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Vegetable Oils in
Production of Polymers
and Plastics
Suresh S. Narine and Xiaohua Kong
Agri-Food Materials Science Centre, University of Alberta
Edmonton, Alberta, Canada

1. INTRODUCTION

Polymers are a group of materials made up of long covalently bonded molecules,


which are obtained either from natural or synthetic sources. Within the life
sciences, the study of polymers has helped to foster the emergence of molecular
biology through focus on natural macromolecular substances such as proteins,
nucleic acids, and polysaccharides. Largely through engineering efforts, a series
of commercially synthetic polymers have been successfully used in many applica-
tions in modern society.
Polymers, in the form of plastics, are used in making articles of daily use, such
as knobs, handles, switches, pipes, heart valves, and so on. An overwhelming per-
centage of the polymers to make these commodities are synthesized from petroleum
sources or natural gas raw materials. The key petrochemicals for polymer synthesis
(ethylene, propylene, styrene, vinyl chloride monomer, and others) are produced
largely from naphtha, one of the distillation fractions of crude oil or from natural
gas. Once synthesized, the polymer materials, such as polyethylene, polypropylene,

Bailey’s Industrial Oil and Fat Products, Sixth Edition, Six Volume Set.
Edited by Fereidoon Shahidi. Copyright # 2005 John Wiley & Sons, Inc.

279
280 VEGETABLE OILS IN PRODUCTION OF POLYMERS AND PLASTICS

polystyrene, and polyvinyl chloride, are passed to major consuming industries.


These synthetic polymers are, however, often not environmentally friendly because
they typically do not undergo the process of biodegradation and, of course, are
dependent on a limited petroleum resource. The urgent need of today is to develop
polymers that are biodegradable so that they become environmentally friendly
(1–3). The common biodegradable synthetic polymers include novel aliphatic
polyesters, such as poly(e-caprolactone) (PCL), poly(b-methyl-d-valerolactone),
polylactide, and their copolymers. The most important aspect of synthesizing
biodegradable polymers relates to their ability to undergo degradation within the
biosphere on coming into contact with micro-organisms, enzymes, or under natural
environmental conditions.
In addition, the natural resource of petroleum is being exhausted at a fast rate
(4). The escalating cost of petrochemicals and the high rate of depletion of this nat-
ural resource present a serious challenge to the innovative potential of chemists (5).
Scientists are therefore investigating opportunities to prevent economic losses and
inevitable crisis of lowered standard of living as a result of oil shortages in the
future. They are searching for new raw materials that can be synthesized into
environmentally friendly polymers so as to make available the materials needed
by various industries at lower costs (6, 7). These new materials are, in fact, not
so new; they stem from natural agricultural sources, called ‘‘renewable resources’’
(4, 6, 8). By definition, renewable resources are the agricultural products that are
synthesized by the use of solar energy (3, 4, 9). Some examples of these resources
are polysaccharides, such as cellulose and starch, and glycerol esters of fats and
oils (3, 10).

2. POLYMERS FROM RENEWABLE RESOURCES

This chapter deals with polymers synthesized from oilseed sources. However, to
provide the reader with an appreciation of the area of renewable, biodegradable
polymers and the place within this area that polymers from oil seeds occupy in
terms of functionality, price, and acceptability, some other polymers from major
renewable sources are also discussed. The most well-known and widely used
renewable biodegradable polymers are those from polysaccharides. The principal
polysaccharides of interest to polymer chemists are starches and cellulose, both
of which are polymers of glucose. In addition to these, fibers, polylactic acid
(PLA), and triacylglycerols of oils are of particular interest for the development
of biodegradable industrial polymers.

2.1. Starch
Starch is the most common polymer found in plants. Large amounts of starch can
be obtained from tubers such as potatoes, from cereals such as rice, and from seeds
such as corn. The starch molecule is heavily hydrated as it contains many exposed
hydroxyl groups, which form hydrogen bonds on coming into contact with water.
Starch is constituted of linear polymers (amylose) and of branched polymers
POLYMERS FROM RENEWABLE RESOURCES 281

(amylopectin) of a-D-glucose. Amylose consists of long linear chains joined by


a (1 ! 4) linkages. Amylopectin, however, is highly branched in that D-glucose
is also joined by a (1 ! 4) linkages, but the branching point linkage between
the two D-glucose molecules have a (1 ! 6) linkages (11). The structures of amy-
lase, amylopectin, and starch are shown in Figure 1.

OH
H
H
O OH
O H H
HO
H
OH O O
H H
HO
OH
H
O

Amylose Unit Linkage α 1 4

HO
H
H
O O
H OH
HO H
OH H
H O
O HO H
OH
H
O
H
H
O
O H
HO
OH
H O
Amylopectin Unit Linkage α 1 4

OH
H
H
O
Branch O HO H OH
H
OH H
H O
O HO H
OH
H 1 6 linkage
O
H
H
O
O H
Chain Main HO
OH
H O

Structure of Starch showing α 1 6 branch point linkage

Figure 1. Structures of amylose, amylopectin, and starch.


282 VEGETABLE OILS IN PRODUCTION OF POLYMERS AND PLASTICS

It may be noted from Figure 1 that the starch molecule contains two important
functional groups, that is the OH group, which is important for substitution reac-
tions, and COC, which is susceptible to chain breakage. As a result of these two
important features, starch and its derivatives are used in the synthesis of biodegrad-
able plastics (1).
Starch is generally regarded as a resource that is competitive with petroleum in
terms of the preparation of a compostable polymer (12). It is used as an additive to
plastics, for cross-linking or bridging to change the structures of plastics into
networks, and as fillers for various purposes. Acetylation of starch yields starch
acetate, which is considerably more hydrophobic than starch and has an improved
solubility so that it can be easily cast into films from simple solvents. Degradation
of acetylated starch films occurs when exposed to buffered amylase solution (1).
Starch is used as filler in various resin systems to produce films that are imperme-
able to water but permeable to water vapors. Griffin (13) reported that starch-filled
polyethylene films become porous after the extraction of starch. This porous film
can then be readily invaded by micro-organisms and rapidly saturated with oxygen,
thereby increasing polymer degradation by biological and oxidative methods. Some
work has also been reported in which starch is used as a filler in manufacturing
polyvinyl chloride (PVC) plastics (1). In addition, the hydroxyl group ( OH) of
starch can react with the extremely reactive groups ( NC O) of isocyanates
spontaneously, (i.e., cross-linking) which can be used to prepare a large number
of reactive resins with reduced cost and improved solvent resistance and strength
qualities (1, 14).

2.2. Cellulose
Cellulose is the most abundantly occurring natural biopolymer. Cellulose is a linear,
unbranched homopolysaccharide. It resembles amylose, which is the primary poly-
meric constituent of starch. However, the major difference is that glucose residues
in cellulose have b configuration (11, 12, 15). Cellulose is now receiving greater
attention from polymer chemists because of the easy manner in which it undergoes
biodegradation by certain micro-organisms. Aerobic soil is rich in floral bacteria
and fungi, which will operate cooperatively to degrade polymers. Primarily, cellu-
lose is biodegraded to glucose and cellodextrin. Then, by the action of enzymes,
these cellodextrins are converted to glucose. The end products of biodegradation
under aerobic conditions are water and carbon dioxide. The final products of bio-
degradation under anaerobic conditions, on the other hand, are carbon dioxide,
hydrogen, methane, hydrogen sulfide, and ammonia (1).
Cellulose is a fibrous, tough, water-insoluble, and crystalline substance. As a
result of these characteristics, it is often converted to its derivatives in order to
make it more useful. The most commonly used derivatives of cellulose are carbox-
ymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose,
cellulose acetate, and cellulose xanthate (12). Among these derivatives, cellulose
acetate and cellulose xanthate are cellulose esters, which are now widely used
in the manufacturing of fibers, films, and in injection molding thermoplastics.
POLYMERS FROM RENEWABLE RESOURCES 283

OH
H H H
H OH H
HO O
O O O
H HO H OH
H H
OH H
n

Figure 2. Structure of cellulose.

Cellulose esters represent a class of polymers that have excellent physical proper-
ties and are relatively low-cost materials with high market potential (1). The struc-
ture of cellulose acetate is shown in Figure 2.

2.3. Fibers
In addition to starch and cellulose, a wide variety of organic materials have signif-
icant commercial importance to the plastic industry. Fibers, among these, are being
currently used as fillers and reinforcing agents in plastic materials. The primary
advantages of using renewable lignocellulosic fibers as additives in polymers are
that they (16):

1. have low densities


2. are low-cost materials
3. have a nonabrasive nature
4. provide high filling levels
5. require low-energy consumption
6. have high specific properties
7. are biodegradable and environmentally friendly
8. have wide varieties available throughout the world

Wood flour, for example, is a finely ground fibrous material obtained primarily from
pine and spruce. Cotton is another plant fiber that is important in thermosetting
molding compounds. Cotton fibers are used in the plastic industry in several forms:
as flock, cordage, woven fabrics, nonwoven fabrics or felts, and chopped fabrics.
The products obtained by using these fibers have reduced cost, increased impact
strength, and other mechanical properties, as well as having improved moldability
and appearance of finished molded parts. Wood flour; cotton fibers; sisal, another
fiber plant; and hemp fiber, obtained from Cannabis sativa (12), are all used as filler
and act as a reinforcing material for plastics. A lot of work has been done by
Mohanty et al. (16–23) using lignocellulosic fibers from jute, pineapple leaf, sisal,
and others, in making biopolymers. They observed that lignocellulosic fibers play
important roles in modifying physical as well as chemical properties of the poly-
mers (17–19). Rout et al. (20) have studied the use of coir as reinforcement in poly-
mer composites. It was found that the efficiency of fiber-reinforced material
284 VEGETABLE OILS IN PRODUCTION OF POLYMERS AND PLASTICS

depends on the fiber/matrix interface and the ability of transferring stress from the
matrix to the fiber. Mohanty et al. (22) studied the chemical modifications of jute
yarns in making biopolymers and found that alkali-treated yarns produce better
mechanical properties than the defatted ones because of the improved fiber matrix
adhesion of the previous ones. Mishra et al. (16) studied surface modifications and
mechanical improvements in pineapple leaf polyesters. It was observed that the
surface-modified pineapple leaf fibers were good reinforcing agents for polyester
matrices as well as having increased tensile and flexural strength.

2.4. Polylactic Acid (PLA)


Polylactic acid is not a new polymer. It belongs to the family of aliphatic polyesters
commonly made from a-hydroxy acids, which can be synthesized via two major
routes. One method involves the removal of water using solvent, under conditions
of high temperature and pressure. The polymer yielded using this method may be
coupled with isocyanates, epoxides, or peroxides to produce a variety of other poly-
mers. The other method involves the removal of water without solvent under milder
conditions to produce a cyclic intermediate dimer referred to as lactide (24). Poly-
lactic acid is one of the few polymers in which the stereochemical structure can
easily be modified by polymerizing a controlled mixture of L- or D-isomers
(meso forms) to yield high-molecular-weight polymers. The properties of polylactic
acid depend entirely on the ratio of these two meso forms of lactic acid. The struc-
tures of the two meso forms are shown in Figure 3.
A great variation in the properties of products can be observed by using D, L,
and different D/L ratios of polylactic acid. A product with high melting point and
high crystallinity is obtained by using the L-isomer of lactic acid. On the other
hand, an amorphous polymer is obtained by using a mixture of D and L isomers.
This feature is very important, particularly in the binder fiber area (24). PLA,
furthermore, is environmentally friendly. The products of PLA can completely
degrade to carbon dioxide and water (24, 25).

2.5. Cashewnut Shell Liquid (CNSL)


Cashewnut Shell Liquid (CNSL) is an agricultural product, which as such, qualifies
its inclusion in the category of renewable resource. Major components of CNSL
have been characterized by various researchers using different techniques such as
ultraviolet (UV), infrared (IR), nuclear magnetic resonance (NMR) spectroscopy,

OH O
OH OH
O HO
CH3 CH3

D-lactic acid L-lactic acid


Figure 3. D and L forms of lactic acid.
POLYMERS FROM RENEWABLE RESOURCES 285

OH

Cardanol

OH O

OH

Anacardic acid

OH

HO
Cardol

OH
H3C

HO
6-Methylcardol

Figure 4. Structure of four major components of cashewnut shell liquid (CNSL).

and chromatography. The four major components of cashewnut shell liquid are
cardanol, cardol, anacardic acid, and 6-methylcardol (26). Structures of these
four components of CNSL are shown in Figure 4.
Several resins have been prepared by Guru et al. (27) using cardanyl acrylate,
which is a derivative of cardanol (major constituent of cashewnut shell liquid)
and furfural in the presence of an acid catalyst and a selective organic compound.
They studied the thermal behavior of these resins as well as their solvent absorptiv-
ity using solvents such as toluene and dimethyl formamide. The organic compounds
used were thiourea, o-hydroxybenzoic acid, m-phenylene diamine, and m-chloro-
phenol. The scheme of the reaction of cardanyl acrylate, furfural, and an organic
compound is shown in Figure 5. Thermal studies of these resins has shown that
the first great loss in weight occurs at 700 C and is a result of segmental
fragmentation of cardanyl acrylate and ring unzipping of organic compounds. It
was observed that resins obtained from thiourea had a higher thermal stability
because of the absence of aromatic rings.
In another study, Nayak et al. (26) prepared CNSL-novalac resins by condensing
cardanyl acrylate with p-aminobenzoic acid and formaldehyde in the presence of an
acid catalyst. Thermogravimetric analysis and degradation studies on these resins
have been carried out. It was observed that this resin decomposed with the removal
286 VEGETABLE OILS IN PRODUCTION OF POLYMERS AND PLASTICS

O
O C CH CH2 NH2
CHO ∆,4−6 hrs, H+
+ O +
R NH2
CA FF MPDA

O
O C CH CH2 NH2

CH

R NH2
O
Resin (CA-FF-MPDA)

Figure 5. Reaction scheme of polycondensation of cardanyl acrylate (CA) with m-Phenylene


Diamine (MPDA) and Furfural (FF) in the presence of acid as the catalyst.

of water. Swain et al. (28) have also reported the preparation of a number of resins
by condensing diazotized cardanol with formaldehyde and organic compounds in
the presence of an acid as a catalyst. They also carried out investigations on the
thermogravimetric properties of the resin, which resulted in a weight loss of this
resin of about 67–74% at 700 C.
Polyesters and polyurethanes can be prepared by bifunctional monomers like
dianhydrohexitols, which are readily available from D-glucose and D-mannose.
The structures of dianhydrohexitols are shown in Figure 6. Okada et al. (2) prepared
polyesters based on furan rings. The scheme of the polyester formation is shown in
Figure 7. They studied the biodegradability of these polyesters by three methods:
hydrolysis in a phosphate buffer solution, soil burial degradation, and enzymatic
degradation. They observed that the hydrolytic degradability of these polyesters
is low, whereas soil burial degradation shows that several spores and hypas of
actinomycetes were grown within 100 days showing erosion of the surface of the
film, meaning these polyesters are biodegradable.

HO HO

O O

O O

OH OH
Figure 6. Structures of dianhydrohexitols.
POLYMERS FROM RENEWABLE RESOURCES 287

HO

O O O
+ O O
O
O O
OH

O
O O
O R O n

Figure 7. General scheme of polyester formation.

2.6. Triacylglycerol Oils


It has been reported above that low-cost biodegradable polymers can be prepared by
using polysaccharides, fibers, and polylactic acid. In addition to these renewable
resources, naturally occurring triacylglycerol (TAG) oils are also significant starting
materials for the production of biodegradable polymers (6, 29). The TAG oils of
linseed, tung, lunaria, Lesquerella gracilis, and crambe have been used as sources
of polymers by virtue of their double bonds; functional groups that can result in
polymerization (8). The double bonds of these and other TAG oils can also be epox-
idized or converted into hydroxyl groups to increase their reactivity (6). Only a few
TAG oils, however, contain naturally occurring special functional groups, i.e.,
hydroxyl and epoxy groups (30, 31). For example, castor oil and Lesquerella pal-
meri (also called bladder pods or pop weed) contain hydroxyl groups in addition to
double bonds. Similarly, vernonia oil contains a natural epoxide functional group
(31–33). The structures of the main triacylglycerols of castor, lesquerella palmeri,
and vernonia oils are shown in Figure 8. The hydroxyl and epoxide functional
groups on these long and complex TAG molecules may be exploited to allow
such molecules to be cross-linked, which allows large macromolecules to be
formed.
Castor oil from castor beans contains high percentage triacylglycerols (TAGs) of
ricinoleic acid (83.6–90%), which is a C-18 fatty acid. Castor oil is unique in that
its TAGs contain both double bonds and nonconjugated hydroxyl groups. The tri-
functional nature of castor oil contributes toughness to the structure, and the long
fatty acid chain imparts flexibility. As a result of its unusual structure, this oil is
very versatile in its applications. It is used in making paints, adhesives, and
urethane foams (34). Lesquerella oil, a C-20 oil, is obtained from a wild plant. It
contains fatty acids similar to ricinoleic acid, but also contains two additional
288 VEGETABLE OILS IN PRODUCTION OF POLYMERS AND PLASTICS

O OH
O OH
O
O OH
O
O
Caster oil (triricinolein)

O OH
O
O OH
O
O OH
O

Lesquerella palmeri oil (trilesquerolic acid)

O O
O
O O
O
O O
O

Vernonia oil (trivernolin)

Figure 8. Chemical structures of triricinolein, trilesquerollic, trivernolin, major triacylglycerols,


respectively of castor, Lesquerella palmeri, and vernonia oils.


CH2  groups on the acid residue. Vernonia oil has a relatively low viscosity
because of high epoxide concentration. It is, therefore, mostly used as a diluent
for coating applications (34).
Soybean oil, another TAG oil, is being used in the manufacturing of plastics,
resins, and adhesives. Soybeans themselves contain 20% oil and 40% proteins;
they contain discrete groups of proteins that have unusual adhesive properties
(35). Soy-based plastics have many applications, which include their use in the pro-
duction of parts for agricultural equipment, such as tractors and farming machines,
and for the automotive industry. The applications also include civil engineering
components for bridges and highways, marine infrastructures such as pipes and off-
shore equipment, rail infrastructure such as carriages, box cars, and grain hoppers,
and in the construction industry such as formaldehyde free particle board, ceilings,
and engineered lumbers (36). Different techniques such as injection molding and
compression molding are used to prepare soy-protein plastics.
Jiratumnukul and Michael (37) have reported the use of different glycol esters
from soybean oil, such as ethylene glycol, propylene glycol, diethylene glycol, and
dipropylene glycol, for making new coalescent aids. They investigated the proper-
ties of these coalescent aids as related to evaporation rates and Minimum Film
EXPLOITATION OF THE FUNCTIONAL GROUPS ON TRIGLYCEROL MOLECULES 289

Formation Temperature (MFFT). Based on their observations, soybean oil glycol


esters are not classified as volatile organic compounds.

3. EXPLOITATION OF THE FUNCTIONAL GROUPS


ON TRIGLYCEROL MOLECULES FOR THE PRODUCTION
OF POLYMERS

Different functional groups on TAG oils, such as carbon-carbon double bonds and
epoxy and hydroxyl groups, play an important part in the formation of polymers.
Oils from various sources contain different functional groups. The occurrence of
these functional groups in oils from different sources and their significance in the
production of polymers is described below.

3.1. Double Bonds


Among the oils that contain carbon-carbon double bonds as the functional groups,
linseed, tung, corn, cottonseed, rapeseed, and soybean are more widely used as
polymeric sources. Linseed oil is extracted from the seeds of the flax plant (Linum
usitatissimum). The major constituents of linseed oil are a-linolenic acid (60%),
linoleic acid (29%), and oleic acid (27%). This composition varies with changes
in climatic conditions. On the other hand, tung oil, also called china wood oil, is
derived from the seeds or nuts of the trees aleurites fordii and A. montana. The
major constituent of tung oil is eleostearic acid (77–82%), whereas the other impor-
tant components of tung oil are oleic acid (3.5–12.7%) and linoleic acid (8–10%). It
is known that the carbon-carbon double bond in oleic acid is at C9, in linoleic acid
it is at C6 and C9, and in linolenic acid it is at C3, C6, and C9, whereas eleostearic
acid has double bonds at positions C5, C7, and C9.
The structures of oleic, linoleic, linolenic, and eleostearic acids are given in
Figure 9. Linseed oil and the tung oil are collectively called ‘‘drying oils,’’ which
are defined as liquid oils that dry in air to form a solid film (these oils have iodine
values greater than or equal to 150 units). Soybean oil, sunflower oil, and canola oil
are semidrying oils, with iodine values between 110 units and 150 units. The drying
power of such oils is directly related to the chemical reactivity conferred on the
TAG molecules by the carbon-carbon double bonds of the unsaturated acids, which
allows them to react with atmospheric oxygen, thus leading to the process of
polymerization to form polymeric networks.
Linseed oil, which contains 60% a-linolenic acid, is an example of a nonconju-
gated oil, which is rich in polyunsaturated fatty acids. These polyunsaturated fatty
acids contain double bonds, which are separated by at least two single bonds. The
linolenic acid content in nonconjugated oils plays an important role in the drying
process that is generally considered to be the result of a process of autoxidation
followed by polymerization when the oil absorbs large amounts of oxygen. The
process of autoxidation in the case of nonconjugated oil systems begins with the
dehydrogenation of unsaturated fatty acids, such as linolenic acid, by means of
atmospheric oxygen. As a result, dehydrogenated radicals are formed and chain
290 VEGETABLE OILS IN PRODUCTION OF POLYMERS AND PLASTICS

HO
C
O
a) Oleic acid

HO
C
O
b) Linoleic acid

HO
C
O
c) Linolenic acid

HO
C
O
d) Eleostearic acid

Figure 9. Structures of oleic, linoleic, a-linolenic and eleostearic acid.

polymerization starts with the formation of hydroperoxide. Furthermore, cross-


linking takes place to form large molecules. A summary of this process is shown
in Figure 10.
Tung oil with eleostearic acid as its major component, on the other hand, is an
example of conjugated oil systems. The conjugated double bonds of oils, such as
those of tung oil, favor polymerization and oxidation more rapidly than nonconju-
gated oils. The principal drying component of tung oil is eleostearic acid. As a con-
sequence of this polymerization, the resultant product obtained is highly resistant to
water and alkali. Drying of films in the case of conjugated oils consists of the fol-
lowing three steps:

1. Induction: This process begins by the autocatalysis of eleostearic acid, and


the oxygen uptake starts increasing slowly.
2. Initiation: The film continues to absorb oxygen from the atmosphere and, as a
result of this absorption, the mass of the film increases and the double bonds
of eleostearic acid undergo a rearrangement process. On rearrangement,
hydroxyl and hydroperoxy groups are formed in the film.
3. Cross-linking: As a result of the above two steps, the number of double bonds
decreases due to cross-linking and, thus, larger molecules are formed.

For many applications, tung oils often cure so rapidly that a highly wrinkled sur-
face forms. Therefore, it is necessary to modify the reactivity of tung oil, which is
EXPLOITATION OF THE FUNCTIONAL GROUPS ON TRIGLYCEROL MOLECULES 291

ROOH
INITIATION Homolytic Cleavage
Heat
of a peroxide

RO OH
RH
ROH O2
R
ROOH
PROPAGATION
RH ROO

PRODUCTS OF TERMINATION RR, ROR, ROOR

MAJOR SOURCE OF RH

POLYMERIZATION
H
R

O2
R
OO

RH polymers
R
OOH

Figure 10. Stepwise drying process of oils with double bond functionality.

possible by reducing the number of double bonds present. The reactivity can be
modified by chemical means, such as the Diels-Alder reaction with a reactive die-
nophile (38) and copolymerization with styrene (39) and diacrylate (40); this
reduces the number of double bonds and causes the cure speed of the copolymers
to be slower, resulting in a nonwrinkled surface. Also, by controlling comonomer
stoichometry, sufficient residual double bonds should remain so that oxidative cure
of the copolymers would be still possible.
On the other hand, the high degree of unsaturation of this type of drying oil has
made it a potential monomer for polymerization into useful polymers. More
recently, Li and Larock (41) reported the conversion of tung oil to solid polymers
by cationic copolymerization with divinylbenzene as a comonomor. The result-
ing polymers have proven to be thermosetting materials with good mechanical
292 VEGETABLE OILS IN PRODUCTION OF POLYMERS AND PLASTICS

properties and thermal stabilities and may find applications in replacing petroleum-
based polymeric materials because of their presumed ability to biodegrade and the
low cost of their preparation from renewable natural resources (i.e., vegetable oils).
Furthermore, the multiple double bonds also make tung oil a thermally polymer-
izable monomer at elevated temperatures. Li and Larock (42) produced a variety of
polymers prepared by thermal copolymerization of tung oil, styrene, and divinyl-
benzene in the temperature range of 85–160 C by varying the stoichiometry, oxy-
gen uptake, peroxides, and metallic catalysts. They found that the stoichiometry
and the addition of metallic catalysts greatly affect the mechanical, thermal, and
physical properties of the resulting polymers. However, the variations of oxygen
uptake and peroxides have little effect. Li and Larock also (43–50) proposed a
direct method to convert soybean oil to polymers by cationic copolymerization
with divinylbenzene or mixtures of styrene and divinylbenzene initiated by boron
trifluoride diethyl etherate or other modified initiators. The polymers obtained can
range from soft rubbers to hard plastics, depending on the reagents, stoichometry,
and initiators used in the synthetic process. The resulting polymers exhibit thermal,
physical, and mechanical properties that were competitive with those of their
petroleum-based counterparts, as well as some other very promising properties,
including good damping and shape memory properties.
Knot et al. (51) converted soybean oil to several monomers for use in structural
applications. They prepared rigid thermosetting resins by using free radical copo-
lymerization of maleates with styrene. The maleates are obtained by glycerol trans-
esterification of the soybean oil, followed by esterification with maleric anhydride.
They also synthesized several TAG-based polymers and composites and compared
their properties. It was found that the moduli and glass transition temperature (Tg)
of the polymers varied and depended on the particular monomer and the resin com-
position. They proposed that the transition from glassy to rubbery behavior was
extremely broad for these polymers as a result of the TAG molecules acting both
as cross-linkers as well as plasticizers in the system.

3.2. Hydroxyl Groups


Triacylglycerol oils, such as castor and lesquerella, are naturally occurring oils that
have hydroxyl groups on their major TAG molecules. The major component of cas-
tor oil is ricinoleic acid (C18), which has a hydroxyl group at C12. On the other
hand, the principal component of Lesquerella palmeri is lesquerellic acid (C21),
having a hydroxyl moiety at C14. The structures of ricinoleic and lesquerolic acids
are shown in Figure 11. Based on the TAG molecules of these acids shown in
Figure 8, these oils are referred to as trihydroxyl polyols or triols. These polyols
are important for the production of cross-linked polymers. The presence of the
hydroxyl groups permit reaction with diisocyanates to form polyurethanes. Polye-
sters are formed when hydroxyl groups react with dibasic acids, such as sebacic
acid obtained from castor oil, to form aliphatic polyesters with the removal of a
water molecule as byproduct (52). Castor oil derivatives, obtained through alkali
pyrolysis can also be useful, such as decanedioic acid (sebacic acid), which is
EXPLOITATION OF THE FUNCTIONAL GROUPS ON TRIGLYCEROL MOLECULES 293

HO
C
O OH
a) Ricinoleic acid

HO
C
O OH
b) Lesquerolic acid

Figure 11. Structures of ricinoleic and lesquerolic acid.

used as a monomer for nylon 610, and undecylenic acid, which forms 11-aminoun-
decanoic acid, which is the monomer for nylon 11 (34). Nylon is an important poly-
mer that is used for engineering plastics in the automotive and transport industry,
for example. Nylon products are also used in powder coating to cast metals that
require abrasion, impact, and corrosion resistance.
Isocyanates are the derivatives of isocyanic acid (HN C O). The functional-
ity of the isocyanate (N C O) group is highly reactive toward proton-bearing
nucleophiles, and the reaction of isocyanate usually proceeds with addition to the
carbon-nitrogen bond. The reactions of isocyanates fall into two main categories:
(1) active hydrogen donor, and (2) nonactive hydrogen reaction. The more signifi-
cant of these is the first category, where isocyanates react with polyols, which
involves reaction with active hydrogen. The second category of reactions involving
nonactive hydrogen reactions usually leads to cycloaddition products and linearly
polymerized products. Some examples of diisocyanates are: 2,4-toluene diisocya-
nate, 2,6-toluene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,5-naphtha-
lene diisocyanate, among others. The reactivity of isocyanates depends on their
chemical structures. Aromatic isocyanates are usually more reactive than their ali-
phatic counterparts. The presence of electron withdrawing substituents on isocya-
nates increases the partial positive charge on the carbon atom and moves the
negative charge further away from the reaction site. As a result of this character,
the reaction between the donor substance and the carbon atom of isocyanates is
fast. Therefore, whenever polyols or triols react with an isocyanate, the resulting
polyurethane is cross-linked. The extent of cross-linking affects the 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. The degree
of cross-linking is entirely dependent on the NCO/OH ratio. Branching occurs at
the urethane linkage when NCO/OH ratio is low. Low degree of cross-linking
allows the molecules freedom of movement resulting in the improvement in
strength and creep resistance. However, a slight loss in the soft, flexible, rubbery
behavior occurs. On the other hand, when NCO/OH ratio is high, the probability
of the formation of urea linkages is greater and, therefore, the branching takes place
at the urea linkage points. A high degree of cross-linking, in contrast, immobilizes
the polymer molecules and, thus, the resulting polymer becomes a thermoset
294 VEGETABLE OILS IN PRODUCTION OF POLYMERS AND PLASTICS

plastic. Das and Lenka (53) and Barrett et al. (34) have reported the preparation of
polymers by using toluene diisocyanate and hexamethylene diisocyanate. They
observed that increased ratio resulted in a highly cross-linked product with high
thermal stability.
It is known that increased cross-linking brings the polymer backbone closer
together. There is, therefore, a reduction in molecular mobility and an increase
in glass transition temperature. The weaker and less stable cross-linkages at high
temperatures tend to reopen and revert back to linear structures. Less cross-linked
polymers absorb large amounts of solvent and, thus, swell to form soft gels. Highly
cross-linked polymers, however, absorb less solvent molecules as a result of less
molecular mobility and, thus, cannot move apart to accept solvent molecules.
The preparation of polyols from vegetable oils, such as castor oil, safflower oil,
linseed oil, and soybean oil, has been studied by several groups. There are many
ways to introduce hydroxyl groups into oils, resulting in different polyol structures
and different polyurethanes ranging from elastomers to rigid foams. Polyurethane
prepared from castor polyols exhibits a broad range of properties. Low-viscosity
urethane polymers have been found extremely useful for potting electrical compo-
nents, for which fast penetration without air voids and fast dispensing cycles are
desirable (54). Meanwhile, very low-viscosity polyurethane systems containing
castor polyols have been prepared for use in telephone cable (55). On the other
hand, polymerization, whether chemical or oxidative, of castor oil resulted in oils
with higher viscosity that were more useful in the polyurethane coating industry
than untreated ones (56).
Castor oil and its derivatives have been used in the preparation of rigid, semiri-
gid, and flexible polyurethane foams. Castor oil’s resistance to hydrolysis, pigment
dispersion ability, and compatibility with polyether polyols has also made it useful
as a modifier for polyether-based foam. Castor oil can also be used to formulate
commercially acceptable rigid polyurethane foams for use as thermal insulations
and structural material (57). Superior rigid polyurethane foams have been prepared
from hydroxymethylated polyol esters of castor acids. Frankel et al. (58, 59) pre-
pared castor, safflower, and linseed oil derivatives with enhanced hydroxyl group by
hydroformylation with a rhodium-triphenylphosphine catalyst, followed by hydro-
genation. The polyurethane foams obtained had good compressive strength and
dimensional stability that met the requirements of commercial products.
Recently, Petrovic and coworkers (60–69) developed two technologies to pre-
pare soybean oil-based polyols for general polyurethane use. In the first technology,
the oil was first epoxized using the standard epoxidation procedure, followed by
alcoholysis to form the TAG polyol. In the second, the double bonds of the soybean
oil were first converted to aldehydes by hydroformylation with either rhodium or
cobalt as the catalyst, followed by hydrogenation to alcohols by nickel. The polyols
were then reacted with a diisocyanate to yield polyurethanes. The resulting polyur-
ethane can behave as a hard rubber or a rigid plastic, depending on the methods
used in the reaction process, such as by controlling the degrees of conversion, using
different diisocyanate components, and varying the stoichiometry. They found that
the rhodium-catalyzed hydroformylation of soybean oil with high conversion of
EXPLOITATION OF THE FUNCTIONAL GROUPS ON TRIGLYCEROL MOLECULES 295

olefins leads to a rigid plastic polyurethane at room temperature, whereas the


cobalt-catalyzed hydroformylation with low conversion of olefins gave a hard rub-
ber. The properties of the product can also be controlled by the cross-linking den-
sity. Polymers prepared with NCO/OH ratio from 1.05–0.8 were glassy, whereas
with the others, less than 0.8 were rubbery. The selection of the diisocyanate com-
ponent affects the cross-linking and properties of the polyurethane as well. Usually,
aromatic isocyanates produce more rigid polyurethanes than their aliphatic counter-
parts, but their oxidative and ultraviolet stability are lower. Within aromatic isocya-
nates, 2,4-toluene diisocyanate (TDI) is chosen to obtain the most flexible product.
Rigid foams can be made from TDI prepolymers but are most often based on a
polymeric diphenylmethane 4,4- diisocyanate (MDI). Aliphatic isocyanates give
rubbery polymers with higher elongation at break, higher swelling, and lower ten-
sile strength. The thermal stability of polyurethanes was also investigated. It was
found that the thermal stability depended on the functionality of the polyol, i.e.,
on the number of urethane groups per unit volume, as well as structural differences.
John et al. (70) studied and compared the properties of polyurethane foam
obtained from soybean oil-based polyols and synthetic polyols and found that the
soybean-based polyols showed enhanced reactivity and that the foaming reactions
proceeded in a very similar way to synthetic polyols. It was also found that their
properties were sensitive to several variables such as water content, isocyanate
index, and catalysts. The reaction rate was mainly controlled by the water and iso-
cyanate content. As the water content increased, the reaction was faster and the
amount of the hard segment increased. In addition, MDI yielded more rigid foams
than TDI.
Polyesters obtained from lesquerella oil have variations in colors and have low
solution viscosity as compared with castor oil polyesters. The viscosity variations
are usually associated with the structural differences of the oil. Solution viscosity of
castor oil-based polyesters is usually high because ricinoleic acid in castor oil
allows extensive hydroxyl hydrogen bonding. Furthermore, lesquerella oil-based
polyesters are effectively plasticized because of longer C20 fatty acid. The hydro-
xyl group of lesquerella oil can be exploited to make acrylates. The scheme for
making lesquerella oil-based acrylates is shown in Figure 12. Lesquerella oil acry-
lates impart excellent gloss to wood, aluminum, and steel and have good adhesive
properties. The hydroxyl groups of lesquerella and castor oil also react with
cycloethers such as propylene oxide, epichlorohydrin, and ethylene oxide. As a
result of these reactions, novel polyhydroxy compounds of much improved reactiv-
ity can be obtained. Epichlorohydrin-modified lesquerella oil has increased reactiv-
ity characteristics. The coatings developed from epichlorohydrin and lesquerella oil
form harder films in shorter dry time. The mechanism is shown in Figure 13.

3.3. Epoxides
Vernonia oil contains a naturally occurring epoxide group on C12. It is, therefore,
important for the productions of polymers. It is also used in making adhesives,
plasticizers, industrial coatings, varnishes, and paints (32). Vernonia oil can be
296 VEGETABLE OILS IN PRODUCTION OF POLYMERS AND PLASTICS

O
O
N O
H
HN O
O
O

O
O

Gly O O
N O

HN
H O
H
O

OH
O
Gly
O

Cl

O
O
O
Gly
O

Figure 12. Synthesis of lesquerella oil acrylates.

polymerized through a variety of reactions. A natural elastomer can be synthesized


by reacting vernonia oil with naturally occurring dibasic acids, such as the sebacic
acid derived from castor oil (4). It is known that castor oil is the major source of
dibasic acids, such as decanedioic and nonanedioic acids (subaric and azelaic acids,
respectively), through pyrolitic decomposition. These acids can also be derived
from vernonia oil via an efficient reaction sequence (71). The obtained aliphatic
dibasic acids are established industrial raw materials that can be used as plasticizers
and impact resistant elastomers as well (30).
On the other hand, the rubbery nature of the polymerized oil may be used as
toughening, rigid epoxy materials because it is phase separated into spherical
domains when mixed and cured with bisphenol-A epoxy compounds (72–75). A
EXPLOITATION OF THE FUNCTIONAL GROUPS ON TRIGLYCEROL MOLECULES 297

O OH
C
HO

Cl
O

HO

Cl
O O
C
HO
Figure 13. Epichlorohydrin modification of lesquerella oil.

reinforced elastomer, however, is formed because the vernonia oil-sebacic acid


polyester forms a continuous phase. The reaction is shown in Figure 14. Sperling
and Manson (30) compared the glass transition temperature of vernonia oil polye-
ster with that of epoxidized linseed oil polyester. They observed that the glass tran-
sition temperature of linseed oil polyester was higher than that of vernonia oil
polyester because of dense cross-linking in epoxidized linseed oil. Vernonia oil is

O O
O
O O
O
O O
O

2 SA

O OH
O
O OH SA
O
O OH
O
SA

O
OH
SA = Sebacic Acid = HO
O

Figure 14. Reaction of sebacic acid with vernonia oil.


298 VEGETABLE OILS IN PRODUCTION OF POLYMERS AND PLASTICS

O O
O
O O
O
O O
O

3 MA

O HO
O
O HO MA
O
O HO MA
O
MA

O
MA = Methyl Acrylate =
OH

Figure 15. Methyl acrylation of vernonia oil.

soluble in many organic solvents and diluents as it contains both oxirane ring and a
double bond. These two features are useful in drying and curing mechanisms.
The epoxide moieties of vernonia oil play an important role in making acrylates,
groups useful in making UV curing formulations. For instance, the methacrylate
ester of vernonia oil is synthesized by reaction with methacrylic acid in the pre-
sence of a tertiary amine. The acrylate ester is UV active and is therefore easily
polymerized through the acrylate vinyl moieties. The mechanism of making verno-
nia oil-based acrylates is shown in Figure 15.
Epoxidized soybean and linseed oils are the two main representatives of the
industrially produced epoxidized vegetable oils. Both are obtained by epoxidation
of the corresponding unsaturated oils, and the degree of epoxidation can be con-
trolled by reaction time. Muturi et al. (76) found that the molecular structures
and properties of partially epoxidized soybean and linseed oils are similar to those
of vernonia oil. They are suitable for the preparation of low volatile organic com-
pound alkyd and epoxy coatings formulations. However, fully epoxidized oils are
not as good as vernonia oil for making reactive diluents for coatings because of
their higher viscosities and melting points. Epoxidized soybean oil is widely
applied as a polyvinyl chloride (PVC) additive to improve PVC processing, stabi-
lity, and flexibility (77). In addition, the double bond of vernonia oil can be con-
verted into an oxirane functional group. These ‘‘super epoxides’’ have the potential
USE OF NATURALLY FUNCTIONALIZED TRIACYLGLYCEROL OILS 299

O O
O
O O
O
O O
O

O O
OH

Cl

O O O
O OH
O
O O O
O +
O O O
O Cl

Figure 16. Epoxidation of vernonia oil.

to serve as the reactive components of epoxide powder coatings. This super epox-
idized vernonia oil possesses a higher glass transition temperature than natural
vernonia oil. This characteristic is, therefore, useful for excessive plasticization.
The epoxidation of vernonia oil is represented in Figure 16.
As these oils contain multiple functionalities, they provide an alternative to pet-
roleum as a chemical feedstock. They are derived from cultivated or wild plants.
There is an international interest in using these naturally occurring oils as the start-
ing material for polymer production because excessive quantities of nonrenewable
petroleum are now being consumed (34).

4. USE OF NATURALLY FUNCTIONALIZED TRIACYLGLYCEROL


OILS IN INTERPENETRATING POLYMER NETWORKS

As mentioned earlier, TAG oils may contain special functional groups that deliver
the potential of converting these oils into biopolymers. Such functional groups
make these oils particularly important as they can be polymerized with an appro-
priate bifunctional reactant to form polymers, if they contain a hydroxyl or epoxide
functional groups (34, 52). These oils contain hydroxyl as well as unconjugated
vinyl groups in their structural backbone. The presence of double bonds can be
exploited via a chain-growth mechanism to form polymerized plastics. On account
of these two features, these oils have the unique quality to control elasticity as well
as plasticity in a single backbone chain structure (78, 79). The cross-linking of
hydroxyl groups in a step-growth polymerization gives rise to ‘‘Interpenetrating
Polymer Networks’’ (IPN) (79). IPN materials contain ‘‘two or more polymers in
a network form with at least one polymer that is polymerized or cross-linked in the
300 VEGETABLE OILS IN PRODUCTION OF POLYMERS AND PLASTICS

immediate presence of the other’’ (80, 81). Two major IPNs have been explored.
These are referred to as sequential and simultaneous IPN. Sequential IPNs involves
the preparation of one cross-linked polymer network and a subsequent swelling
with the monomer. This is then cross-linked with a second component and polymer-
ized in a network to a form sequential IPN. These two polymer networks are pre-
pared separately before polymerization. On the other hand, simultaneous IPN
involve the simultaneous mixing of all the components in one step followed by
the formation of both networks via independent reactions proceeding in the same
reaction vessel (32, 52, 80, 81).
Polyurethanes and polyurethane-based IPN have gained great importance in
recent years. Polyurethanes are divided into several classes. Some polyurethanes
are used in foams, whereas others are used for making fibers. Segmented elastomers
are perhaps the most interesting class of polyurethanes. This category of polyur-
ethanes is a kind of multiblock copolymer (82). The block copolymer is defined
as a type of polymer blend that contains two polymer chains that are linked end
to end (81, 83). In addition to various other uses, polyurethane materials are
extensively used in the medical field, such as in the production of medical-grade
tubing (82).

4.1. Use of Castor Oil-Based Polyurethanes/Polyesters for Making


Interpenetrating Polymer Networks
Several scientists have worked on the production of IPN and their characterization
based on a castor oil polyurethane model. Sperling and coworkers (84, 85) have
published a number of very interesting papers on IPNs from castor oils. The hydro-
xyl groups were reacted with 2,4-toluene diisocyanate for polyurethane formation.
Styrene and divinylbenzene were polymerized, and thus interpenetrated, to prepare
IPN and simultaneous interpenetrating networks (SIN) by using either individually
or mixed polyester-urethane. These IPNs and SINs can be tough plastics or rein-
forced elastomers depending on their compositions, which were shown from mod-
ulus-temperature, stress-strain, and impact-resistant studies. Furthermore, the
morphology of these IPNs and SINs depended on the synthetic method, such as
reaction time, stirring time, and time to pour into the mold. Yenwo et al. (84, 85)
synthesized sequential IPNs using castor oil and studied the dynamic mechanical
properties of the IPN. The experimental data showed that the molecular mixing
of the two networks was extensive but incomplete. Mechanical properties of such
systems were related to the degree of phase continuity and inversion.
Siddaramaiah et al. (86) employed an X-ray diffraction method to determine the
microstructural parameters of IPNs of castor oil-based polyurethanes and polystyr-
ene and correlated the changes of microstructural parameters to the physical macro
changes, such as hardness. They found that the addition of polystyrene (PS) resulted
in an increase in hardness that was due to an increase in crystal size.
Nayak and coworkers (7, 29, 87) prepared a series of IPNs by first reacting
castor oil with diisocyanate to form a prepolymer then polymerizing with
methacrylate, acrylamide, and cardanyl acrylate, respectively, using ethylene glycol
USE OF NATURALLY FUNCTIONALIZED TRIACYLGLYCEROL OILS 301

dimethacrylate as cross-linker and benzoyl peroxide as initiator, and studied their


high-temperature degradation mechanism and mechanical properties. The thermo-
gravimetric analysis was followed by a computer analysis method for assisting the
kinetic mechanism and a new mechanism of degradation was suggested based on
these kinetic parameters.
A special case of IPN is the SIN (88). The existence of SINs provides a novel
way to control the phase states and mechanical behavior of two-phase materials. As
a result of the multiple chemical compositions and synthetic routes involved in the
formation of SINs, polymers can be made with very different mechanical behavior.
Among the features that control the behavior of the resulting blends, microphase
structures and molecular interactions are of greatest importance for the determina-
tion of mechanical properties of the two coexisting phases. There are usually two
ways of forming a SIN. One involves the simultaneous polymerization of two poly-
mers, whereas the second involves the mixing of two kinds of monomers together,
which are polymerized sequentially (88). The two techniques give different pro-
ducts with different morphologies and different mechanical behaviors. Various
studies have been done on the properties and structures of the resulting SIN.
Devia-Manjarres et al. (88) and Devia et al. (89) studied the morphology and glass
transition behavior of SIN based on elastomeric polymers derived from castor oil
and cross-linked polystyrene by using electron microscopy and dynamic mechan-
ical spectroscopy techniques, respectively. A two-phase morphology was revealed
by electron microscopy. Depending on the synthetic conditions, either phase can be
continuous. Morphological details, however, can be determined by compatibility of
the polymer networks, speed of stirring, and reaction rates of network formation
(80). Dynamic mechanical spectroscopy results showed two glass transition tem-
peratures around the homopolymer glass transition temperatures but shifted inward.
These materials proved to be tougher than their corresponding homopolymer
networks. The toughness of these SINs increased with a decreasing domain size
of the dispersed phase. The use of castor oil-based elastomers in the brittle polymer-
polystyrene produces toughened plastic with an enhanced tensile strength and
impact properties (89).
Suthar and coworkers (83, 90, 91) investigated the SIN prepared from radical
copolymerization of liquid polyester based on castor oil and dibasic acid with poly-
styrene initiated by benzoyl peroxide in the presence of the cross-linker 1,4-divinyl-
benzene. This group also reported the preparation and morphology of sequential
IPN composed of castor oil polyurethane and various polyacrylates using ethylene
glycol dimethacrylate as a cross-linker and benzoyl peroxide as initiator. These
materials were characterized in terms of resistance to chemical reagents, the static
mechanical properties (tensile strength, Young’s modulus, and percent elongation),
thermal properties, and morphology (scanning electron microscopy).
Xie et al. (92, 93) synthesized simultaneous IPN from castor oil polyurethane
and copolymers of vinyl monomers, including styrene, methyl methacrylate, and
acrylonitrile, without cross-linker using a redox initiator at room temperature and
both the formation kinetics of cross-linking and grafting on phase separation were
examined. It was demonstrated that the resulting materials were mainly grafted IPN
302 VEGETABLE OILS IN PRODUCTION OF POLYMERS AND PLASTICS

with vinyl or acrylic polymer grafted on the double bonds of castor oil. These IPN
exhibited good properties, including high strength, good resilience, solvent resis-
tance, and high abrasion resistance.

4.2. Use of Polyethylene Terephthalate and Castor or Other Naturally


Functionalized Triglyceride Oils for Making Semi-Interpenetrating
Polymer Networks
Polyethylene terephthalate (PET) is a semicrystalline thermoplastic (79). Semicrys-
talline PET is of particular importance because of its properties, which are suitable
for the production of engineered plastics. It is a widely used polymer because of its
high strength, low price, and good solvent resistance. It is a primary material for the
production of bottles, textile industry components and auxiliaries, recording tapes,
and packaging films. However, it cannot be used in injection molding as it has a
slow crystallization rate. As a result of its slow crystallization rate, the parts molded
with PET have poor dimensional stability. PET, in combination with castor or other
naturally functionalized triglyceride oils, may be used to improve characteristics
such as toughness and faster crystallization rate (32).
As PET is a semicrystalline thermoplastic, the process of synthesizing semi-
IPNs based on PET is different from the above-mentioned method. It is known
that PET is a condensation product of terephthalic acid and ethylene glycol. Castor
oil would polymerize with terephthalic acid in competition with ethylene glycol if
SIN formation method were used. On the other hand, PET is aromatic, whereas cas-
tor oil is aliphatic in nature; they are, therefore, immiscible, which makes sequential
IPN formation impossible. In order to obtain a PET and castor oil network, the two
components must be either miscible or well mixed. It was observed that a miscible
mixture of PET and castor oil could be obtained by continuously heating the blend
together. A bond exchange reaction between ester groups of PET and ester and
hydroxyl groups of castor oil occurs during heating. As a result of this interchange,
a miscible copolymer mixture is formed and a hybrid semi-IPN structure is
obtained (79, 94). The castor oil was shown to improve the crystallization rate of
poly (ethylene terephthalate), and after the polymerization of castor oil, it offered a
mechanism for toughening the materials.
In addition, PET can be used to form semi-IPNs with other naturally functiona-
lized triglyceride oils, such as vernonia oil (31). The procedures for PET/vernonia
semi-IPNs are essentially the same as those of PET/castor ones, but with important
differences. For PET/castor mixtures, the diisocyanate cross-linker was added at
240 C and the mixture was poured into the molds rapidly before the castor gel point
had been reached. In this case, PET/castor polyurethane semi-IPNs were formed, in
which crystallization and gelation occurred simultaneously resulting in a single,
broad glass transition temperature. For PET/vernonia, the sebacic acid was added
at 280 C, which reduced the temperature to about 250 C, where the mixture was
held for another 5 min, then poured into a preheated mold and allowed to cool, dur-
ing which time the PET crystallizes. In this case, PET/vernonia polyester network
was formed, and the PET crystallized prior to network formation because the latter
REFERENCES 303

one took place more slowly. This network displayed two glass transition tempera-
tures. In another case, rather than allowing the mixture to cool, it was kept at 250 C,
which is above the crystallization temperature of PET. Under this condition, the
network is formed prior to crystallization of PET, therefore, the material was
much more rubbery and tough, and it was amorphous. In these semicrystalline
semi-IPNs, network formation before or after crystallization or phase separation
are factors that affect the crystalline and phase morphology considerably. These
factors, in turn, are reflected in the physical properties of the resulting materials.
The amounts of bond interchange, phase separation, crystallization of PET, and net-
work formation of cross-linking are factors that control the morphology and proper-
ties of materials in this and similar polymer systems.

5. CONCLUSIONS

As the world arrives closer to the global realization of our dwindling fossil fuel
resources, concern is increasing about continuity of our way of life, as so much
of the materials and energy we depend on are sourced from petroleum. As scientists
and innovators begin to search in earnest for alternative sources of some of the more
ubiquitous materials in our environment, such as plastics, other important factors,
such as degradability and environmental sustainability, are being considered. Vege-
table oils and other lipids form an important renewable source of such materials,
and based on the work reported here by a growing number of researchers, natural
and modified triacylglycerol oils can be used to produce polymers with important
functional properties. This is an important and growing area of research, and by the
time this chapter has been printed, it will almost certainly be dated, given the rate at
which research is being performed in this area. However, the material presented
here does present a snapshot of the various areas of endeavor to convert TAG
oils into polymers.

Acknowledgments

The help of Asma Saeed and Elizabeth Verghis in preparation of this manuscript is
gratefully acknowledged, as is the financial assistance of the Alberta Crop Industry
Development Fund, AVAC Ltd., the Alberta Agricultural Research Institute,
NSERC, and the Alberta Canola Producers Commission.

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