach a higher level of MW and cross-link density, as
well as to incorporate chemical functionalities known
to impart stiffness in a polymer network (e.g. aro-
matic or cyclic structures) [14].
There are three main routes to obtain polymers
from plant oils: (1) direct polymerization through
the double bonds, or through other reactive func-
tional group present in the fatty acid chain,
(2) chemical modification of the double bonds,
which introduces functional groups to facilitate the
polymerization, and (3) chemical transformation of
plant oils to produce platform chemicals that can be
used to produce monomers for the polymer synthe-
sis, usually through the conversion of the triglycer-
ides into mono/diglycerides or into simple fatty
acids [12].
Direct Polymerization of Natural Oils
Double bonds present in fatty acids can be poly-
merized through a free radical or cationic mechanism.
Drying oils, such as linseed or tung oil, are
vegetable oils which polymerize through a free-radical
mechanism [18]. The double bonds react with atmo-
spheric oxygen, which leads to the formation of a net-
work in a reaction called oxypolymerization, as can be
seen in Figure 15.2. These oils are film-formers and
are mostly used in paints, coatings, inks, and resins.
The reaction mechanism can be summarized as
O
Figure 15.2 Oxypolymerization of triglycerides.
follows: an initial hydrogen abstraction on the methy-
lene group between two double bonds that leads to the
formation of conjugated peroxides, and then, radical
recombination that produces cross-linking (alkyl,
ether, or peroxy bridges [19
21]. Oils with high
iodine value can also be polymerized directly via cat-
ionic polymerization using boron trifluoride diethyl
etherate as initiator [20].
Direct cationic homogenous copolymerization of
some vegetable oils with olefinic copolymers such
as styrene, divinylbenzene, norbornadiene, or dicy-
clopentadiene can be achieved using BF3OEt2 mod-
ified with methyl oleate or Norway fish oil ethyl
ester as initiator [12]. Ronda et al. [12] has shown
that a cationic polymerization of soybean oil with
styrene, divinylbenzene, and trimethylsilylstyrene
can lead to flame retardant bio-based thermosets. In
order to accelerate the reaction that usually pro-
ceeds for long periods of time due to low reactivity
of the internal double bonds, microwave irradiation
was used as an alternative to a heat source.
Chemical Modification of the Double
Bonds of Natural Oils
There are two different sites in triglycerides
available to chemical modification: ester groups,
which can be readily hydrolyzed or trans-esterified,
582 HANDBOOK OF THERMOSET PLASTICS

double bonds along the aliphatic chains, and
hydroxyl groups [22]. Some of the important chem-
ical pathways of functionalization are described in
the following sections.
Epoxidation of Triglycerides
Epoxidized triglycerides can be found in natural
oils, such as vernonia (see vernolic acid,
Figure 15.3), or can be obtained from unsaturated
oils by a standard epoxidation reaction. Different
pathways of epoxidation can be found in the litera-
ture. Epoxides of fat and oils and their ester deriva-
tives are usually used as plasticizes, toughening
agents, and stabilizers in plastics industry, espe-
cially as alternative plasticizers for the polyvinyl
chloride (PVC) industry. Linseed oil is the most
epoxidized oil due to the high content of double
bonds (linolenic acid), and is commercially avail-
able. Epoxidized soybean oil is also commercially
available, usually with a functionality of 4.1
4.6
epoxy rings per trygliceride [14]. The oxirane ring
is useful for further chemical modifications and for
the synthesis of thermosetting resins by cross-
linking with anhydride or amine compounds or by
homopolymerization of the oxirane rings initiated
by catalysts [23]. Epoxidation can be done using
organic and inorganic peroxides together with a
metal catalyst; it can also be obtained using halohy-
drins (haloalcohols), molecular oxygen, and by in
situ epoxidation with percarboxylic acid.
A suitable technique for clean and efficient epoxi-
dation of vegetable oils is the epoxidation in situ
CO2H
O
Figure 15.3 Vernolic acid.
with percarboxylic acid using Acidic Ion Exchange
Resin (AIER) as the catalyst [24]. It is possible to
use either acetic acid or formic acid as the carbox-
ylic acid in the epoxidation process. Peroxy-acid is
created by the reaction between hydrogen peroxide
and the carboxylic acid. The process can be con-
trolled by the quantitative analysis of oxirane rings
and iodine number [25]. Different catalysts have
been studied, including ion-exchange resins, phos-
photungstic acids, rhenium catalysts, titanium cata-
lysts, and enzyme catalysts [26,27]. A schematic
example of a triglyceride epoxidation process can
be seen in Figure 15.4. Chemo-enzymatic epoxida-
tion is a relatively new process and has the advan-
tage of suppressing undesirable ring opening of the
epoxide. In this method, unsaturated fatty acid or
ester is initially converted into unsaturated percar-
boxylic acid by a lipase-catalyzed reaction with
hydrogen peroxide and is then self-epoxidized via
an intermolecular reaction [28,29]. The epoxidation
of triglycerides makes them capable of reacting via
ring opening [30]. Arkema is already commercializ-
ing a line of epoxy plasticizers from renewable
sources under the trade name of Vokoflex based
on epoxidized linseed oil, soybeans, and tall oil of
fatty acids [31]. The preparation of bio-based epoxy
resins from epoxidized vegetable oils will be dis-
cussed later.
Acrylation of Epoxidized Oils
Acrylation of epoxidized oil can be achieved
from the synthesis reaction of acrylic acid with
epoxidized triglycerides [14,32]. Acrylated trigly-
cerides can react via additional polymerization.
Acrylated epoxidized soybean oil is commercially
available for the surface coatings industry. The
reaction of acrylic acid with epoxidized soybean oil
occurs through a standard substitution, as can be
seen schematically in Figure 15.5. Although the
reaction of epoxidized soybean oil with acrylic acid
is partially catalyzed by the acrylic acid, the use of
additional catalysts such as tertiary amines or

O
O O
O Formic/acetic acid O
O O O
O O
O
O Catalyst O
O O O
Peroxide

Figure 15.4 Epoxidation process.

15: BIOBASED THERMOSETS
Figure 15.5 Acrylation of epoxidized triglyceride oil (soybean oil).
organometallic catalysts is common. The resulting
polymer properties can be controlled by changing
the molecular weight of the monomer or the func-
tionality of the acrylated triglyceride, residual
amounts of unreacted epoxy rings, as well as newly
formed hydroxyl groups, both of which can be used
to further modify the triglyceride by reaction with a
number of chemical species (such as diacids, dia-
mines, anhydrides, and isocyanates). The polymer
can be stiffened by the introduction of cyclic or
aromatic groups [14].
Maleinization of Acrylated Epoxidized Oils
According to Wool [14], oligomers of malei-
nizated acrylated epoxidized oils can be obtained
by reacting the acrylated epoxidized oil with maleic
anhydride (Figure 15.6). The maleinization reaction
introduces more double bonds in the triglycerides.
The reaction, if not controlled, can lead to an
increase in the viscosity, which leads to gelation of
the oligomer. After maleinization the oligomer can
be cured with styrene.
Hydroxylation of Triglycerides
The introduction of hydroxyl groups at the posi-
tion of double bonds creates polyols that can be
used in the polyurethane and polyester industry, as
well as for creating new pathways for triglyceride
functionalization [33]. Natural occurring hydroxyl
groups can be found in ricinoleic acid (castor oil).
The hydroxylation can be done by reacting an
epoxidized triglyceride with an acid, or alterna-
tively by the hydroxylation of the double bonds.
Ring opening of epoxidized triglycerides can be
obtained by reacting with hydrochloric or hydrobro-
mic acid or by an acid-catalyzed ring-opening reac-
tion with methanol (yielding methoxylated polyol),
or reacting with water forming vicinal hydroxyl
groups, or even through a catalytic hydrogenation
583
[30]. The cross-linking density of thermoset poly-
mers obtained from hydroxylated oils depends on
the number of hydroxyl groups in the oil and the
position in the fatty acid (end or middle of the fatty
acid chain) [33]. The hydroxylation process can be
controlled, measuring the hydroxyl values accord-
ing to the ASTM titration method (D 1957-86). The
reactivity of the polyol obtained is relatively low
due to the nature of the secondary alcohol.
Furthermore, multiple numbers of hydroxyl groups
with varied reactivity are also obtained, which leads
to premature gelation [34].
Hydroformylation is another method for prepar-
ing polyols; hydrogenation of the formyl group pro-
duces hydroxyl, using cobalt or rhodium as
catalysts, at high temperatures [35]. In this process
aldehydes are formed and an extra carbon is intro-
duced per double bond. Hydroformylation creates
primary hydroxyl groups which are more reactive
than the secondary polyols created via epoxidation
(Figure 15.7) [13].
Ozonolysis is another alternative chemical pro-
cess utilized to synthesize polyols with terminal
hydroxyl groups from vegetable oils. Ozone, a very
powerful oxidation agent, is used to cleave and oxi-
dize the double bonds in the vegetable oil and then
the ozonides formed are reduced to alcohols using
NABH4 or similar catalysts. Tran et al. [34] devel-
oped a method to synthesize vegetable oil-based
primary polyol (soybean oil) in a single-step ozono-
lysis procedure. When the oil is exposed to ozone
in the presence of ethylene glycol and an alkaline
catalyst, double bonds are cleaved, yielding a mix-
ture of polyols that is dependent on the relative
concentration of the unsaturated fatty acids present
(Figure 15.8). In this type of ozonolysis, the ozo-
nides produced react with the hydroxyl group of
the glycol to form an ester linkage with a terminal
hydroxyl group.
584 HANDBOOK OF THERMOSET PLASTICS

H2COH

H2COH CH2

CH2 H2COH
CH2
OH
H2COH HO CH
OCH3 CH2

CH3 CH HCO
CH3O CH3O
CH O CH
HCOH CH3O
HOC CH CH2OH HC (Carbohydrate) H2COH
OH OCH3
HC O OCH3
O H2COH HC O
CH3O
H2COH
CH3O OCH3 HC OH O CH
CH3O
O CH

HC O HC O C2H H2COH

OCH3 HC O
HC HC CH H2COH
CH3O
O CH O CH HCOH
HOCH2 OH H2C H2COH
HOCH OCH3 HOCH HC O
HC H2COH OCH3 CHO
CH3O CHO
H2C O CH O CH
O CH CH3O
HOC CH CH2OH HC O CH
O CH
CH3O O HOCH H2COH
HOCH2
CH3O O CH HC
OCH3 OCH3
CH3O
HCOH2 HC O
CO OH
H2OCH CO
O CH
CH3O
CH3O HC CH HC O CH2
HOCH2 OCH3
HC CH2 HO CH HC O
O
H2OCH HCOH
HCOH

HCOH CH3O
O
H2CO OCH3
OH

Figure 15.6 Maleinization of acrylated epoxidized triglyceride oil (soybean oil).

H CH O H CH2 OH
Catalyst H2
C C + CO + H2 C C C C
Pressure Catalyst

Figure 15.7 Hydroformylation process [13].

15: BIOBASED THERMOSETS 585

(a)
O
O
O
O O3 OH O
O OH
O
OH O
HO +
O O
O
HO R

(b)
O
O
O
O O3 OH O
O OH
O
O
OH
HO +
O O
O O
HO OH
O O

+
O
HO
O
(c)
O
O
O
O O3 OH
O
O OH
O
OH O
HO +
O O O
O
HO OH
O O

+ O
HO
O

Figure 15.8 Alkaline-catalyzed ozonolysis of soybean oil with ethylene glycol using triglyceride containing
different fatty acids: (a) oleic acid, (b) linoleic acid, and (c) linolenic acid [34].

Maleinization of Hydroxylated Oils to obtain enone-containing triglycerides from high

The synthesis of maleinized hydroxylated oil is
similar to that used to obtain acrylated epoxidized
oil. After the hydroxylation, the oil is reacted with
maleic anhydride in order to functionalize the tri-
glyceride with maleate half-ester, as can be seen in
Figure 15.9. The reaction can be catalyzed with
N,N-dimethylbenzylamine [14].
Enone-Containing Triglycerides
According to Ronda et al. [12], allylic hydroper-
oxides can be readily prepared by reacting
alkenes with photochemically generated singlet
oxygen, which results in a mixture of enones
(Figure 15.10). The researchers utilized this process
oleic sunflower oil. Enone-containing triglycerides
are interesting alternatives to epoxidized oils for
the production of thermosets by cross-linking with
amines via aza-Michael addition [12].
Conversion of Triglycerides into Mono/
Diglycerides/Simple Fatty Acids
The conversion of the triglycerides into mono/
diglycerides or into simple fatty acids can produce
platform chemicals for producing monomers toward
polymer synthesis. Mono or diglycerides can be
obtained using a transesterification reaction with
glycerol (glycerolysis). Standard glycerolysis
586 HANDBOOK OF THERMOSET PLASTICS

Figure 15.9 Maleinization of hydroxylated triglycerides.

O O
O O
O
High oleic sulflower oil (85% oleic acid)
O

O2, TPP, h, CH2CI2, 6h

OOH O O OOH
O O
O
OOH O

Ac2O/Et3N, 4h
O O O O
O O
O Mixture of isomers. 2.6 enone
O O groups per triglyceride molecule

H2N NH2
90C to 120C, 12h

O
O
O
O
O O O
HN

Aza Michael cross-linked triglycerides

Soft rubbers Tg (DMTA) = 16C

O HN O O
O
O
O O

120C to 160C, 12h

Tough thermosets Tg (DMTA) = 64C

Figure 15.10 Synthesis of enone-containing triglycerides from high oleic sunflower oil, cross-linked with 4,40 -
diaminodiphenylmethane [12].
15: BIOBASED THERMOSETS 587

O C OH 230-240C
O
2 OH %1 Ca(OH)2
1 O C +
O
OH
O C
z
Glycerol
Soybean oil
O
O

O C O C
O

O C
OH
+

OH
OH
Diglyceride
Monoglyceride

O O
CH2 C C O C C CH2
55C CH3 CH3
Pyridine,
Hydroquinone
Methacrylic anhydride

O O

O C O C
O O
O CH3
O C CH2 C C OH
O C C CH2 +
+
CH3
O CH3 O CH3
O Methacrylic acid
C C CH2 C C
O CH2

Figure 15.11 Glycerolysis reaction of soybean oil followed by methacrylation.

requires high temperatures and the use of an inor-
ganic homogeneous catalyst such as sodium, potas-
sium, or calcium hydroxide. Although this process is
energy consuming it has high conversion rates and
relatively short reaction times [36]. Enzymatic gly-
cerolysis of fats and oils at atmospheric pressure at
nearly ambient temperatures has been investigated in
the last decade and has been found to be an attractive
and advantageous route compared to the chemical
process [37,38]. Usually the product of glycerolysis
is a mixture of monoglycerides, diglycerides, and
glycerol. According to Can et al. [39] maleinization
of soybean oil and castor oil monoglycerides can
produce maleate half-esters which in turn can react
via addition polymerization. Maleates are relatively
unreactive with each other and the addition of sty-
rene increases the polymerization conversion rate
and the stiffness of the resultant polymer.
Methacrylation of Monoglycerides
Methacrylation of monoglycerides can be per-
formed after the glycerolysis of the triglyceride (soy-
bean oil). The glycerolysis product can be reacted
with methacrylic anhydride to form the methacrylic
ester of the glycerides and methacrylic acid using
pyridine as catalyst and hydroquinone as inhibitor of
the radical polymerization of the methacrylic esters
(Figure 15.11).
588
Glycerol
Glycerol is a non-toxic, edible, biodegradable
compound. It is an extremely versatile building
block. Glycerol is usually found in pharmaceuticals,
cosmetics and personal care products, alkyd resins,
etc. Glycerol is produced in two forms: natural
glycerol, as a by-product of the oleochemical and
biodiesel industries, and as synthetic glycerol, from
propylene. Glycerol forms the backbone of trigly-
cerides and is mainly produced by saponification of
oils as a by-product of the soap industry. Around
75% of the glycerol produced in the United States
is derived from natural sources [40]. Glycerol can
be used as oligomers or co-monomers in copoly-
mers. Catalyzed self-condensation of glycerol
yields a mixture of linear and branched oligomers.
Linear growth involves only the primary hydroxyl
groups while the secondary ones can have conse-
quences. The preparation of hydroxyesters or
hydroxyacids from glycerol and their polyconden-
sation by transesterification can lead to exquisite
polymers such as hyperbranched polycarbonates
and polyesters [41]. In recent years the amount of
natural glycerol-based monomers increased consid-
erably, and includes diols, diacids, hydroxyacids,
oxiranes, acrolein, and acrylic acid, among others.
Ethylene and propylene glycol are particularly rele-
vant for the polyester market (polyethylene tere-
phthalate and polytrimethylene terephthalate).
Saccharides
Carbohydrates are considered a very important
renewable source of monomers for the preparation
of a variety of polymers since they are the most
abundant class of organic compounds found in liv-
ing organisms. Sugars and starches are carbohy-
drates used as sources of metabolic energy in plants
and animals, while cellulose, also a carbohydrate,
serves as structural material. Carbohydrates are also
called saccharides, and small molecules of sacchar-
ides are called sugars. They can be divided into
three categories: (1) monosaccharides (glucose,
galactose, and fructose); (2) oligosaccharides, a
combination of two to ten monosaccharides; and
(3) polysaccharides such as cellulose, starch, glyco-
gen, and hemicellulose [42]. The most abundant
oligosaccharide is sucrose, a disaccharide of glu-
cose and fructose. The vast majority of carbohy-
drates present in nature are polysaccharides, with
HANDBOOK OF THERMOSET PLASTICS
starch and cellulose being the most abundant.
Starch is a branched polymer while cellulose is a
long, rigid molecule. Sugar-based monomers can be
introduced into polymer architecture as follows:
(1) Addition reactions involving vinyl-type sacchar-
ides; (2) functionalization based on appending the
carbohydrate to a reactive backbone; and (3) poly-
condensation reactions of sugar-based monomers
[41]. Sugars are basically polyols with a high num-
ber of hydroxyl groups along the chain. In order to
control the reactivity of the many different
hydroxyl groups on carbohydrates, simple mole-
cules with two hydroxyl groups are desired.
Dianhydrohexytols, such as isosorbide, isomannide,
and isoidide (Figure 15.12), are a result of intramo-
lecular dehydratation; having two reactive hydroxyl
groups, they can be used as raw material for poly-
condensation, which leads to polyester, polyether,
or polyurethane chiral polymers. Isosorbide is pre-
pared from starch, isomannide from D-mannose,
and isoidide from isosorbide [41]. Isosorbide, or
1,2,3,6-dianhydrosorbitol, is the product of a multi-
step process, starting with starch, and passing
through D-glucose and sorbitol. It is produced from
biomass in a combination of enzymatic and chemi-
cal technologies [44]. Due to steric effects and
hydrogen bonding, isomannide with two endo
hydroxyl groups is the least reactive compound
compared with isoidide, which has two exo
hydroxyl groups. However, isoidide is rare in
nature while isosorbide is widely available [45].
Isosorbide, which is water soluble and non-toxic,
can be a substitute for bisphenol A in different
polymers, especially in epoxy polymers. It can be
attached to glycidyl ether or allyl ether to make
cross-linkable epoxy monomer with similar proper-
ties to bisphenol A-diglycidyl ether [46]. According
to Feng et al. [45] the bisisosorbide diglycidyl ether
can be prepared by heating isosorbide with sodium
hydroxide solution with a large excess of epichloro-
hydrin. Two equivalents isosorbide are linked to
Figure 15.12 Structures of isosorbide, isomannide,
and isoidide [43]. (Reprinted with permission from
the National Academy of Engineering.)
15: BIOBASED THERMOSETS 589

three molecules of epichlorohydrin to form the centers accommodate the inter-flavonoid bonds. A-
epoxide dimer (Figure 15.13). rings in tannins are highly reactive to aldehydes
Xylitol, sorbitol, mannitol, and maltitol (formaldehyde) in wood adhesive compositions and
(Figure 15.14) are additional naturally occurring the reaction kinetics can be controlled by the addi-
sugar alcohols; polyols that can be polycondensated tion of alcohols to the system. Self-condensation
with dicarboxylic acids such as sebacic acid, citric reactions of polyflavonoid tannins are used to pre-
acid, glutaric acid, and others [47]. The polymer pare adhesives in the absence of aldehydes. The
obtained can be made photo-cross-linkable by add- reaction is based on the opening under alkaline or
ing methacrylate units to the polymer. acid conditions of the flavonoid repeating unit and
the subsequent condensation of the reactive center
with free sites of a flavonoid unit on another tannin
Polyphenols chain [48].
Naturally occurring polyphenols are character-
ized by the presence of multiple phenol structural
units. Tannins are a naturally occurring broad class
of polyphenols present in trees and shrubs. Tannins
can appear in nature as condensed tannins (polyfla-
vonoids) or hydrolyzable tannins [41]. Condensed
tannins are oligomeric in nature while hydrolyzable
tannins are non-polymeric. Tannin has been used
for centuries in leather treatment. Tanning leather
involves a process which permanently alters the
protein structure of leather, thus increasing its dura-
bility. Condensed tannin constitutes more that 90%
of the total world production of commercial tannins
(Figure 15.15). Hydrolyzable tannins are a mixture
of phenols based on complex substances built with
simple molecules such as gallic acid, ellagic acid,
flavogallonic acid, valoneic acid, etc. Hydrolyzable
tannins have relatively low reactivity. In condensed
tannins the main polyphenolic pattern is represented
by flavonoid moieties based on resorcinol A-rings
and pyrogallol B-rings. A-rings contain one highly
reactive nucleophilic center while the other reactive Figure 15.14 Naturally occurring polyols.

HO
O NaOH
CI H2O
3 +
O
O
OH

Epichlorhydrin Isosorbide

O
O

O O O
O O
O
OH O
O

Bisisosorbide diglycidyl ether

Figure 15.13 Bisisosorbide diglycidyl ether preparation [45].

590
Figure 15.15 Condensed tannin.
Lignin is the second most abundant organic poly-
mer on Earth, after cellulose, and the most abun-
dant polyphenol in nature. It is most commonly
derived from wood. Lignin is an integral part of the
secondary cell wall of plants and some algae and
has the function of bonding cells together in the
woody stems, giving the stem rigidity and impact
resistance [14]. Lignin accounts for 24 to 33% of
the dry matter of softwood and 16 to 24% of the
hardwood [49]. Lignin chemical structure is based
on syrigyl, guaiacyl, and p-hydroxyphenol, bonded
together by a set of linkages to form a complex
matrix [50], as can be seen by the schematic
structure in Figure 15.16. Lignin is a complex,
three-dimensional, amorphous, cross-linked pheno-
lic-based polymer. It is a by-product of paper pulping
and biorefineries, and is considered a waste product.
Lignin is separated from wood during pulping and
papermaking operations where it serves as fuel for the
process. Major differences exist between lignin
derived from different pulping processes [51]. Sulfite
processes generate water-soluble sulfonate lignin
while kraft processes generate alkaline soluble lignin.
Hydrolysis lignin is produced by strong hydrolysis,
organosolv lignins are produced from different
organic solvent-based systems, and steam-explosion
lignin is obtained through high temperature/pressure
treatment with steam [42]. Recent pulping trends
involving organic solvents (organosolv) produce less-
modified, sulfur-free lignins, which simplifies the
pyrolysis process for obtaining low-molecular-weight
HANDBOOK OF THERMOSET PLASTICS
lignin sub-products [52]. All chemical pulping pro-
cesses are associated with the chemical splicing of
natural lignin producing fragments with high molecu-
lar weights [41].
Polymeric lignins can be used in thermosetting
resins and as additives in thermoplastic polymers.
Lignin can be chemically modified to improve
polymer-lignin compatibility and to introduce reac-
tive sites. The phenyl propane units in lignin
are generally bonded through carbon and ether
bonds, where only ether bonds can be easily dis-
rupted. The methoxy group substituted at the ortho
positions also influences the reactivity and solubility
of the lignin [49]. Lignin and its degradation pro-
ducts can originate various polymers such as
phenol
formaldehyde, poly(azophenylenes), polyi-
mides, polyurethanes, polyesters, polyamides, poly-
phenylene oxides, polyphenylene sulfide, and others.
Due to the high number of reactive hydroxyl groups
present, esterification and etherification are the most
common reactions used for chemical modification of
the lignin. According to Lora et al. [51], etherifica-
tion with alkylene oxides (ethylene oxide, propylene
oxide, and butylene oxide [53,54]) results in hydro-
xyalkyl lignin derivatives with aliphatic hydroxyl
groups. Nonphenolic hydroxypropyl lignins are
already commercially available in the market.
Extended alkyl ether chain lignins can be also pre-
pared, although propylation through heterogeneous
reaction of lignin with propylene oxide can lead to
unpredictable and even dangerous reactions [51].
Etherification and acetylation of lignin provide solu-
bility in a variety of organic solvents such as ace-
tone, tetrahydrofurane, and chloroform. Lignins can
also be sulfonated, sulfomethylated, aminated, halo-
genated, and nitrated.
According to Wool et al. [14], grafting of lignin
is another possible chemical modification, despite
the inhibiting effect of the phenolic hydroxyl
groups, which reduces the efficiency of the process.
The addition of polar solvents, such as alcohols,
can increase the efficiency though swelling the lig-
nin molecules improves the accessibility of the
reagents. Lignin has reportedly been grafted with
methyl methacrylate, vinyl acetate, styrene, acrylo-
nitrile, acrylic acid, acrylamide, maleic anhydride,
and others. Methacrylated lignin can form cross-
linked networks when copolymerized with methyl
methacrylate. Other grafting techniques such as
ionic chain polymerization and chemo-enzymatic
grafting have also been reported [14]. A great deal
15: BIOBASED THERMOSETS 591

H2COH

H2COH CH2

CH2 H2COH
CH2
OH
H2COH HO CH
OCH3 CH2

CH3 CH HCO
CH3O CH3O
CH O CH
HCOH CH3O
HOC CH CH2OH HC (Carbohydrate) H2COH
OH OCH3
HC O OCH3
O H2COH HC O
CH3O
H2COH
CH3O OCH3 HC OH O CH
CH3O
O CH

HC O HC O C2H H2COH

OCH3 HC O
HC HC CH H2COH
CH3O
O CH O CH HCOH
HOCH2 OH H2C H2COH
HOCH OCH3 HOCH HC O
HC H2COH OCH3 CHO
CH3O CHO
H2C O CH O CH
O CH CH3O
HOC CH CH2OH HC O CH
O CH
CH3O O HOCH H2COH
HOCH2
CH3O O CH HC
OCH3 OCH3
CH3O
HCOH2 HC O
CO OH
H2OCH CO
O CH
CH3O
CH3O HC CH HC O CH2
HOCH2 OCH3
HC CH2 HO CH HC O
O
H2OCH HCOH
HCOH

HCOH CH3O
O
H2CO OCH3
OH

Figure 15.16 Generic structure of lignin.

of effort and research has been done to determine
the possible effects of lignin addition to polymers,
introducing functional groups to increase chemical
interactions. Lignin can be used as a co-monomer
in phenolic thermosetting polymers in wood adhe-
sive applications. Lignin can also be co-reacted
with epoxy resins and polyurethane precursors [14].
Star-like macromers from lignin were obtained by
Oliveira et al. [55] through a combination of chain
extension and etherification reaction, synthesizing
lignin with propylene oxide following capping of
OH functional groups with aliphatic ethers.
Polyurethane films were prepared by Kelley et al.
[56] based on hydroxypropyl lignin. In order to
reduce rigidity of the network polyethylene glycol
and polybutadiene glycol extended lignin-based
polyurethanes were prepared mixing two polyol
components prior to cross-linking. Feldman et al.
[50] modified a bisphenol A-based epoxy adhesive
poly-blending with Kraft lignin.
592
Cardanol is the main constituent (97%) of ther-
mally treated cashew nut shell liquid and is based
on phenolic compounds (Figure 15.17). In the last
few decades several new methodologies were
developed for the preparation of polymers using
cardanol [16]. Cardanol is a phenol derivative with
a meta-substituent of a C15 unsaturated hydrocar-
bon chain with one to three double bonds; it has
potential applications in surface coatings and resins.
Cardanol is used to industrially produce phenolic
resins with formaldehyde (novolac) for coatings
applications, generating high-gloss films for indoor
use [57]. Ikeda et al. [57,58] studied oxidative poly-
merization of cashew nut shell liquid using iron-N,
N0 -ethylenebis(salicylideneamine) (Fe-salen) as cat-
alyst, in bulk and at room temperature. A soluble
cross-linkable polymer was obtained. The polymer
was cross-linked using heat and a hard, glossy
film was obtained. Gopalakrishnan et al. [59] devel-
oped a novel polyurethane based on cardanol, con-
densing cardanol with formaldehyde using sebacic
acid as catalyst. The resulting resin (novolac
phenol
formaldehyde resin) was epoxidized, fol-
lowed by hydrolysis in order to obtain a hydroxyl
alkylated derivative, a polyol. The resulting polyol
was reacted with hexamethylene diisocyanates,
generating rigid polyurethanes. Benedetti et al. [60]
developed cardanol-based polyurethanes by react-
ing cardanol derivatives with diisocyanates or poly-
isocyanates and blowing agents in order to obtain
foamed polyurethanes. Cardanol was derivatized by
condensing cardanol with alkylic aldehydes or
acrylic aldehydes with an acid catalyst. The product
was epoxidized and hydrolyzed to obtain polyols,
which in turn were reacted with isocyanates using
blowing agents. Cardanyl acrylate prepolymers
with controlled molecular weight and polydispersity
can be used in the formulations of inks, coatings,
and adhesives with good adhesion and gloss [16].
Campaner et al. [61] investigated the use of
cardanol-based novolac resins as curing agents of
commercial epoxy resins. The novolacs were pre-
pared by the condensation reaction of cardanol and
paraformaldehyde using oxalic acid as catalyst.
Proteins
Proteins are readily available raw materials from
plants (wheat gluten, soy, sunflower, and zein) and
animals (collagen, keratin, casein, and whey) [62].
Proteins are macromolecules consisting of one or
HANDBOOK OF THERMOSET PLASTICS
Figure 15.17 Structure of cardanol.
more polypeptides, based on amino acids (up to 19
different amino acids) bonded together by peptide
bonds. Polypeptides are usually folded into globular
or fibrous form according to their biological func-
tion [63]. Proteins hold together, protect, and pro-
vide structure to the body of living organisms in
the form of skin, hair, calluses, cartilage, muscles,
tendons, and ligaments. Proteins can catalyze, regu-
late, and protect the body chemistry as enzymes,
hormones, antibodies, and globulins [64]. Most pro-
teins fold into 3-dimensional structures. The pri-
mary structure of proteins is defined by the
sequence of amino acids in the chain; the folding
pattern defines the secondary structure, resulting
from the rigidity of the amide bond and from intra-
molecular hydrogen bonding. Coiling and aggrega-
tion of polypeptides creates the tertiary structure.
The quaternary structure refers to the spatial
arrangement of a protein, as an oligomeric structure
containing several subunits [42]. Covalent disulfide
cross-linking bonds stabilize the tertiary and quater-
nary structures. The shape into which a protein nat-
urally folds is known as its native conformation.
Denaturation is the breakdown of the tertiary
structure of a protein, and involves structural or
conformational changes to native structure, such as
unfolding of the protein molecule [14]. These
changes can be induced by pH, detergents, heat,
etc., and are accompanied by irreversible enthalpy
changes [63]. Plasticization of proteins can be
obtained by the interaction between molecules of
plasticizer and protein macromolecules via polar
interactions (with hydroxyl groups) that increase, as
a result, the free volume. Through plasticization,
proteins can be transformed using various
15: BIOBASED THERMOSETS
processing methods [42]. According to Verbeek
[62], melt extrusion of proteins can occur through
denaturation, dissociation, unraveling, and align-
ment of polymer chains. The presence of disulfide
cross-links in this case is unfavorable, and
decreases chain mobility, increases viscosity, and
prevents homogenization. Proteins usually decom-
pose at temperatures below the softening tempera-
tures, and the introduction of plasticizers helps to
avoid degradation. Animal and vegetable proteins
can be cross-linked by the reaction of tannic acid,
chromic acid, or formaldehyde. The use of proteins
as raw materials for polymers is not new. Some of
the earliest plastics were based on casein, phospho-
proteins found in abundance in cow milk. Casein-
based paints were used until the late 1960s, when
they were replaced by acrylic-based paints.
Another important cow milk protein is the whey
protein, isolated from the whey, a liquid by-product
of cheese production. The protein in cows milk is
20% whey protein and 80% casein protein. Whey
protein films and coatings have been the focus of
recent research as potential materials for high oxy-
gen barrier packaging [65,66]. Whey protein can be
plasticized using glycerol and sorbitol [66]. Gao
et al. developed whey protein-based aqueous
polymer-isocyanate adhesives. The adhesive prop-
erties improved cross-linking of the resulting poly-
mer with methylene bisphenyl diisocyanate [67].
Zein, a class of prolamine protein found in corn,
was historically used as polymeric resins and coat-
ings in a variety of applications such as fibers and
tough, glossy, and grease-resistant coatings. Zein
has also antimicrobial resistance and can be cured
with formaldehyde. Zein has regained interest in
the last few years, and the water resistance was
improved by chemical modification where hydro-
phylic groups such as aNH2, aOH, aCOOH, and
aSH were modified by hydrophobic groups or
polymer segments. Plasticizers can be introduced in
order to flexibilize zein films. Wu et al. [68] intro-
duced dibutyl L-tartarate (DBT), which contains
ester and hydroxyl moieties to form potential
hydrogen bonds with zein. Sessa et al. [69] intro-
duced isocyantes and diisocyanates to reduce the
hydrophilicity of zein and, as a consequence,
decrease the water moisture uptake. Cross-linking
through isocyanate moieties should improve dimen-
sional stability. Lai et al. [70] used oleic acid to
plasticize zein, thus creating more flexible and
tough films.
593
Collagen, a triple helical, self-organizing protein,
is the main component of connective tissue and is
the most abundant protein in mammals. Mano et al.
[71] has shown that collagen can be effectively
cross-linked with glutaraldehyde in order to over-
come the drawbacks of fast biodegradation and
lack of mechanical properties.
Albumin usually refers to any protein that is
water soluble and denatures by heat. Oss-Ronen
et al. [72] conjugated serum albumin to polyethyl-
ene glycol (PEG) and cross-linked it to form
PEGylated albumin hydrogels. The main applica-
tion is as scaffolds for controlled drug release.
Gluten is a protein composite based on gliadin and
glutenin, forming, together with starch, the endo-
sperm of grass-related grains. The term gluten comes
from Latin, meaning glue, due to its adhesive prop-
erties. Gliadin and glutenin comprise around 80% of
the overall protein in wheat grains. Wheat gluten is
an important resource for bio-based polymers due to
its viscoelastic properties, mechanical strength, excel-
lent gas barrier properties, low price, and large-scale
availability [73]. Gliadin and glutenin form a cross-
linked network that contributes to the extensibility of
mixed dough. In order to reduce the strong intramo-
lecular interactions, plasticizers are usually required,
which leads to an undesired reduction in mechanical
properties. Gluten has found applications in the
pressure-sensitive adhesives field [74]. A gluten-
based PSA, with internal plasticizer, was developed
by Aranyi et al. [75]. An acetic acid soluble hydroly-
sate was obtained using a hydrochloric and acetic
acid mixture. The gluten hydrolysate was then epoxi-
dized using ethylene oxide, and generated a water
soluble, epoxidized gluten hydrolysate. This hydroly-
sate was then reacted with hydroxyethyl methacrylate
giving rise to an acrylic copolymer of gluten with
PSA properties. A reduction in water vapor transmis-
sion of gluten coatings was obtained by Cho et al.
[76] using glycerol as plasticizer and oleic acid as a
hydrophobic component. Kim et al. [77] developed a
gluten/zein composite with flexural properties similar
to those of polypropylene.
Soy protein is the major co-product of soybean
oil extraction comprising around 50% of the
defatted soy flour [42]. Soy protein is a storage pro-
tein held in discrete particles called protein bodies
which provide amino acids during soybean seed
germination. Soy protein comprises a high percent-
age of water soluble albumins and salt solution sol-
uble globulins. Water is considered a major
594
plasticizer in the processing of soy proteins. High
quantities of water content reduce the denaturation
temperature of soy proteins. Soybean protein plas-
tics can be prepared using a variety of different
processes: compression molding, injection molding,
and lamination [78]. According to Sun [14], smooth
surface soy protein plastics can be prepared by hot
pressing soy protein at 150C, the temperature at
which soy protein molecules melt and unfold, lead-
ing to a homogeneous distribution. A posterior
interaction between the molecules leads to entan-
glement upon curing.
Plastics based exclusively on soy protein are
rigid and brittle and plasticizers are usually intro-
duced in order to increase the flexibility and tough-
ness. Polyols have often been used as plasticizers.
Plasticizers disrupt molecular interactions, decreas-
ing the forces holding the chains. According to Sun
[14], polypropylene glycol and glycerol appear to
be more compatible with soybean protein and eas-
ier to introduce between protein chains. Mo et al.
[78] studied the effect on soy protein properties of
different plasticizers, such as glycerol, polyethylene
glycol, and butanediols (1,2- and 1,3-substituted).
Ethylene glycerol, propylene glycerol, sorghum
wax, and sorbitol have also been studied for this
purpose [42,79]. Addition of cross-linking agents
such as formaldehyde, glutaraldehyde, and adipic/
acetic anhydride improve mechanical properties as
well as the water resistance of the resulting soy
protein plastic [80]. Gonzalez et al. [81] used the
naturally occurring cross-linker genipin, a chemical
compound found in gardenia fruit extract, in order
to tailor mechanical properties and biodegradabil-
ity. Denaturants such as sodium dodecyl sulfate and
urea also act as plasticizers, reducing the glass tran-
sition temperature and increasing tensile strength,
elongation, and water resistance. A high degree of
entanglements and cross-links is expected when a
high degree of denaturation is obtained, leading to
an increase in stiffness and strength. Su et al. [82]
investigated the moisture barrier properties of
blends of soy protein with polyvinyl alcohol using
glycerol as plasticizer. Water vapor transmission
was significantly affected by the PVA content.
Studies on chemical modification of soy proteins
with monomers or oligomers have been done based
on functional groups able to react with hydroxyl or
amino groups in the protein. Acetylation and esteri-
fication are known pathways for chemical modifi-
cation [80].
HANDBOOK OF THERMOSET PLASTICS
Soy protein can be modified using polycapro-
lactone/hexamethylene diisocyanate prepolymer
[68]. It was found that HDI-modified PCL forms
urea
urethane linkages with the amino acids in the
protein, increasing substantially the water resistance
and the elongation. Grafting can be obtained with
acrylate-based polymers via free radical reaction,
although branching is created, disrupting the strong
inter and intramolecular interactions [80]. Grafting
with polyurethane pre-polymer has been proved to
enhance toughness and water resistance [42].
Soy can be used as an adhesive and the perfor-
mance can be controlled depending on the particle
size and structure of the protein, viscosity, and pH
[83]. In order to enhance the adhesion strength of
soy protein, a chemical modification is needed to
break the internal bonds and uncoil or disperse the
polar molecules. Dispersion and unfolding of pro-
tein is obtained by hydrolysis or by an alkali
environment.
Thermoset from Renewable
Sources
Epoxy
Approximately 90% of all non-bio-based epoxy
in the market is based on diglycidyl ether of
bisphenol A (DGEBA) derived from epichlorohy-
drin and bisphenol A. Epichlorohydrin is an epox-
ide. The conventional, petrochemical process of
producing epichlorohydrin is the chlorohydrination
of allyl chloride, which in turn is made by chlorina-
tion of propylene. Until recently, epichlorhydrin
has also been used to produce glycerol (glycerine).
The large availability of bio-based glycerol,
obtained as a by-product of biodiesel production,
has made the production of glycerol using epichlo-
rohydrin superfluous [4]. Epichlorohydrin can be
produced using glycerol from renewable feedstock.
The glycerin-to-epichlorohydrin (GTE) is a process
based on two chemical steps: (1) hydrochlorination
of glycerin with hydrogen chloride gas at elevated
temperature and pressure using a carboxylic acid as
catalyst, and (2) conversion of the dichlorohydrin
formed in the first step to epichlorohydrin with a
base [84]. This new glycerin-to-epichlorohydrin
process reduces energy consumption by about one-
third, generates less than one-tenth the waste water,
and produces less chlorinated organics, when
15: BIOBASED THERMOSETS
compared to conventional processes [85]. Solvay
Chemicals produces epichlorohydrin from bio-
based glycerol, a by-product of biodiesel produc-
tion using rapeseed, according to EPICEROL
technology [86]. The Dow Chemical Company,
currently the worlds largest producer of epichloro-
hydrin, also announced its intent to manufacture
epichlorohydrin via a novel, acid-catalyzed hydro-
chlorination process using bio-based glycerin [4].
Krafft et al. [87] developed a process from glyc-
erol via 1,3-dichloropropanol. Bio-based DGEBA is
chemically identical to the fossil one, and the bio-
based epichlorohydrin accounts for approximately
20% of the molecular weight of DEGBA. Glycerol-
based epoxy resins such as glycerol polyglycidyl
ether and polyglycerol polyglycidyl ether are indus-
trially available, and have been used in the textile
and paper industry as processing agents, tackifiers,
coatings, etc. Shibata et al. [88] developed a bio-
based epoxy system based on a mixture of commer-
cially available sorbitol polyglycidyl ether (SPE,
DENACOL EX-614B) [89] and glycerol polyglyci-
dyl ether (GPE,DENACOL EX-313) [89] cured
with e-poly(L-lysine) as the bio-based curing agent.
Sorbitol polyglycidyl ether is a multifunctional
epoxy resin obtained by the reaction of epichloro-
hydrin and sorbitol, which in turn is obtained by
the reduction of glucose. Tannic acid was used as
the bio-based curing agent.
Bio-based epoxy can also be obtained using
plant oils and fatty acids. Unsaturated vegetable
oils can be converted into epoxidized oils using
performic acid and peroxide (see the section on nat-
ural oils) or through enzymatic processes [90].
Natural epoxidized oil can be found in vernolic
acid, present in Vernonia species. Epoxidized UV-
curable resins can be synthesized via transesterifi-
cation of vernonia fatty acids with hyperbranched
hydroxyl functional polyether. The resin can then
be cationically polymerized in the presence of ver-
nolic acid and methyl ester as diluents [17].
Epoxidized vegetable oils (castor oil, soybean
oil, linseed oil, etc.) are currently used in epoxy
compositions [91]. Epoxidized oils can be polymer-
ized in the presence of latent catalysts or in the
presence of curing agents, such as anhydrides. The
low reactivity of the epoxy groups together with a
tendency for intramolecular bonding lead to a low
degree of cross-linking. As a result, poor mechani-
cal and thermal properties are obtained with higher
water uptakes, compared to fossil epoxy systems.
595
On the other hand, the polymer obtained is poten-
tially biodegradable via hydrolytic cleavage of
glycerol ester bonds present in the triglyceride oils.
Blends of epoxidized oils and fossil epoxy resins
have also been studied. Epoxidized soybean oil
(EBSO) is considered to be the second largest
epoxide following epichlorohydrin, and it is pre-
pared commercially by epoxidation with percar-
boxylic acids. Epoxidized linseed oil (ELSO) can
be produced by epoxidation with formic acid and
hydrogen peroxide [4].
Tan et al. [92] added epoxidized palm oil to a
fossil-based epoxy blend of diglycidyl ether of
bisphenol A/cycloaliphatic epoxide resin/epoxy
novolac resin in order to obtain a thermal curable
partially bio-based epoxy system. The epoxidized
palm oil acts as plasticizer, thus reducing the glass
transition temperature of the system. In order to
overcome those limitations, Tan et al. [93] synthe-
sized a thermally curable epoxidized soybean oil in
the presence of tetraethylammonium bromide cata-
lyst. Increasing catalyst concentrations led to a
reduction of curing cycles and temperatures, and to
higher degrees of conversion and cross-linking den-
sity. As a result, higher storage modulus and glass
transition temperatures were obtained.
Chemical modification of the epoxidized oils is
another method used to improve final properties.
Transesterification of soybean oil with allyl alcohol
followed by epoxidation in the presence of benzoyl
peroxide, and cured with anhydride, resulted in
highly cross-linked polymers with better mechanical
properties. cis-9,10-Epoxy-18-hydroxyoctadecanoic
acid is a naturally occurring epoxidized monomer
present in birch tree. Lipase-catalyzed condensation
polymerization of this naturally occurring epoxi-
dized acid creates epoxidized oligomers [91].
Lu et al. [94] synthesized high stiffness polymers
from epoxidized linseed oils as a result of the
high degree of unsaturation of the linseed oil.
Chandrashekhara et al. [95] developed a soy-based
epoxy resin consisting of mixtures of epoxidized
fatty acid esters, specifically, epoxidized allyl
soyate. Epon 9500 and Epicure 9550 from Shell
Chemical Company were used as base epoxy resin.
Epoxidized allyl soyate (EAS) was synthesized
through a lab-scale process from food grade soybean
oil. The epoxidized allyl soyate was prepared by
transesterification of triglycerides, and yielded fatty
acid methyl ester and allyl ester using methyl alco-
hol and allyl alcohol, respectively. The fatty acid
596
esters were then epoxidized and yielded soyate
epoxy resins. The resin formulations were prepared
by directly mixing the epoxidized soyate resins into
base Epon resin and curing in one step. The follow-
ing ratios of Epon/epoxidized soyate resins were
used: 100% Epon resin, 90/10%, 80/20%, and 70/
30%. Tensile tests results can be seen in
Figure 15.18. An increase in the ductility could be
noticed with the increase of the epoxidized soyate
resin content, accompanied by a corresponding
decrease in the ultimate strength and modulus. The
increase in the ductility was related to the higher
molecular weight of the soybean oil. It could be con-
cluded that epoxidized allyl soyate provided better
intermolecular cross-linking, yielding tougher mate-
rials as compared to commercially available epoxi-
dized soybean oil. The addition of epoxidized allyl
soyate to a commercial epoxy resin led to a viable
low-cost, high-performance thermoset product with
improved properties when used with glass fibers in
the pultrusion process. The pultruded composites,
based on soy-based resin systems, have shown com-
parable mechanical properties compared to neat
resin. The presence of soybean oil increased the
lubricity, thus reducing the pull force during the pul-
trusion process, an additional bonus.
Espana et al. [96] cured epoxidized soybean oil
of commercial grade (Traquisa S.A.
Barcelona,
Spain, EEW of 238 g/equivalent) with maleic anhy-
dride (AEW index of 98.06 g/equivalent) with the
aid of a mixture of catalysts (1,3-butanediol anhy-
drous and benzyldimethylamine). The mixture was
cured at various temperatures for 5 hours using dif-
ferent epoxidized soybean oil (EBSO):anhydride
(AEW) ratios. The best-balanced mechanical and
thermal properties were obtained for a ratio of 1:1,
representing a high level of cross-linking.
Maximum values of flexural modulus (432 MPa)
and Shore D (70) were obtained for an EBSO:AEW
ratio of 1:1, while maximum glass transition tem-
perature (42.6C) was obtained for a ratio of 1:0.9.
Lignin can be used as the hard segment in epoxy
resin networks, increasing the glass transition of the
resultant polymer. Hirose et al. [97] investigated
the properties of ester-type epoxy resins derived
from lignin. An ester-carboxylic acid derivative of
lignin was previously obtained from the alcoholysis
of lignin with succinic acid anhydride. The ester-
carboxylic acid obtained can be reacted with ethyl-
ene glycol diglycidyl ether to form epoxy resins.
Glass transition temperature increased with
HANDBOOK OF THERMOSET PLASTICS
80
10% EAS
60
Stress (MPa)
Pure epon
40
20% EAS
20
0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07
Strain (m/m)
Figure 15.18 Mechanical properties of soy-based
resin systems [95].
increasing ester-carboxylic acid derivative content,
suggesting that lignin indeed acts as the hard seg-
ment (reaching a maximum value of 211C).
Sugar-based epoxy systems were also developed.
East et al. [98] developed substitutes for bisphenol
A based on bisglycidyl ethers of anhydro-sugars,
such as isosorbide, isomannide, and isoidide
(Figure 15.12). The curing agent used could be
either bio-based polyamines or polycarboxylic
acids. The novel sugar-based epoxy system devel-
oped can be synthesized to be water soluble.
Isosorbide epoxy with equivalent weight 230 g/eq
was cured with methylenedianiline (MDA, with
equivalent weight of 49.6 g/eq) at 80C for 2 hours
and 16 hours at 120C. The glass transition temper-
ature obtained for the cured epoxy was 89C.
Boutevin et al. [99] developed epoxy pre-
polymers from phenol compounds based on flavo-
noids, condensed tannin, or hydrolyzable tannin,
and derivatives of catechin (Figure 15.19), epicate-
chin, gallocatechin, epigaloctechin, etc. Those fla-
vonoids can be epoxidized with epichlorohydrin
according to the schematic reaction shown in
Figure 15.19. The resulting epoxidized flavonoid
can be cross-linked with amine or anhydride, or
mixed with resorcinol diglycidyl ether for posterior
cure. Epoxidized catechin was added to DGEBA at
different ratios: 25:75% and 40:60%. The mixtures
were cured using cycloaliphatic Epamine PC 19
(PO.INT.ER SRL, Italy). Glass transition tempera-
tures obtained for the cured resin containing 25%
epoxidized catechin mixed with 75% DGEBA
(Epikote 828 Resolution Performance Products)
was 48C, while the commercial DGEBA/Epamine
15: BIOBASED THERMOSETS 597

Figure 15.19 Reaction of epoxidation of catechin using epichlorohydrin [99].

O
NH2
O S R
O O
O HO N N OH

O
O
O
O S
NH2
O HO N O

O S S
H2N NH2
O S
AGSO
O

O
+ O

O O S S O
O
O N
R R
O O O
O
HO N N OH
O O O
O
O
O
O O O O

N OH O
ELO

Figure 15.20 Cross-linking reaction between epoxidized linseed oil (ELO) and amine grapeseed oil
(AGSO) [90].

PC 19 system Tg is 47C. For the ratio of 40:60%,
a Tg of 32C was obtained.
Stemmelen et al. [90] developed cross-linking
materials from renewable resources and created
fully bio-based epoxy systems. Amines are consid-
ered the most popular cross-linking agent due to
their nucleophilicity, which makes possible reactiv-
ity at room temperature. Functionalization of natu-
ral oils, such as grapeseed oil, with amine groups
involving the reaction of cysteamine chloride and
UV initiated thiol-ene chemistry created bio-based
cross-linking agents. The curing reaction with a
commercial epoxidized linseed oil can be seen in
Figure 15.20. An additional bio-based curing agent
was developed by Takahashi et al. [100].
A terpene-derived acid anhydride (TPAn) was syn-
thesized by Diels-Alder reaction of maleic anhy-
dride and allo-ocimene obtained by the
isomerization of -pinene, a terpene found in conif-
erous trees.
The authors compared the thermal and mechani-
cal properties of epoxidized soybean oil (ESO)
cured with three different curing agents: terpene-
based acid anhydride (TPAn), hexahydrophthalic
anhydride (HPAn), and maleinated linseed oil
(LOAn). ESO-TPAn showed a higher glass transi-
tion temperature (67.2C) and a higher tensile mod-
ulus and strength.
Wang et al. [101] used rosin as a bio-based cur-
ing agent. Rosin is a natural and abundant product
598
Figure 15.21 Structure of abietic acid, one of the
main components of rosin.
obtained from coniferous trees. The acidic compo-
nent of rosin is mainly a mixture of isomeric
abietic-type acids (Figure 15.21). Rosin and its
derivatives have been used as tackifiers for adhe-
sives, varnishes, paints, etc.
The researchers have studied a rosin-based,
anhydride-type curing agent and rosin-based glyci-
dyl ether-type epoxies. Glycidyl ether of abietic
alcohol was synthesized, reducing first the carboxyl
group of rosin acid to a hydroxyl group, and then
reacting with epihalohydrin to obtain glycidyl
ether.
Cimteclab [102] developed a series of products
based on the phenolic structure currently derived
from cashew shell oil, a by-product of the cashew
nut industry. Novocardt is a curing agent devel-
oped for epoxy systems based on the reaction of
cardanol and paraformaldehyde using oxalic acid as
catalyst [61]. Using Novocardt (18%) as a curing
agent for a composite matrix based on DGEBA
epoxy (EC01, Camattini, Spa, Italy), a Tg of 110C
was obtained, compared to the 122C obtained using
a regular amine hardener. Mechanical properties
obtained were similar to the conventional system
except for the impact strength. The bio-based hard-
ener increased the impact strength from 9.2 kJ/m2 to
24.3 kJ/m2 [103].
Wang et al. [104] synthesized rosin-based flexi-
ble anhydride-type curing agents based on
maleopimarate-terminated polycaprolactone (MPA-
terminated PCL). Commercial epoxy resin (DER
332 Epoxy resin, DOW) was cured with (MPA-
terminated PCL) in different stoichiometric ratios,
HANDBOOK OF THERMOSET PLASTICS
using 2-ethyl 4-methylimidzole as accelerator.
Epoxide/anhydride ratio affects the mechanical
properties. At a ratio of 3:2, the cured resin exhib-
ited clear stress yield. As the ratio increased to 5:2,
the cured resin became less ductile, stronger, and
stiffer. These changes can be attributed to an
increase in the amounts of rigid polyether segments
formed. The length of the soft segment in the cur-
ing agent affected the cross-linking density. As the
molecular weight of the PCL segment increased,
the corresponding cured epoxy became more duc-
tile and less strong.
It can be concluded that the obstacles to replace
petroleum-based epoxy resins with bio-based poly-
mers in commercial applications are mainly due to
inferior mechanical and thermo-physical properties.
In the meantime, bio-based epoxy systems can be
used to partially replace conventional epoxy
systems.
Bio-Based Unsaturated Polyester
Unsaturated polyester resins are widely used as
the matrix in commodity composite materials, usu-
ally reinforced with fiber glass. Unsaturated polye-
sters are produced by polycondensation of
unsaturated and saturated dicarboxylic acids with
diols. Curing reactions are usually performed
through radical or thermal processes in the presence
of vinyl monomers, such as styrene. Polyester resins
are usually classified as: (1) Ortho resins, (2) Iso-
resins, (3) Bisphenol A-Fumarates, (4) Chlorendics,
and (5) Vinyl ester [105]. The most widely used diol
for standard unsaturated polyester is propylene glycol
(1,2-propanediol). Additional polyols are dipentaery-
thritol, glycerol, ethylene glycol, trimethylpropane,
and neopentylglycol [91]. Maleic anhydride and
fumaric acid are among the most common unsaturated
acid monomers used. Phthalic acid (iso or ortho acid)
is the saturated dicarboxylic acid used in all standard
unsaturated polyester resins [4]. Ortho resin is the
least expensive among all polyester resins. Monomers
of styrene are usually used as cross-linking agents,
and solutions of unsaturated polyesters and styrene
vinyl monomers (reactive diluents) are known as
unsaturated polyester resins (UPR). The curing reac-
tion of UPR is a free-radical chain growth polymeri-
zation between reactive diluent (styrene) and the
resin. Curing procedures are considered versatile,
from room temperature to elevated temperature,
according to the catalyst used [105].
15: BIOBASED THERMOSETS 599

These building blocks can be substituted by bio- O O O

based analogs, either partially or even totally, in
some cases. Bio-based propylene glycol (1,2-propa- O O O
nediol) and 1,3-propanediol (PDO) are currently + +
being commercially produced from glycerol. In the
presence of metallic catalysts and hydrogen, glyc- Maleic Phthalic
erol can be hydrogenated to propylene glycol (1,2- anhydride anhydride
(MA) (PA)
propanediol), 1,3-propanediol, or ethylene glycol.
1,3-Propanediol (PDO) is also being used for pro-
duction of bio-based unsaturated polyesters [86]. HO OH
Several entities are working to develop and/or com- 1,3-propanediol
mercialize glycerin-to-propylene glycol technology: (1,3-PDO)
Senergy/Suppes (University of Missouri), Cargill/
Ashland, Archer Daniels Midland (ADM), UOP/ O O O
Pacific Northwest National Laboratory (PNNL),
Virent Technologies (University of Wisconsin), O O
O
Huntsman, and Dow Chemical. The cost of produc- O
tion for propylene glycol made from crude O
O O O
biodiesel-based glycerin is compared to conven-
tional propylene oxide-based propylene glycol
[106]. Page et al. [107] detailed the polymerization
of unsaturated polyester resins based on biologi- O

cally derived 1,3-propanediol. PDO monomers can

be obtained via a fermentation process of corn feed
stocks, using bacterial strains able to convert glyc-
erol into 1,3-propanediol (Susterrat, DuPont).
Maleic anhydride was chosen as the unsaturated
diacid, and anhydride was added in order to
increase the solubility in styrene since aromatic dia-
cids increase the solubility of unsaturated polyesters
in vinyl monomers (Figure 15.22). Solubility in sty-
rene enables storage, handling, and processing of
the unsaturated polyester/vinyl monomer solution.
The solubility is dependent on the ratio between the
saturated and unsaturated diacids, e.g. the ratio
between phthalic anhydride (PA) and maleic anhy-
dride (MA). Compositions containing ortho-
phthalic acid, maleic anhydride, and Susterrat
1,3-PDO were compared to compositions containing
ortho-phthalic acid, maleic anhydride, and 1,2-pro-
pylene glycol (instead of 1,3-PDO) using the same
ratio between the components. The curing was
obtained using styrene (60%). The bio-based com-
position has shown higher tensile strength (70 MPa
compared to 44 MPa), higher flexural strength
(112 MPa compared to 67 MPa), but slightly lower
HDT (67C compared to 75C) [107].
Szkudlarek et al. [108] synthesized low-viscosity
unsaturated polyester resins based on bio-based 1,3-
propanediol and C5-C10 unsaturated dicarboxylic
building blocks, such as bio-based itaconic acid or
Fumaric
fragment
(FA)
Figure 15.22 Unsaturated polyesters based on bio-
based 1,3-propanediol [107].
anhydride. Maleic anhydride was added as the
unsaturated diacid and ortho/isoanhydride was
added as the aromatic saturated diacid building
block. A styrene or methacrylate-containing com-
pound was used as reactive diluent. Radical inhibi-
tors based on phenolic groups such as
hydroquinones, catechols, or phenothiazines may
be added. A tertiary aromatic amine was used as
co-initiator for the free radical polymerization. The
composition containing bio-based itaconic acid and
1,3-propanediol were compared to a fossil-based
composition containing maleic anhydride and 1,2-
propylene glycol (with similar ratio between the
components). The compositions were cured using
the same amount of styrene (65%). The bio-based
unsaturated polyester compositions showed compa-
rable mechanical properties to similar fossil compo-
sitions with higher elongation and slightly lower
HDT (105C compared to 109C). Fatty acids or
oils can be used as polyacids, while rigid carbohy-
drates, such as isosorbide, can be used as polyols.
600
Szkudlarek et al. [109] also synthesized unsaturated
polyester resins using corn-based isosorbide and
1,3-propanediol, corn-based itaconic acid/anhy-
dride, and maleic anhydride in styrene solution.
Isosorbide provides the aromatic building block
needed to obtain the solubility in styrene. Low ther-
mal stability obtained by Szkudlarek et al. was
improved by introducing bio-based itaconic, citra-
conic, and mesaconic ester units [110]. The unsatu-
rated polyester described by the researchers can be
obtained by polycondensation of a polyol (bio-
based 1,3-propanediol or 1,2-propanediol) and
itaconic, citraconic, and/or mesaconic acid or anhy-
dride as unsaturated dicarboxylic acids. The heat
deflection temperature of this new composition was
considerably improved (from 70 to 105C). Citric
acid can also be converted into bio-based polyol.
Kraft lignin, esterified with anhydrides, is soluble
in styrene, and can be used as an additive in unsatu-
rated polyesters, which improves toughness and
connectivity in the polymer network [91].
Epoxidized vegetable oils can be used as a replace-
ment for polyester resins. Robert et al. [111]
reported a new strategy, based on tandem (serial)
catalysis, to obtain alternating polyesters from
renewable sources, using available complexes to
catalyze the cyclization of dicarboxylic acids fol-
lowed by alternating copolymerization of the result-
ing anhydrides with epoxides. Rosh et al. [112]
prepared cross-linked partially bio-based polyesters
by curing epoxidized soybean oil with various
dicarboxylic acid anhydrides in the presence of
cure catalysts such as tertiary amines, imidazoles,
or aluminum acetylacetonate. The anhydride dic-
tates the final thermal and mechanical properties.
Anhydrides of hexahydrophthalic acid, succinic
acid, and norbornene dicarboxylic acid have led to
high flexibity with glass transition temperatures
below room temperature. Maleic anhydrides gave
rise to more rigid, stiff polyesters with higher glass
transition temperatures between 43 and 73C.
Haq et al. [113] replaced partially petroleum-
based unsaturated polyester with functionalized
vegetable oils such as epoxidized methyl soyate.
Ortho-unsaturated polyester resin (UPE, Polylite
32570, Reichhold Inc., USA) containing 33.5 wt.%
styrene was used in the research. The bio-resin
based on epoxidized methyl soyate (EMS) was
obtained from Arkema Inc., USA (Vikotex 7010).
The amount of bio-based portion in the resin varied
from 0 to 20%. A reduction in the tensile modulus
HANDBOOK OF THERMOSET PLASTICS
of 28% was observed for polyester resins contain-
ing 10% EMS in the blend, and 42% for 20%
EMS, relative to neat UPE. The failure strain
increased, while the tensile strength decreased,
which led to increased toughness with increasing
EMS content. The blend containing 10% EMS
showed 44% higher toughness relative to neat UPE.
The addition of EMS also increased the moisture
absorption of the resulting bio-based resin.
Acrylated epoxidized vegetable oils can be cured
alone or mixed with unsaturated polyester resins.
Grishchuk et al. [114] developed hybrid thermosets
with interpenetrating network (IPN) structures
based on vinyl ester/acrylated epoxidized soybean
oil hybrids with IPN structure, cross-linked with
styrene, and anhydride as an additional cross-linker.
The styrene diluted (B30 wt%) bisphenol A-type
vinyl ester (VE; Daron-XP-45-A2) was obtained
from DSM Composite, Nederland, and the acry-
lated epoxidized soybean oil (AESO) containing
monomethyl ether hydroquinone as inhibitor, was
obtained from Sigma-Aldrich Chemie GmbH. The
following vinyl ester (VE)/AESO combinations
were synthesized: 75/25, 50/50, and 25/75 wt.%.
Lower storage moduli were obtained for combina-
tions containing AESO. Two Tg were detected for
the polymerized AESO (at 250 and 15C), proba-
bly due to the multi-functionality and high unsa-
turation level of the AESO generating hard and soft
segments. The presence of the acrylated epoxidized
soybean oil in the hybrid system led to a reduction
of the flexural modulus (around 50% lower for the
50/50 composition) and to an increase in the tough-
ness of the system. The resistance to thermal
decomposition of the hybrid resin system was
improved due to the interpenetrating network struc-
ture created.
Liu et al. [115] obtained unsaturated polyester-
like resins from functionalized tung oil. Tung oil is
extracted from the seeds of tung trees. The princi-
pal compound of this oil is a glyceride based on
alpha-elaeostearic acid (cis-9, trans-11, trans-13-
octadecatrienoic acid). This compound is a highly
unsaturated conjugated system that is used as a dry-
ing oil, mostly for coatings, paints, and varnishes,
but cannot compete with the properties of a general
purpose unsaturated polyester. In order to obtain
unsaturated polyester-like resin with enhanced
properties, tung oil was functionalized in two steps:
(a) alcoholysis with pentaerythritol to produce tung
oil pentaeritritol; and (b) maleination to produce
15: BIOBASED THERMOSETS 601

tung oil pentaerithritol (maleinated). The product
was blended with styrene, and cross-linking
took place via a free radical polymerization, as can
be seen in Figure 15.23. Promising mechanical
properties were obtained: tensile strength was
35.9 MPa, tensile modulus was 1.94 GPa, flexural
strength was 46.2 MPa, and flexural modulus was
2.08 GPa.
Ashland Performance Materials, a commercial
unit of Ashland Inc., developed the first commer-
cially available bio-based unsaturated polyester
resin (Envirezt) based on soybean oil triglycerides.
Different grades of Envirezt are available that con-
tain from 8 to 22% bio-based content [116].
Envirezt is obtained by a process where a carbox-
ylic acid or corresponding anhydride containing an
ethylenic unsaturation is first reacted with a satu-
rated, monohydric alcohol to form the half ester of
the acid or anhydride. The half ester is then reacted
with a polyol to form the polyester. Soybean oil is
introduced in the reaction step of the half ester and
the poyol [117]. A comparison between mechanical
properties of one of Envirezt grades and a standard
UPR can be seen in Table 15.2.
Bio-Based Polyurethanes
Polyurethanes are extremely versatile polymers
with a great variety of applications: flexible and
rigid foams, elastomers, coatings, adhesives, and
sealants. Polyurethanes can be thermoplastic or
thermoset. Polyurethanes are synthesized by the
reaction of a polyol and a diisocyanate. The func-
tionality of the polyol determines the properties of
the final polyurethane. Diols lead to linear thermo-
plastic polyurethane whereas polyols with three or

O
O C
CH2OH
O (1) 200210C

C O + 2 HOH2C CH2OH
1 O Ca(OH)2
CH2OH
O C

Tung oil (TO) Pentaerythritol (PER)

O O
O
CH2OH
CH2OH (2)
O
O
HOH2C CH2 O C
+ O C N,N-Di methyl benzylemine

Hydroquionone
CH2OH
CH2OH T = 95C

Pentaerythritol alcoholysis products (TOPER)

O O

C H2C O C CH CH COOH
H2C O CH CH COOH

O O O

HOOC CH CH C O CH2 CH2 O C + O C

O O

H2C O C CH CH COOH
H2C O C CH CH COOH

Malinated products (TOPERMA)

Styrene unt (St)

(3)
Rigid thermoset polymer
Free radical copolymerization

Figure 15.23 Synthesis of tung oil-based unsaturated polyester-like polymer [115].

602
more hydroxyl groups are required to prepare ther-
moset, polyurethane networks.
The terminology bio-based polyurethanes usu-
ally refers to polyurethanes based on renewable
source polyols [42]. Bio-based isocyanates have
been introduced only recently and the results have
not yet been conclusive. Bio-based content of poly-
ols can range from 30 to 100%, and as a result,
polyurethane bio-based content varies from 8 to
70%, depending on the building blocks chosen [4].
Bio-based polyols available in the market for poly-
urethane production are divided into three groups:
polyether polyol, polyester polyol, and oleochem-
ical polyols from vegetable oils.
a. Bio-based polyether polyols: Sucrose and sor-
bitol are short-chain polyether polyols used for
rigid foams [4]. Polyether polyols can also be
obtained by condensation of 1,3-propanediol
synthesized for bio-based glycerol [118]. Bio-
based 1,3-propanediol can be used to produce
polytrimethylene ether glycol as the soft seg-
ment in elastomers and spandex fibers.
b. Bio-based polyester polyols: These can be
obtained by polycondensation of bio-based
dicarboxylic acids such as adipic or succinic
acid with bio-based polyols (1,3-propanediol)
[118]. Polyester-based polyurethanes have
better mechanical properties and are more
resistant to oil, grease, solvents, and oxida-
tion, compared to polyether-based. Polyester-
based polyurethanes are more sensitive to
hydrolysis and microorganism attack [119].
Longer and hydrophobic chain polyols can
result in greater flexibility and hydrolytic sta-
bility of the resulting polyurethane.
c. Vegetable oil-based polyols: These can be pre-
pared using distinct methods such as
Table 15.2 Mechanical Properties of Envirezt 70302 [116]
Property Bio-based Envirezt 70302
Tensile Strength (MPa) 73
Tensile Modulus (MPa) 2500
Elongation at Break (%) 4.0
Heat Deflection Temperature (C) 90

Envirezt 7030 (Ashland) is an isophthalic-based resin with 22% bio-content used for pultrusion.

Aropolt S 542 H (Ashland) is a standard reference unsaturated polyester resin used for pultrusion.
HANDBOOK OF THERMOSET PLASTICS
epoxidation of the double bonds with further
oxirane ring opening with alcohols or other
nucleophiles [120], transesterification with
multifunctional alcohols, and the combination
of hydroformylation or ozonolysis with subse-
quent reduction of carbonyl groups (see the
section on natural oils for more details). Fatty
acids can be easily isolated from triglycerides
and can be used to prepare diols and polyols.
Triglycerides of castor oil and lesquerella oils
are characterized by the presence of ricinoleic
and lesquerolic fatty acids, respectively, both
presenting hydroxyl groups on their backbones
[42]. Both oils are important sources of natu-
rally occurring polyols, however, the number
of hydroxyl groups in castor oil are substan-
tially higher compared to lesquerella oil.
Polyurethanes from Vegetable Oils
Most of the bio-based polyols for polyurethanes
are synthetized from vegetable oils. The hydroxyl
groups present in oils can react with isocyanates to
form branched polyurethanes. Natural oils vary
greatly regarding the type, composition, and distri-
bution of fatty acids in the triglycerides molecules.
The principal variation in fatty acid composition of
the oils results from variations in chain length,
degree of unsaturation, and position of the double
bond in the fatty acid chains. As a result, there is a
great variation in the length of elastically active
network chains (related to the double bonds/
hydroxyl groups) and dangling chains (the soft seg-
ments resulting from the saturated portions) in
polyurethane networks obtained from vegetable oil-
based polyols [33]. The functionality of the polyol
determines the properties of the final polyurethane
polymers. Diols lead to linear thermoplastic polyur-
ethanes, whereas polyols with three or more
Aropol S 542 H (Std ref. resin)
75
4300
2.9
94
15: BIOBASED THERMOSETS
hydroxyl groups are required to obtain thermoset
polyurethane networks [120]. Petroleum-based
polyols usually present hydroxyl groups as primary
alcohols while the majority of functional groups in
vegetable oils are secondary. The reaction rate of
primary alcohols with isocyanate is about 3.3 times
faster than that of the secondary ones [121].
Additionally, when polyurethane foams are created
from secondary polyols, slower reaction rates dur-
ing gas expansion might weaken the three-
dimensional network of the polyurethane foam,
thus creating more open cells with lower carbon
dioxide content and reduced thermal isolation prop-
erties [121].
Castor oil can be used in the synthesis of cross-
linked polyurethanes and interpenetrating networks.
Soybean oil, palm oil, and rapeseed oil are more
popular and cheaper oils compared to castor and
lesquerella oils (natural polyols). In order to obtain
polyols from these oils, chemical modifications
have to be made (refer to the section on natural oils
for more details). Polyurethanes produced from
vegetable oil-based polyols include elastomers
obtained from oils with low hydroxyl content and
rigid foam and plastics from high hydroxyl content.
The extent of unsaturation conversion to hydroxyl
groups can tailor the final properties of the polyure-
thane since the hydroxyl content controls the degree
of cross-linking and the resulting stiffness of the
polymer. The polymer structure must be highly
cross-linked when a rigid foam is required, whereas
less cross-linking gives rise to flexible foams [115].
The degree of cross-linking is also dependent on the
NCO/OH ratio. Highly cross-linked and stiffer poly-
urethanes are obtained when the ratio is high [122].
Most vegetable oil-based polyols are of relatively
low molar mass (around 1000 Da) with a functional-
ity distribution that ranges from 1 to 8 hydroxyl
groups per molecule. As a result, the average
Figure 15.24 Polyester diol obtained from ricinoleic acid [13].
603
hydroxyl equivalent (molecular weight divided by
the hydroxyl functionality) varies from 200 to 300,
making them suitable for rigid and semi-rigid appli-
cations, rigid foams, cast resins, coatings, and adhe-
sives [13]. Rigid polyurethane foams can be obtained
from 100% vegetable oil-based polyols, while flexi-
ble foams are obtained by mixing vegetable oil-
based polyols with petroleum-based polyols.
Castor oil, for example, is a naturally occurring
polyol with a functionality of 2.7 hydroxyls per
molecule. Polyurethane obtained from castor oil
with diphenylmethane diisocyanate is a hard elasto-
mer with a glass transition temperature around 7C.
According to Petrovic [13], in order to obtain flexi-
ble foams and elastomers, polyols with molecular
weight greater than 3000 Da and hydroxyl equiva-
lent weight of 1000 and higher are required. These
polyols were synthesized by Petrovic from ricino-
leic acid via transesterification, which produced
polyricinoleic acids (Figure 15.24). The dangling
chains act as plasticizers, and inhibit crystallization.
Elastomers with glass transition temperatures rang-
ing from 233C to 258C were obtained when
polyricinoleic acids were polymerized with diphe-
nylmethane diisocyanate. According to Petrovic,
lower glass transition temperatures and higher elon-
gations can be achieved using a triol polyricinoleic
acid obtained by introducing a triol during the
transesterification step.
Zlatanic et al. [33] synthesized polyurethanes
from different vegetable oils
midoleic sunflower,
canola, soybean, sunflower, corn, and linseed oil

with 4,4-diphenylmethane diisocyanate. The func-
tionality of the polyols ranged from 3.0 for the mid-
oleic sunflower polyol to 5.2 for the linseed oil.
The conversion of the double bonds to epoxy
groups during the epoxidation reaction was rela-
tively high for all the oils, and ranged from 91 to
94%. The polyols were obtained by epoxidation
604
followed by ring opening. Polyurethanes were
obtained by reacting the polyols with MDI. Linseed
oil-based polyurethanes presented higher cross-
linking density, better mechanical properties, and
higher glass transition temperatures. The lowest Tg
was obtained for the polyurethane from midoleic
sunflower oil (33C), and the highest was observed
for the linseed oil-based polyurethane (77C).
Tensile strengths of all polyurethanes ranged from
15
23 MPa, except for the polyurethane based on
linseed oil, which showed tensile strength three
times higher than the others (56 MPa). The tensile
modulus of linseed oil-based polyurethane was near
four times higher (2.0 GPa) compared to other oil-
based polyurethanes. The variation in properties
resulted primarily from the different cross-linking
densities and less from the position of the reactive
sites in fatty acids chains.
DwanIsa et al. [122] used soy phosphate ester
polyol with hydroxyl content ranging from 122 to
145 mg KOH/g and diphenylmethane diisocianate
to prepare highly cross-linked bio-based
polyurethanes.
Del Rio et al. [124] obtained polyols with differ-
ent hydroxyl contents using the synthesis of poly-
ether polyols through the combination of cationic
ring-opening polymerization of epoxidized methyl
oleate and the reduction of carboxylate groups to
hydroxyl groups. Polyurethanes were obtained from
the reaction of the polyols with MDI or L-lysine
diisocyanate (LDI), a non-toxic diisocyanate. It was
observed (as expected) that the higher the function-
ality of the polyol, the higher the degree of cross-
linking that occurred, which in turn led to higher
Tg values. Additionally, the aromatic MDI led to
higher Tg values compared to the aliphatic LDI.
Lligadas et al. [120] synthesized diols and polyols
from oleic acid (C18 fatty acid found mostly in olive
oil) and undecylenic acid (C11 fatty acid derivative
with a terminal double bond obtained from castor
oil) using click chemistry. Click chemistry was tai-
lored to generate substances quickly and reliably,
mimicking nature, and was designed to generate sub-
stances by joining small units together.
Undecylenic acid was obtained by heating rici-
noleic acid under vacuum pyrolysis to create unde-
cylenic acid and heptaldehyde. Using thiol-ene
click chemistry, Lligadas et al. [120] applied photo-
initiated coupling of 2-mercaptoethanol and methyl
esters of oleic and undecylenic acids, followed by
reduction (Figure 15.25).
HANDBOOK OF THERMOSET PLASTICS
Bio-based triols were also obtained by transition
metal-catalyzed cyclotrimerization of methyl
10-undecynoated and methyl 9-octadecynoated
compounds that can be synthesized from oleic and
undecylenic acid via bromination and further elimi-
nation to alkyne functionality, and then subsequent
reduction of carboxylate groups to obtain primary
hydroxyl groups (Figure 15.26). The resulting poly-
ol was reacted with methylene diphenyl isocyanate
(MDI) using 1,4-butanediol as the chain extender.
Desroches et al. [125] synthesized ester-
containing diols of fatty acids via transesterification
with diol compounds followed by thiol-ene radical
coupling. Polyurethanes were prepared from the
synthesized oleochemical pseudo-telechelic diols,
which were reacted with methylene diphenyl-4,4
diisocyanate (MDI). In Desroches study, soybean
oil was used as raw material, and contained differ-
ent fatty acids with 0 to 3 double bonds. The soft
segments of vegetable oils were based on ester
groups or amide groups with various spacer lengths
in between. These were obtained through the trans-
esterification with a diol or amidification with
hydroxylamine or through thio-ene radical cou-
pling. Amide groups containing polyurethanes
exhibited the highest glass transition temperatures
(62C) due to hydrogen bonding enhancement.
Miao et al. [126] developed a polyol with high
hydroxyl value from epoxidized soybean oil and iso-
propanolamine (Figure 15.27). Both ester groups and
epoxide groups in epoxidized soybean oil reacted
with amino group generating hydroxyls, leading to a
hydroxyl value of 317 mg KOH/g. The resulting poly-
ol was reacted with 1,6-diisocyanato-hexane to obtain
polyurethane, and additionally used 1,3-propanediol
(PDO) as the chain extender. A single glass transition
was noticed (24.4 to 28.7C).
Natural oil polyols are produced commercially
by several companies
Agribusiness Cargill
(BiOH, soybean-based polyol), Dow Chemical
(Renuva soybean-based polyols), Urethane Soy
Systems Company, and BioBased Technologies
(Agrol) BASF (BALANCE, castor oil-based poly-
ol), Bayer (BAYDUR, castor oil-based polyol) and
Mitsui Chemicals (castor oil-based polyols)
for
making polyurethane foams for the automotive, fur-
niture, spray insulation, and other industries.
Polyurethane rigid foams are widely used as insula-
tion and structural materials for construction, trans-
portation, decoration, and appliances, which
accounts for approximately one-third of the
15: BIOBASED THERMOSETS 605

OH
(a)
SH
O HO S O
O HO

O O S
OH 7 DMPA/h 7
7 p-TSA/reflux
UD 80% 85%
UDA UDA-diol OH

CH3OH
p-TSA/reflux
85%

OH OH
SH
O HO LiAIH4/THF
S O S
O
7 DMPA/h O 84% OH
7 7
UDM 95%
UDM-diol

(b)
OH
O
O SH O
HO HO
OH S
4 O
4 O
4
DMPA/h
6 p-TSA/reflux S
6 6
80% 70%
OL HO
OLA OLA-diol

CH3OH
p-TSA/reflux
85%
OH OH
O SH
HO O LiAIH4/THF
O S S
4 O OH
DMPA/h 4 75% 4
6
80% 6 6

OLM OLM-diol

Figure 15.25 Preparation of undecylenic and oleic acid-derived diols using thiol-ene click chemistry [120].

polyurethane market. Flexible polyurethane foams application in cushioning and vibration-damping

are used in automobile seating, upholstered furni- materials [127]. The visco-elastic effect is obtained
ture, carpet backing, and bedding (mattresses and due to small open cells (with little opening, which
pillows). Bayer recently developed a visco-elastic delays the air re-entrance after compression and
polyurethane foam based on castor oil polyol for leads to a slow-down recovery). A summary of bio-
606
Figure 15.26 Preparation of undecylenic aromatic triol (UDT) and oleic aromatic triol (OLT) using
cyclotrimerization process [120].
based polyols, raw materials, and producers can be
seen in Table 15.3.
Polyols from Lignocellulosic Materials
Lignocellulosic materials including wood, agri-
cultural, or forestry wastes are a mixture of natural
polymers based on lignin, cellulose, and hemicellu-
lose, and tannins with more than two hydroxyl
groups per molecule, and can be used as polyols
HANDBOOK OF THERMOSET PLASTICS
for polyurethane preparation [137]. In order to
obtain polyols from lignocellulosic materials, they
must first be liquefied by chemical or thermochem-
ical treatments at high temperatures and high pres-
sure [42,138,139]. In the presence of alcohols such
as ethylene glycol, liquefied wood with hydroxyl
content suitable to reaction with isocyanate is
obtained. Foam with varied densities can be
obtained with properties similar to conventional
rigid polyurethane foams.
15: BIOBASED THERMOSETS
Figure 15.27 Synthesis of bio-based polyurethane
from epoxidized soybean oil and isopropanolamine
[126].
Polyols from Carbohydrates
Sugars and starches are carbohydrates that are
considered a very important renewable resource for
polyols (see the saccharides section for more
details). Sugars are basically polyols with a high
number of hydroxyl groups along the chain, and
therefore are potential raw materials for polyur-
ethanes [22,41]. Starches and cellulose can be liq-
uefied in the presence of alcohols in order to obtain
polyols to be used in the preparation of polyur-
ethanes. The process includes the use of liquefac-
tion solvents based on polyethylene glycol,
glycerol, and sulfuric acid. The solution obtained is
then neutralized with caustic soda [122].
607
Polyols from Natural Polyphenols
As detailed in the section on polyphenols, natu-
rally occurring polyphenols such as tannins and lig-
nins are characterized by the presence of multiple
phenol structural units. Polyurethanes having
mechanical properties ranging from soft to hard
were synthesized by varying the kraft lignin con-
tent. High content (30
35%) of kraft lignin results
in rigid and brittle materials, while lower amounts
provide soft polyurethanes [122]. Kelley et al.
[140] synthesized polyurethanes from kraft hydro-
xypropyl lignin with varied molecular weights and
hexamethylene diisocyanate. The mechanical prop-
erties of the polyurethane obtained improved as the
molecular weight of the hydroxypropyl lignin
increased. Kelley et al. [56] tried to increase the
elongation and toughness of polyurethanes based
on lignins by introducing chain extenders to the lig-
nin. Polyethylene glycol and polybutadiene glycol
were used as chain extenders. In order to eliminate
phase separation, a polyether soft segment was
attached to the lignin derivative by propylene oxide
chain extension, which created a star-like copoly-
mer with rigid aromatic core and flexible polyether
arms. Saraf et al. [141] compared the properties of
polyurethanes synthesized from two types of lignin:
kraft and steam explosion lignin. Kraft lignin
showed inferior mechanical properties.
Cashew nut-based phenols, especially cardanol,
are considered an attractive raw material for poly-
urethanes. Cardanol can be recovered from cashew
nut shell liquid by double vacuum distillation and
can be converted into a diol to be reacted with a
diisocyanate [60]. According to Mohanty et al.
[123], cardanol can be reacted with glycol in the
presence of phosphoric acid as catalyst. The result-
ing mixture can be reacted with aromatic diisocya-
nate to obtain films of polyurethane. Mixtures of
cardanol, formaldehyde, and diethanolamine,
blended first with polyethylene glycol and then
with methylene diphenyl diisocyanates; MDI and
hexmethylene diisocyanate led to rigid polyure-
thane foams [59].
Isocyanate-Free Polyurethanes and
Bio-Based Isocyanates
Isocyanates are the derivatives of isocyanic acid
(H-NQCQO). The functionality of the isocyanate
(R-NQCQO) group is highly reactive toward
608 HANDBOOK OF THERMOSET PLASTICS

Table 15.3 Summary of Bio-Based Polyols for Polyurethanes [4]

Trade
Source Material Name Producer Application Reference
Soybean oil BiOH Cargill Flexible foams [128]
Renuva Dow Flexible foams and CASE [129]
SoyOil Urethane Soy Flexible and rigid foams, [4]
Systems spray foams, elastomers
Baydur BAYER Rigid and flexible foams [130]

Agrol BioBased CASE , molded foams [131]
Technologies
Castor oil Lupranol BASF Rigid foams, mattresses [132]
BALANCE
Polycin Vertellus Coatings [133]
Mistui Rigid and flexible foams [134]
Chemicals
Renewable and Enviropol IFL Chemicals Rigid foams for insulation [135]
recycled natural oil and refrigeration
Rapeseed/ Metzeler- Flexible foam [136]
Sunflower oil Schaum
GmbH

CASE: Coatings, Adhesives, Sealants, and Elastomers.

proton-bearing nucleophiles, and the reaction of
isocyanate proceeds with addition to the carbon-
nitrogen bond [142]. Important isocyanates used
in polyurethane manufacturing include 2,4-toluene
diisocyanate, 2,6-toluene diisocyanate, 1,6-hexam-
ethylene diisocyanate, and 1,5-naphthalene diiso-
cyanate, among others (all petroleum-derived). The
reactivity of isocyanates depends on their chemical
structures. Aromatic isocyanates are usually more
reactive than their aliphatic counterparts. The pres-
ence of electron-withdrawing substituents on iso-
cyanates increases the partial positive charge on the
carbon atom and moves the negative charge further
away from the reaction site, which results in a fast
reaction. Isocyanate is obtained from the reaction
between amines and phosgene, a hazardous chemi-
cal that requires special precautions, is toxic, and is
an irritant to mucous membranes. Polyurethanes are
currently being produced from bio-based polyols
with toxic isocyanate. Environmental and public
health concerns motivate the research for alterna-
tive routes to create bio-based, non-toxic isocya-
nates. Isocyanate-free, environmentally friendly
polyurethane systems can be obtained from
vegetable oils. Mahendran et al. [143] developed
a new bio-based non-isocyanate urethane by the
reaction of a cyclic carbonate synthesized from a
modified linseed oil and an alkylated phenolic
polyamine from cashew nut shell liquid
(Figure 15.28). Cyclic carbonates can be synthe-
sized from any epoxy monomers. The cyclic car-
bonate groups were added to the triglyceride by
reacting epoxidized linseed oil with carbon dioxide
in the presence of a catalyst.
Cayli et al. [144] synthesized isocyanate deriva-
tives from unsaturated plant oil triglycerides. The
triglyceride was first brominated at the allylic posi-
tions by a reaction with N-bromosuccinimide, and
then, the brominated species were reacted with
AgNCO to convert them to isocyanate-derivative
triglycerides (Figure 15.29).
Polyurethanes and polyureas were synthesized
curing the fatty isocyanates obtained with alcohol
and amines, respectively. Glycerin polyurethane
exhibited a glass transition temperature of 19C,
castor oil polyurethane showed two glass transition
temperatures at 24 and 36C, and triethylene tetraa-
mine polyurea showed a glass transition
15: BIOBASED THERMOSETS 609

Figure 15.28 Isocyanate free urethane: Reaction of cyclic carbonate with phenylalkylamine [143].

Br O

C C CH O
O
H H

O O

AgNCO in THF
R.T.

NCO O

C C CH O
H H O

O O

Figure 15.29 Bio-based isocyanate from vegetable oil [144].

temperature of 31C. The polyurethanes synthe-
sized demonstrated similar mechanical properties
(tensile modulus around 50 kPa and tensile strength
around 100 kPa). Despite the low tensile strength
and modulus, castor oil polyurethane and glycerin
polyurethane showed excellent elongation, 410%
and 353%, respectively.
Hojabri et al. [145] described the synthesis of
linear saturated terminal aliphatic diisocyanates
from fatty acids via Curtis rearrangement, a thermal
610
Figure 15.30 Synthesis of bio-based isocyanate from oleic acid [145].
decomposition of acyl azide. Diacids such as azea-
lic acid, can be produced from oleic acid, as in
Figure 15.30.
Saturated diacids can be prepared by ozonolysis
of oleic acid to the corresponding aldehyde fol-
lowed by purification and oxidation of the aldehyde
to obtain the diacid. Hojabri et al. compared physi-
cal properties of polyurethanes obtained using the
same polyol with fatty acid-derived diisocyanate
(1,7-heptamethylene diisocyanate, HPMDI) and a
similar but petroleum-derived commercially avail-
able diisocyanate: 1,6-hexamethylene diisocyanate
(HDI). Canola polyols were synthesized using ozo-
nolysis and hydrogenation. Desmophen 800 (Bayer)
was used as the commercial polyol. The polyur-
ethanes obtained had comparable properties to
fossil-based diisocyanates.
Bio-Based Alkyd Resins
Alkyds are polyesters obtained by polycondensa-
tion of three monomers: polyols, dicarboxylic acids,
or anhydrides, and natural fatty acids or triglycer-
ides. The term alkyd is a modification of the origi-
nal name alcid coined by R. H. Kienle, meaning
from alcohol and organic acids [146]. Since alkyd
resins emerged in the market in the late 1920s, they
have always had a substantial bio-based content
[4]. These resins are used in paints and coatings. In
1927 Kienle combined fatty acids with unsaturated
esters while searching for a better insulating resin
for General Electric [146]. Double bonds present in
the fatty acids are capable of oxidative coupling
reactions that lead to air drying of plant oils, thus
creating film coatings. This is the chemistry behind
the alkyd resins [14]. When the resin is applied to a
substrate, heat or oxidizing agents are achieved by
changing the oil length or chemical modification,
HANDBOOK OF THERMOSET PLASTICS
such as introducing chain stopping agents, phenolic
resins, acrylic monomers, styrene, vinyl toluene,
silicones, isocyanates, etc. Alkyd resins are compat-
ible with a vast number of polymers, making them
very versatile to produce coatings, binders, paints,
lacquers, and varnishes, both transparent and semi-
transparent [147]. Fatty acids are produced from
vegetable oil. The common polyols are synthetic
glycol or glycerol, although bio-based glycerol can
be used instead, which increases the bio-based con-
tent of the final polymer [4] and extends up to 70%
of the bio-based content [147]. Fossil-based phtha-
lic acid and maleic acid (and anhydrides) are the
most commonly used organic acids; glutaric and
succinic anhydrides can also be used in alkyd for-
mulations [17]. Drying times can be controlled by
the type and amount of anhydride, with drying
times increasing with the amount of anhydride. An
illustrative reaction between glycerol and phthalic
anhydride is shown in Figure 15.31.
Alkyd resins can be classified according to oil
length, which refers to the oil percentage in the
alkyd. Short oil alkyds contain below 40% oil;
between 40 and 60% they are called medium, and
above 60%, long oil alkyds [17]. The oil length
affects the properties of the final product. A typical
long oil alkyd is made of 60% soybean fatty acids,
21.5% polyol (pentaerythritol), and 25.4% phthalic
anhydride [4]. Most alkyd-based coatings are used
for industrial goods (vehicles, wood products, etc.)
and infrastructure (traffic control striping, bridges,
etc). Alkyd coatings are inexpensive, durable, and
heat resistant. Durability and abrasion resistance
can be increased by modifying alkyd with rosin
(pine resin) [146]. Phenolic and epoxy resins
improve hardness and resistance to chemicals and
water. Styrene extends flexibility of coatings and
can be used to cross-link alkyd resins (using
15: BIOBASED THERMOSETS
O O
CH2-OH
O
CH-O-CO-R
O
CH2-OH
Figure 15.31 Synthesis of alkyd resin [17].
peroxides as initiators). Thermoset alkyds can be
used to produce billiard balls, appliance housings,
motor cases, switches, electronic encapsulations,
etc. More ecological friendly versions of alkyds
were produced based on the synthesis of alkyd
resins with relatively high acid value, and neutral-
ized using amines to form colloidal solutions in a
mixture of water and water miscible solvents such
as glycol ether [147]. Nevertheless, solvents present
in alkyd formulations at an amount of 20 to 30%
present an environmental problem. High-quality
alkyd coatings with low solvent amounts are an
important target in the coating industry. High solid
content alkyd resins can be obtained by reducing
polymer viscosities using lower-molecular-weight
polymers, thus enabling a reduction in the solvent
content [17]. The same effect can be obtained by
synthesizing highly branched and star-structured
resins [148]. Hyperbranched alkyd resins can be
obtained using trimethylpropane and dimethylolpro-
pionic acid. Saturated polyesters with hydroxyl end
groups are first obtained. The alkyd resin is
obtained by the esterification of the polyester
obtained in the first step, with unsaturated fatty
acids. According to Gruner [17], star-like resins
with three or four arms can be formed by the esteri-
fication of dipentaerythritol with fatty acids.
In the 1980s and 1990s, environmentally
friendly, zero VOC (Volatile Organic Contents)
versions of alkyd waterborne resins were devel-
oped. In order to obtain water-based resins, alkyd
resins with high acid numbers were prepared and
neutralized by amines. Amines were avoided by
using suitable surfactants. According to Hofland
[147], surfactants can also be eliminated by in situ
polymerization of hydrophilic monomers within
solvent-less alkyd resin, followed by inverse-phase
emulsification. Water-soluble alkyd resins were
synthesized by the copolymerization of acrylic
acid, glycidyl methacrylate esterified with unsatu-
rated fatty acid, styrene, and methyl methacrylate
[17]. Kuhneweg [149] developed a waterborne
611
O
O C C O CH2 CH CH2 O
n
O
C O
R
acrylic-modified alkyd resin based on the polymeri-
zation of a sulfonated alkyd resin with an acrylated
fatty acid. After polymerization, the polymer could
be dissolved in water.
Hofland [147] described an ultimate low carbon
footprint alkyd resin that had not only a low con-
tent of fossil carbon, but also low energy content
(i.e. low energy bio-based raw materials such as
succinic acid, colophonium (rosin), glycerol, and
isosorbide). Water-based alkyd and high-solid alkyd
resins can be ecological friendly solutions. High-
solid alkyd solvents can be replaced by bio-based
ones like ethanol, methyl ester of soybean fatty
acids, or methyl lactate.
Kemwerke (Philippines) developed eco-friendly
short oil coconut alkyd resins for paint formula-
tions. Coconut alkyds are a range of tough resinous
products formed by reacting polybasic organic
acids or anhydrides with polyhydric alcohols in the
presence of coconut fatty acid or the monoglyceride
state of the refined coconut oil [150]. Soy
Technologies LCC (KY, EUA) produces soy-based
alkyd emulsions for coating formulations (Soyanol)
[151]. Perstop (Sweden) produces bio-based glyc-
erol in medium oil-length, soybean oil-based, air-
drying alkyd resin formulations [103].
Bio-Based Phenolic Resins
Phenol
formaldehyde is one of the oldest com-
mercial synthetic polymers, first introduced by Leo
Hendrik Bakeland in 1907 [152]. The polymer is
the result of a step-growth polymerization of two
simple chemicals: phenol or a mixture of phenols
and formaldehyde using an acidic or basic catalyst
[153]. Phenol is reactive towards formaldehyde at
the ortho and para sites, allowing up to three units
of formaldehyde to attach to the aromatic ring. The
main product of the reaction between them is the
production of methylene bridges between aromatic
rings, as can be seen in Figure 15.32.
612
Figure 15.32 Structure of phenol formaldehyde.
The ratio between formaldehyde and phenol deter-
mines the degree of cross-linking. When the molar
ratio is one, theoretically, every phenol can be
linked together via methylene bridges, enabling total
cross-linking. Novolacs (novolaks originally) are
phenol
formaldehyde resins where the molar ratio
of formaldehyde to phenol is less than one. The poly-
merization is catalyzed by acids such as oxalic acid,
hydrochloric acid, or sulfonate acids; the reaction
is slow and relatively low molecular weights are
obtained [153]. In a second step, a hardener such as
hexamethylenetetramine can be added to cross-link
the resin. The hexamine forms methylene and
dimethylene amino bridges between the aromatic
phenol rings at high temperatures. Resoles are
one-stage phenol
formaldehyde resins obtained
with formaldehyde/phenol ratios greater than one
(B1.5) using a basic catalyst. Hydroxymethyl
phenols and benzylic ether groups are formed in the
first step of the reaction, at around 70C. Cross-
linking occurs when the temperature reaches around
120C to form methylene and methyl ester bridges
through the elimination of water molecules. A
three-dimensional, cross-linked network is formed.
Resole-type phenol
formaldehyde resin becomes
hard, and heat and chemically stable, after curing.
HANDBOOK OF THERMOSET PLASTICS
Resoles are used as adhesives (plywood, oriented
strand boards, laminated composite lumber, etc.) and
in composite materials (glass and carbon compo-
sites). Resole and novolac are soluble and fusible
low-molecular-weight products at A-stage, rubbery
at B-stage, and rigid, hard, and insoluble at C-stage
[153]. One of the most common applications of
novolac phenol resins is as photoresists.
Since phenol
formaldehyde is one of the major
adhesive resins in the manufacture of plywood, and
the raw materials are petroleum-based, their
replacement by bio-based, non-toxic substitutes has
become a necessity. In the polyphenols section,
bio-based polyphenols were presented as well as
the chemical pathways used to transform them into
raw materials for polymers. Lignin, a renewable,
non-toxic, widely available, low-cost raw material
was presented as having a high potential to be used
as a phenol substitute in phenol
formaldehyde
resins; it is a relatively expensive petroleum-based
chemical [154].
Lignin is highly cross-linked; three-dimensional
aromatic polymers with phenyl
propane units are
linked together by carbon-carbon or ether bonds
with phenolic and hydroxyl groups (Figure 15.16).
Lignin is the second most abundant polymer in
15: BIOBASED THERMOSETS
nature, after cellulose, and it is produced as a by-
product of the paper industry. One of the functions
of lignin in plants, together with hemicellulose, is
to bind cellulose fibers, although isolated lignins
have proven to be poor adhesives for wood compo-
sites [155]. Lignin is not structurally equivalent to
phenol. Phenol has five free sites on the aromatic
ring and no ortho and para substituents around the
hydroxyl group. In lignin, the aromatic ring is para-
substituted by the propyl chain of the propylphen-
4-ol(coumaryl) structural unit, which affects lignin
reactivity during cross-linking with formaldehyde
[155]. Lignin presents most ortho and para sites as
blocked by functional groups, which leads to
slower reaction with formaldehyde when compared
to phenol. For this reason, lignin is used to replace
phenol in a limited amount, between 40 to 70% in
adhesives formulations. Brosse et al. [156] added
lignin to phenol-formaldehyde resins without dete-
riorating the mechanical and adhesion properties,
and observed that an additional environmental ben-
efit was obtained: the presence of lignin reduced
the formaldehyde emissions for both the resin and
the finished products.
Phenolic precursors can also be prepared by liq-
uefying wood, bark, and forest and wood industry
residues using a fast pyrolysis process. Monomeric
phenols can be produced by thermochemical con-
version of biomass using fast and vacuum pyrolysis
[51,147]. Liquefation, phenolysis, and fractionation
methods can be also used. Fast pyrolysis is based
on fast heating rates using temperatures between
400 and 600C. Chum et al. [157] synthesized
novolac and resole resins using phenol derivatives
obtained by fast pyrolysis from softwood, hard-
wood, and bark residue. Reactive components for
resin synthesis were obtained by fractioning the
pyrolysis oils and isolating phenolic and neutral
fractions, which were directly polymerized
[154,157]. These pyrolytic oils contained a complex
mixture of compounds including phenolics, guaia-
col, syringol and para-substituted derivatives, car-
bohydrate fragments, polyols, organic acids,
formaldehyde, acetaldehyde, furfuraldehyde, and
other oligomeric products. The fraction containing
phenolic and neutral components substituted for not
only the phenol, but also some of the formaldehyde
present in the fraction.
Giroux et al. [158] developed a technology
called Rapid Thermal Processing [159] based on
fast pyrolysis or rapid destructive distillation that
613
Figure 15.33 A- and B-ring in tannin, where R1
can be resorcinol or phlorogucinol and R2 can be
pyrocathecol or pyrogallol [91].
enables one to obtain natural resins from a ligninic
fraction of the liquid pitch produced, all without
having to extract the phenol fraction using solvents.
The total phenolic content obtained ranged from 30
to 80 wt.% and was considered highly reactive and
suitable for use within resin formulations without
requiring any further fractionation procedure.
Resole-type resins were used in the production of
oriented strand board and plywood, with similar
results compared to fossil-based resins [154].
Vergopoulo-Markessini et al. [160] used a mix-
ture of phenol compounds obtained from pyrolysis
and cashew nut shell liquid. A synergistic effect
between phenolic-based pyrolysis products and
cashew nut shell liquid was noticed, which enabled
the substitution of up to 80 wt.% of the phenolic
component of a standard formaldehyde-based resin.
Cashew nut shell liquid contains cardanol, a pheno-
lic compound (Figure 15.17) that can be used to
substitute phenol in novolac or resole resins.
Cardanol
formaldehyde resins have shown
improved flexibility due to an internal plasticization
effect of the long chain and better processability.
Additionally, hydrophobic behavior was noticed
due to side chains, making the resin water-repellent
and resistant to weathering [91].
Tannins are also polyphenolic compounds
(Figure 15.15), with good reactivity towards form-
aldehyde. Tannins are composed mostly of flavan-
3-ol units, for which two phenolic rings are joined
together by a heterocyclic ring, as can be seen in
Figure 15.33 [91]. The high reactivity of the tannin
towards formaldehyde is due to the A-ring. In
novolac resins, the presence of tannins enable
614
NaOH
+ CH2O
CH3O
OH
Coniferyl monolignols
Figure 15.34 Methylolation reaction of bio-oil with formaldehyde [167].
reactions with hexamine at lower temperatures,
compared to fossil-based phenol formulations.
However, the high reactivity and the large mole-
cules of tannin can result in premature gelation,
which leads to brittleness [91]. Pizzi et al. [161]
developed polymers derived from the cross-linking
of condensed tannins by polycondensation reactions
with furfuryl alcohol and small amounts of formal-
dehyde. The addition of blowing agents created
tannin-based rigid foams with fire resistance similar
to synthetic phenolic foams.
Lignin has fewer reactive sites compared to
petroleum-based phenol. More than half of the
potentially reactive aromatic hydroxyl groups in
kraft lignin, for example, are blocked by methyl
groups, which hinders the aromatic hydroxyl group
[162]. Sulfur-mediated demethylation can be used
to remove methyl groups on the aromatic ring, thus
increasing the reactivity. Methylolation or hydroxy-
methylolation can be used to introduce hydroxy-
methyl groups (aCH2OH) to lignin molecules
using formaldehyde in an alkaline medium.
Methylolated lignin can be directly incorporated in
phenol
formaldehyde resin, replacing part of the
phenol, in wood adhesives compositions [155,162].
El-Mansouri et al. [163] replaced the formaldehyde
in the methylolation process by glyoxal, a bio-
based, non-toxic dialdehyde. The process was
called glyoxalation.
Lignin can be treated with phenol in the presence
of organic solvents such as methanol or ethanol in
a process called phenolation or phenolysis [154].
The phenolation process is based on a thermal
treatment of lignin with phenol in an acidic
medium, which leads to the condensation of phenol
with the aromatic ring of the lignin and side chains.
A reduction of the molecular weight of the lignin is
also observed, as a result of ester bond cleavage
HANDBOOK OF THERMOSET PLASTICS
CH2OH
CH3O
+
O Na
Figure 15.35 Guaiacol and syringol chemical
structures (in lignin) [154].
[162]. Cetin et al. [164,165] utilized phenolated-
lignin (20
30% of overall phenol) instead of
unmodified lignin in phenol
formaldehyde resins
to achieve an improvement in mechanical and
physical properties when utilized as wood adhesive
in particleboard. Hu et al. [166] modified a foamed
resole resin using phenolated lignosulfonate (lignin
from the sulfite process) to achieve mechanical and
physical properties similar to fossil-based phenol-
formaldehyde foams. Perez et al. [167] synthesized
two types of novolac resins based on lignin:
(a) ammonium lignosulfonate, which was used
directly, as filler, and (b) ammonium lignosulfonate
modified by methylolation. Cheng et al. [168]
obtained bio-oil from hydrothermal liquefaction of
pine sawdust. The bio-oil obtained was methylo-
lated with formaldehyde (Figure 15.34) in the pres-
ence of sodium hydroxide. The methylolated bio-
oil was polymerized with formaldehyde, replacing
up to 75 wt.% of phenol in the resin for the produc-
tion of plywood. The methylolation treatment
improved the thermal stability of the bio-based phe-
nolic resin. Phenolation and methylolation have
shown the best results in terms of number of reac-
tive sites created. The origin of the lignin may
affect the reactivity. Softwoods may yield more
reactive phenolics than hardwoods due to the
15: BIOBASED THERMOSETS
relatively high presence of guaiacol with one meth-
oxy group (Figure 15.35) [154].
Formaldehyde-containing resins (urea
formal-
dehyde, melamine
formaldehyde, and phenol

formaldehyde) for applications as wood adhesives
and mineral fiber binders for thermal insulation are
under intense pressure to reduce or eliminate form-
aldehyde content due to ecological concerns and
toxicity issues [152]. There is a need to develop non-
toxic, bio-based formaldehyde substitutes. Ramires
et al. [169,170] utilized glyoxal (OCHaCHO), a bio-
based chemical obtained by the oxidation of lipids, a
non-toxic and non-volatile dialdehyde that can be used
as a substitute for formaldehyde in phenolic resins.
Both resole and novolac resins based on glyoxal-
phenol resins were developed for application in com-
posite materials using sisal fibers as reinforcement, and
showed improved results for novolac-type resins in
terms of mechanical and physical properties. The novo-
lac glyoxal-phenol composite showed higher impact
strength (237 J m21) than the resole glyoxal
phenol
composite (118 J m21), indicating a better fiber/matrix
interaction. The novolac glyoxal
phenol composite
exhibited a higher storage modulus (E), and conse-
quently was more rigid than the resole composite. In
addition to glyoxal, oxazolidine, solid resole, epoxy,
resorcinol, and tannins are being examined to substitute
formaldehyde in phenol resins [152].
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