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Prog. Polym. Sci. 31 (2006) 983–1008


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Addition polymers from natural oils—A review


Vinay Sharma, P.P. Kundu
Department of Chemical Technology, Sant Longowal Institute of Engineering and Technology, Sangrur, Punjab 148106, India
Received 23 January 2006; received in revised form 14 September 2006; accepted 15 September 2006

Abstract

Emerging technological knowledge is leading research into new ventures. One such is the conversion of natural oils to
polymers to augment the use of petroleum products as the source of polymeric raw materials. Natural oils, such as vegetable
oils, now mainly used in the food industry, offer alternatives, and recent research has studied new routes of synthesis of
polymers from natural oils. This review paper discusses the synthesis and characterization of new polymers from different
natural oils such as soybean, corn, tung, linseed, castor, and fish oil. The effects of different levels of unsaturation in the
natural oils and various types of catalysts and comonomers on the properties of copolymers are considered.
r 2006 Elsevier Ltd. All rights reserved.

Keywords: Natural oils; Dynamic mechanical analysis; Cross-linking; Polymerization; Drying oil; Glass transition temperature

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 984
2. Polymers from natural oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 985
2.1. Soybean oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 985
2.1.1. Unmodified soybean oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 985
2.1.2. Modified soybean oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 992
2.2. Fish oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 994
2.3. Corn oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 995
2.4. Tung oil polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 996
2.5. Linseed oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 998
2.5.1. Natural linseed oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 998
2.5.2. Epoxidized linseed oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1002
2.6. Castor oil polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1003
2.7. Polymers from other oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1004
3. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1005
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1006
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1006

Corresponding author. Tel.: +91 16 7283606; fax: +91 16 7283657.


E-mail address: ppk923@yahoo.com (P.P. Kundu).

0079-6700/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2006.09.003
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1. Introduction epoxies, hydroxyls, cyclic groups and furanoid


groups) [2]. It is apparent that on a molecular level,
In recent years natural oils have attracted these oils are composed of many different types of
renewed attention as raw materials for the prepara- triglyceride, with numerous levels of unsaturation.
tion of resins and polymeric materials, to replace or In addition to their application in the food industry,
augment the traditional petro-chemical based poly- triglyceride oils have been used for the production
mers and resins. Natural oils such as linseed and of coatings, inks, plasticizers, lubricants and agro-
tung oil have long found various uses in the paint chemicals [3–9]. In general, drying oils (these can
and varnishes industries. These oils have tradition- polymerize in air to form a tough elastic film) are
ally been used in organic coatings either as resins or the most widely used oils in these industries,
as a raw material for the preparation of resins. although the semi-drying oils (these partially harden
Soybean oil, safflower oil, sunflower oil and canola when exposed to air) also find use in some
oil have also been used in polymerizations. applications. The polymers obtained from natural
Natural oils are tri-glyceride esters of fatty acids, oils are biopolymers in the sense that they are
the general structure of which is shown in Fig. 1. generated from renewable natural sources; they are
Triglycerides comprise three fatty acids joined by a often biodegradable as well as non-toxic.
glycerol center [1]. Most of the common oil contains Some biopolymers obtained from natural oils are
fatty acids that vary from 14 to 22 carbons in flexible and rubbery. Generally, they are prepared
length, with 1–3 double bonds. The fatty acid as cross-linked copolymers. Bacterial polyesters are
distribution of several common oils is shown in obtained from a large number of bacteria when
Table 1 [1]. In addition, there are some oils comprise subjected to metabolic stress. The cross-linking
fatty acids with other types of functionalities (e.g., process for unsaturated bacterial polyester is shown

fatty acid chain


glycerol center O

O oleic acid chain


O
O linoleic acid chain

O linolenic acid chain


O

three ester bonds

Fig. 1. The triglyceride chain containing three fatty acid chains joined by a glycerol center. Reprinted with permission from Polymer 2001;
42: 1569 r Elsevier Science Ltd., [10].

Table 1
Main fatty acid contents in different oils

Fatty acid [#C: #DB] Canola oil Corn oil Cottonseed oil Linseed oil Olive oil Soybean oil Tung oil Fish oily

Palmitic 16:0 4.1 10.9 21.6 5.5 13.7 11.0 — —


Stearic 18:0 1.8 2.0 2.6 3.5 2.5 4.0 4 —
Oleic 18:1 60.9 25.4 18.6 19.1 71.1 23.4 8 18.20
Linoleic 18:2 21.0 59.6 54.4 15.3 10.0 53.3 4 1.10
Linolenic 18:3 8.8 1.2 0.7 56.6 0.6 7.8 — 0.99
a-elaeostearic acid — — — — — — — 84 —
Average #DB/triglyceride. — 3.9 4.5 3.9 6.6 2.8 4.6 7.5 3.6

Reproduced with the permission from J Appl Polym Sci 2001; 82: 703 r John Wiley and Sons, Inc. [1].
 #C stands for number of carbon atoms in chain and #DB stands for the number of double bonds in that chain.
y
Fish oils tend to contain a high double bond content; for example, the composition of a Norway fish oil examined in one study
contained a fatty acid (ethyl ester) composition with 8.90% having no double bonds, 6.03% having four double bonds, 37.25% having
EPA or DPA and 24.72% (DHA) having six double bonds [29].
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V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 983–1008 985

in Fig. 2, describing the cross-linking of the with cyclohexane dicarboxylic acid. Scheme 2(b)
unsaturated bacterial polyesters prepared from shows the oligomerization with maleic acid, which
soybean oily fatty acids. It is observed that cross- introduces more double bonds in the oligomers.
linking occurs in at least two polyester chain double
bonds. Scheme 1 describes the representative 2. Polymers from natural oils
process of cationic copolymerization of the trigly-
ceride oil with styrene and divinylbenzene in the 2.1. Soybean oil polymers
presence of a modified boron trifluoride diethyl
etherate. Scheme 2 shows the oligomerization of a 2.1.1. Unmodified soybean oil polymers
modified acrylated epoxidized soybean oil (AESO) Polymers derived from soybean oils have been
with reagents selected to stiffen the polymer chain. extensively investigated by Larock et al. [10–15];
Scheme 2(a) shows the oligomerization of an AESO soybean oils are biodegradable vegetable oil, readily

O O
O

CH CH2 C O CH CH2 C O HC CH2 C O

O O O

CH CH2 C O CH CH2 C O CH CH2 C O

Fig. 2. The cross-linking process of bacterial polyester obtained from soybean oily fatty acids. Reprinted with the permission from Polym
Bull 2001; 46: 393 r Springer-Verlag, Inc. [24].

CH CH CO2

CH CH CO2
+ +
CH CH CO2

H2C C CH CH

O O
C O C O
CH2 CH HC CH CH CH CH2 CH CH2 CH

m n m

Scheme 1. The proposed process of cross-linking of natural oil with styrene and divinylbenzene in presence of modified initiator.
Reprinted with the permission from J Appl Polym Sci 2003; 90: 1832 r Wiley Periodicals, Inc. [30].
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986 V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 983–1008

Scheme 2. The modification of acrylated epoxidized soybean oil (AESO) shown using cyclohexane dicarboxylic anhydride or maleic
anhydride. These AESOs were cured with styrene or other comonomers. Reprinted with the permission from J Appl Polym Sci 2001; 82:
707 r John Wiley and Sons, Inc. [1].

available in bulk; specification of soybean oils used various polymers. Cationic copolymerization of
by the Larock group are reported in Table 2. regular soybean oil, low saturated soybean oil or
Natural soybean oil possesses a triglyceride struc- conjugated low saturated soybean oil with styrene
ture with highly unsaturated fatty acid side chains. and divinylbenzene leads to various copolymers.
The 1H NMR spectra of some example oils are These copolymers have been characterized by
shown in Fig. 3. The unsaturation in these oils various techniques, including dynamic mechanical
makes them ideal monomers for the preparation of analysis (DMA), thermogravimetric analysis
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Table 2
The composition of the soybean oils used for the preparation of copolymers

Soybean oil CQQC Fatty acidsb

Type No.a C16:0 C18:0 C18:1 C18:2 C18:3

Regular soybean oil Non-conjugated 4.5 10.5 3.2 22.3 54.4 8.3
Low saturated soybean oil Non-conjugated 5.1 5.0 3.0 20.0 64.0 9.0
Conjugated saturated soybean oil Conjugated 5.1 5.0 3.0 20.0 64.0 9.0

Reproduced with the permission from J Polym Sci: Part B: Polym Phys 2000; 38: 2722 r John Wiley and Sons, Inc. [12].
a
The average number of carbon-carbon double bonds was calculated by 1H NMR spectral analysis.
b
For example, C18:2 represent the fatty acid (ester) that possesses 18 carbons and 2 CQQC bonds.

Fig. 3. The 1H NMR spectra of different soybean oils. (a) regular soybean oil, (b) low saturated soybean oil and (c) conjugated low
saturated soybean oil. Reprinted with permission from J Appl Polym Sci 2001; 80: 660 r John Wiley and Sons, Inc. [11].

(TGA), differential scanning calorimetry (DSC), stoichiometry and type of the triglyceride oil used
scanning electron microscopy (SEM) and thermal [11]. The gelation time and yield for various
mechanical analysis (TMA). copolymers prepared from varying concentrations
Cationic polymerization of the soybean oil with of the oils, comonomers and modified initiators is
divinylbenzene comonomer initiated by boron tri- reported in Table 3. The yield of the cross-linked
fluoride diethyl etherate results in polymers ranging product depends on the concentration of the cross-
from soft rubbers to hard thermosets, depending on linking agents, such as divinylbenzene, dicyclopen-
the oil and the stoichiometry employed [10]. It was tadiene, etc. As usual, cross-linking increases the
found that the initiator was immiscible with these glass transition temperature of the polymer. Poly-
oils, but that miscibility was vastly improved when mers from different soybean oils show different
the initiator was modified with a norway fish oil properties, and the cross-linking density of the bulk
ethyl ester. The copolymerization of soybean oil polymers considerably affected their thermophysical
with styrene and norbornadiene or dicyclopenta- properties [12]. Several copolymers obtained from
diene initiated by boron trifluoride diethyl etherate copolymerization of a soybean oil with divinylben-
resulted in polymers with good mechanical proper- zene were characterized by DMA, TGA and soxhlet
ties and thermal stability. extraction, with the results shown in Tables 4 and 5.
It has been observed that the copolymerization of From these results, it was clear that the composition
soybean oils with other comonomers results in a of the copolymer dictated the properties. For
network, with a gelation time dependent on the example, the oily component of the copolymer
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Table 3
The results from copolymerization of different soybean oils using different modified initiator system with styrene and divinylbenzene,
norbornadiene or dicyclopentadiene

Original composition (wt%) Gelation time (s) Yield (%) of cross linked
polymer after extraction
Triglyceride oil Comonomers Initiators

45% LSS 32%ST+15%DVB 5%SG-I+3%BFE 3.0  102 83


45% LSS 32%ST+15%DVB 5%SG-II+3%BFE 3.0  102 82
45% LSS 32%ST+15%DVB 5%SG-III+3%BFE 3.0  102 83
45% LSS 32%ST+15%DVB 5%NFO+3%BFE 3.0  102 84
45% SOY 32%ST+15%DVB 5%NFO+3%BFE 2.4  102 80
45% LSS 32%ST+15%DVB 5%NFO+3%BFE 3.0  102 84
45% CLS 32%ST+15%DVB 5%NFO+3%BFE 6.6  102 92
45% CLS 32%ST+15%DVB 5%NFO+3%BFE 6.6  102 92
45% CLS 32%ST+15%NBD 5%NFO+3%BFE 3.5  103 89
45% CLS 32%ST+15%DCP 5%NFO+3%BFE 2.1  105 80

Reproduced with the permission from J Appl Polym Sci 2001; 80: 662 r John Wiley and Sons, Inc. [11].

Table 4
The DMA, TGA, and Soxhlet extraction results for the samples prepared by copolymerization of soybean oil and divinylbenzene in the
presence of modified initiator

Polymer samplea Eroom(Pa)  108 ne(mol/m3)  103 Tg(1C) Structure (wt%) TGA (1C)
b
a1 a2 Cross-linked Free oil Inc. oil T10 T50

SOY60-DVB35-BFE5 4.0 7.60 27 — 69 31 29 415 490


SOY50-DVB35-(NFO10-BFE5) 5.0 11.6 70 10 77 23 37 425 491
SOY55-DVB30-(NFO10-BFE5) 2.5 6.51 15 5 75 25 40 380 475
SOY60-DVB25-(NFO10-BFE5) 1.7 4.18 20 0 73 27 43 360 470
LSS60-DVB35-BFE5 6.0 10.4 37 - 82 18 42 423 485
LSS50-DVB35-(NFO10-BFE5) 7.0 13.0 70 0 84 16 44 425 486
LSS55-DVB30-(NFO10-BFE5) 3.8 8.35 30 8 80 20 45 405 486
LSS60-DVB25-(NFO10-BFE5) 1.9 4.18 17 0 77 23 47 395 485
CLS50-DVB35-(NFO10-BFE5) 12 18.9 90 - 88 22 48 440 485
CLS55-DVB30-(NFO10-BFE5) 10 11.4 80 - 86 14 51 436 486
CLS60-DVB25-(NFO10-BFE5) 7.8 7.21 68 - 86 14 56 433 483

Reproduced with the permission from Polymer 2001; 42: 1573 r Elsevier Science Ltd., [10].
Eroom ¼ Young’s modulus at room temperature.
ne ¼ Cross-linking density.
a
Here SOY represents regular soybean oil, LSS—Low saturated soybean oil, CLS—conjugated low saturated soybean Oil, DVB—
divinylbenzene, NFO—Norway Pronova fish oil ethyl ester and BFE —boron trifluoride diethyl etherate. The numerals, such as SOY60
represents 60 wt% of soybean oil.
b
Wt% of oil incorporated into the cross-linked network.

induces reduction in the glass transition tempera- at temperatures dependent on the oil, e.g., 68 1C for
ture, stiffness and modulus. regular soybean oil, 61 1C for low saturated soybean
The variation of the storage modulus (E0 ) and loss oil and 76 1C for conjugated low saturated soybean
factor (tan d) with temperature is shown in Figs. 4 oil. This single loss peak indicates that the polymers
and 5, respectively, for several copolymers prepared had a homogeneous phase. From these results, it is
from regular soybean oil. In Fig. 4, E0 is minimum clear that in all soybean oils used, the conjugated
for regular soybean oil and maximum for conju- low saturated soybean oil gave the highest cross-
gated low saturated soybean oil. In Fig. 5, the linking density, glass transition and storage moduli.
polymers from these oils exhibited a single loss peak Copolymers were also prepared from soybean oil
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Table 5
The tensile test results for various soybean oils

Polymer sample Tg (1C) ne (mol/m3)  102 E (mpa) sb (mpa) eb (%) Toughness (mpa)

SOY45st32-DVB15-(NFO5-BFE3) 68 1.8 71 4.1 57.1 1.67


LSS45st32-DVB15-(NFO5-BFE3) 61 5.3 90 6.0 64.1 2.86
CLS45st32-DVB15-(NFO5-BFE3) 76 22 225 11.5 40.5 4.00

Reproduced with the permission from J Polym Sci: Part B: Polym Phys 2000; 39: 62 r John Wiley and Sons, Inc. [13].
Tg ¼ Glass transition temperature.
ne ¼ Cross-linking density.
E ¼ Young’s modulus.
sb ¼ Ultimate tensile strength.
eb ¼ Elongation at break.

1. E+10 1.5
SOY45-ST32-DVB15-(NFO5-BFE3)
LLS45-ST32-DVB15-(NFO5-BFE3)
1. E+09 CLS45-ST32-DVB15-(NFO5-BFE3)
Storage Modulus (Pa)

1
1. E+08
Tan δ

1. E+07

0.5
1. E+06
SOY45-ST32-DVB15-(NFO5-BFE3)
LSS45-ST32-DVB15-(NFO5-BFE3)
CLS45-ST32-DVB15-(NFO5-BFE3)
1. E+05
-35 -15 5 25 45 65 85 105 125 0
Temperature (°C) -35 -15 5 25 45 65 85 105 125
Temperature
Fig. 4. The temperature dependence of the storage modulus (E0 )
on the copolymers prepared from regular soybean oil (SOY), Fig. 5. The temperature dependence of the loss modulus (tan d)
Lowsat soy oil (LSS) and conjugated Lowsat soy oil (CLS) with for the copolymers prepared from regular soybean oil (SOY),
styrene (ST) and divinylbenzene (DVB), using Norway fish oil Lowsat soy oil (LSS) and conjugated Lowsat soy oil (CLS) with
modified initiator. Reprinted with permission from J Polym styrene (ST) and divinylbenzene (DVB), using Norway fish oil
Sci: Part B: Polym Phys 2000; 38: 2726 r John Wiley and Sons, modified initiator. Reprinted with permission from J Polym
Inc. [12]. Sci: Part B: Polym Phys 2000; 38: 2727 r John Wiley and Sons,
Inc. [12].

and divinylbenzene, using boron trifluoride diethyl low saturated soybean oil polymers show a yield
etherate, resulting in heterogeneous polymeric point.
materials [10]. The tensile fracture surface of polymer samples
The tensile properties of several soybean oil (with 35 weight % conjugated low saturated
polymers ranging from elastomers to hard, ductile soybean oil) was observed under a scanning electron
and relatively brittle polymers are shown in Fig. 6 microscope and shown to be very similar to those of
[13]. Generally, it is observed that the ultimate epoxies [Fig. 7]. The SEM micrograph of the
tensile strength increases and the elongation at fracture surface and the mist region of the fractured
break decreases with an increase in the degree of surface are shown in Figs. 7(a) and 7(b), respec-
cross-linking. At lower strain (o10%), the increase tively, for one sample.
in stress is rapid, while at higher strain (410%), the The results for damping properties of several
regular and low saturated soybean oil polymers soybean oils over a broad range of temperature and
exhibit a slow increase in the stress. The conjugated frequency are reported in Table 6 [14]. The high
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SOY45-ST32-DVB15-(NFO5-BFE3)
LLS45-ST32-DVB15-(NFO5-BFE3)
CLS45-ST32-DVB15-(NFO5-BFE3)

12
Stress (MPa)

0
0 20 40 60 80
Strain (%)

Fig. 6. The tensile stress-strain curves from three soybean oil


polymers i.e. regular (SOY), low saturated (LSS) and conjugated
low saturated (CLS) soybean oil polymers for same percentage of
oil and comonomers styrene (ST) and divinylbenzene (DVB).
Reprinted with permission from J Polym Sci: Part B: Polym Phys
2000; 39: 63 r John Wiley and Sons, Inc. [13].

damping intensities are ascribed to the contribution Fig. 7. The SEM micrograph of sample CLS35ST39-DVB18-
(NFO5-BFE3) highlighting the mechanically fractured surface of
from the large number of ester groups directly
the sample and the mist region of the mechanically fractured
attached to the soybean oil–styrene–divinylbenzene surface. Reprinted with permission from J Polym Sci: Part B:
copolymer chains. The variation in the glass Polym Phys 2000; 39: 75 r John Wiley and Sons, Inc. [13].
transition temperature with cross-linking density is
shown in Fig. 8 for several soybean oil polymers.
The three soybean oil polymers showed the same materials to remember a specific shape on demand,
glass transition temperature, but differ in the value even after very severe deformation. Such materials
of the loss tangent maxima. The broad damping have applications in civil construction, mechanics
regions were attributed to segmental inhomogeneity and manufacturing, electronics and communica-
induced on cross-linking. However, cross-linking tions, printing and packaging, medical equipment,
also reduced the damping intensities by restricting recreation and sports, and household items.
the polymer segmental motions of the homogeneous A shape-memory polymer exhibits mechanical
polymeric materials. Thus, it is expected that behavior that includes fixing the deformation of
efficient damping materials (for sound and vibra- the plastics at room temperature and recovering the
tional applications) would result on the chemical deformation as elastomers at relatively high tem-
or physical combination of two or more struct- peratures [16–19]. Shape-memory polymers basi-
urally dissimilar soybean oil-based polymers cally consist of two phases: a reversible phase and a
to form interpenetrating networks (IPN) with a fixed phase. The reversible phase refers to the
phase separated morphology. In such a case, polymer matrix, which has a glass transition
broad damping regions would be facilitated by temperature (Tg) or a melting temperature (Tm)
phase microheterogeneity resulting from the forma- well above the application temperature. The fixed
tion of IPNs, rather than by the segmental phase is composed of either chemical or physical
inhomogeneity [14]. cross-links that are relatively stable at a temperature
Some soybean oil polymers prepared by cationic higher than the Tg or Tm of the reversible phase.
copolymerization show a good shape-memory effect At a temperature above Tg or Tm, the shape-
[15]. Shape-memory refers to the ability of some memory polymer achieves a rubbery elastic state in
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Table 6
Results for the damping properties of the copolymers prepared from different soybean oils

Polymer sample Tg(1C) ne(mol/m3) (tan d)max (tan d)rt DT at tan d40.3 (1C) TA (K) Half-width (1C)

SOY35st39-DVB18-(NFO5-BFE3) 79 4.7  102 0.88 0.12 52–115 (63) 37.5 47


SOY45st32-DVB15-(NFO5-BFE3) 68 1.8  102 0.85 0.32 23–113 (90) 48.4 61
SOY55st25-DVB12-(NFO5-BFE3) 30 1.0  102 0.84 0.83 2–65 (67) 36.3 51
LSS35st39-DVB18-(NFO5-BFE3) 80 7.3  102 0.86 0.11 23–113 (90) 48.4 51
LSS45st32-DVB15-(NFO5-BFE3) 61 5.3  102 0.89 0.37 19–97 (78) 46.2 52
LSS55st25-DVB12-(NFO5-BFE3) 32 3.9  102 1.00 0.96 6–83 (89) 50.1 57
CLS35st39-DVB18-(NFO5-BFE3) 82 3.4  103 0.94 0.07 58–116 (58) 41.8 42
CLS45st32-DVB15-(NFO5-BFE3) 76 2.2  103 0.79 0.18 48–120 (72) 43.1 53
CLS55st25-DVB12-(NFO5-BFE3) 38 6.5  102 1.08 0.80 10–77 (67) 52.9 44

Reproduced with permission from Polymers for Advanced Technologies 2002; 13: 439,441 r John Wiley and Sons, Ltd., [14].
Tg ¼ Glass transition temperature.
ne ¼ Cross-linking density.
(tan d)max ¼ Loss tangent maxima.
(tan d)rt ¼ Loss tangent at room temperature.
TA ¼ tan d area.

120 the strong relaxations of the oriented polymer


chains between the cross-links.
100
Table 7 shows the shape-memory properties of
several soybean oil polymers. It is observed that the
type of soybean oil greatly affects the shape-
80 memory properties of these polymers (e.g., see
No. 1–3). The polymers from reactive soybean oil
Tg (°°C)

60 show higher degree of fixed deformation (FD value)


and a lower deformability at a temperature higher
than Tg (D value). All of the polymeric materials
40 show 100% recovery (R) of fixed deformation upon
reheating to Tg plus 50 1C.
20 The time for gelation and vitrification of various
SOY45-(ST+DVB) 47-(NFO5-BFE3)
LSS45-(ST+DVB) 47-(NFO5-BFE3) soybean oil polymer systems has been investigated
CLS45-(ST+DVB) 47-(NFO5-BFE3) over a range of isothermal curing temperatures [20].
0
All the fully cured thermosets were first made at
10 100 1000 10000 100000
room temperature and then subjected to post-curing
υe (mol/ m3)
at elevated temperatures. The thermal stability and
Fig. 8. The dependence of the glass transition temperature (Tg) dynamic mechanical behavior of the resulting
on cross-linking density (ne) for different soybean oil polymers. thermosets were not particularly sensitive to the
Reprinted with permission from Polym Adv Technol 2002; 13: curing conditions. However, varying the curing time
444 r John Wiley and Sons, Ltd. [14]. at low and high temperatures did affect the
structural characteristics of the polymer backbone,
which it can be easily deformed by an external force. affecting the shape-memory and tensile mechanical
When the polymer is cooled to room temperature, properties. The isothermal time–temperature–trans-
the deformation is fixed due to the frozen micro formation (TTT) cure diagram, developed to study
Brownian motion of the reversible phase. The the epoxy systems [21–23], is a very useful tool for
hardened reversible phase effectively resists elastic investigating the cure process of the soybean oil
recovery resulting from the tendency of the ordered systems. The cure temperatures between Tg,gel, (Tg
chains to return to a more random state, but the at which the system gels and vitrifies simulta-
deformed shape readily returns to its original shape neously) and TgN (maximum Tg of fully cured
upon heating above Tg or Tm. The driving force for system), where gelation precedes vitrification, are of
the shape recovery is primarily entropy, especially practical importance. It was observed that gelation
ARTICLE IN PRESS
992 V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 983–1008

Table 7
Shape memory properties of soybean oil polymers

Polymer sample Tg (1C) ne (mol/m3) Shape memory results (%)

D FD R

SOY45ST32-DVB15-(NFO5-BFE3) 68 1.8  102 100 80 100


LSS45ST32-DVB15-(NFO5-BFE3) 61 5.3  102 86 96 100
CLS45ST32-DVB15-(NFO5-BFE3) 76 2.2  103 77 98 100
SOY45ST32-(DVB5-NBD5-DCP5)-(NFO5-BFE3) 42 9.8  10 100 63 100
(SOY22.5-LSS22.5)-ST32-(DVB5-NBD5-DCP5)-(NFO5-BFE3) 43 1.3  102 100 74 100
(SOY15-LSS15-CLS15)-ST32-(DVB5-NBD5-DCP5)-(NFO5-BFE3) 44 2.7  102 100 75 100
SOY45ST20-(DVB9-NBD9-DCP9)-(NFO5-BFE3) 68 3.1  102 100 97 100
(SOY22.5-LSS22.5)-ST20-(DVB9-NBD9-DCP9)-(NFO5-BFE3) 70 3.7  102 100 98 100
(SOY15-LSS15-CLS15)-ST20-(DVB9-NBD9-DCP9)-(NFO5-BFE3) 74 5.2  102 100 99 100

Reproduced with permission from Journal of Applied Polymer Science 2002; 84: 1539 r John Wiley and Sons, Ltd., [15].
Tg ¼ Glass transition temperature.
ne ¼ Cross-linking density.
D ¼ Deformability of the material at temperature higher than Tg.
FD ¼ Degree to which the deformation is fixed at ambient temperature.
R ¼ Final shape recovery.

Fig. 9. The 1H NMR spectra of acrylated epoxidized soybean oil (AESO). Reprinted with the permission from J Appl Polym Sci 2001;
82: 710 r John Wiley and Sons, Inc. [1].

occurs at approximately 15% conversion of the group. Various chemical pathways for functionali-
reactants, and the yield of cross-linked polymers zation of these triglycerides have been studied.
continued to increase following gelation. However, LaScala and Wool et al. [1] analyzed optimization
only about 50% of the soybean oil reactants were of the effect of chemical functionalization on the
converted into cross-linked polymers when the mechanical properties and thermal stability of some
system vitrified. Thus, in order to obtain fully cured resins. The viscoelastic properties of resin samples
networks, the materials were subsequently post- made of AESO and cured at room temperature with
cured at elevated temperatures. varying amounts of styrene were studied. The 1H
NMR spectra of AESO are shown in Fig. 9. Some
2.1.2. Modified soybean oil polymers triglyceride-based monomers prepared from acrylic
Several types of functionalization can be obtained acid are shown in Fig. 10. It was found that both E0
at various active sites within the triglyceride and Tg increased with increasing styrene content in
structure, such as the double bond, the ester group, the copolymers. The styrene content at 33.3 wt%, or
the allylic carbons, and the carbons a to the ester a 2:1 AESO to styrene ratio, was considered optimal
ARTICLE IN PRESS
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O O O O

O
O O O OH

O OH
OH OH
O
O
O

Acrylated Epoxidized Soybean Oil (AESO) O

OH
O
O C
O
O
O

O
O OH

Maleinated Soybean Oil Monoglyceride (SOMG/MA)


O O
HO
O O O
O
O O OH
HO O
O OH
O O
O HO

OH OH
O
O
O
HO
O
O

Maleinated Hydroxylated Soybean Oil (HSO/MA)

Fig. 10. Different triglyceride-based acrylic monomers. Reprinted with the permission from J Appl Polym Sci 2001; 82: 706 r John Wiley
and Sons, Inc. [1].

with respect to the properties. The variations of prevailing conditions, the esterification reaction
damping peak (tan d) of AESO–styrene copolymer proceeds along with cross-linking via a free radical
with temperature are shown in Fig. 11. The different mechanism. A bacterial polyester containing olefinic
compositions of the AESO–styrene copolymers groups in the side chains was prepared by feeding
were used to study the dynamic mechanical pseudomonas oleovorans with soybean fatty acids.
behavior of the copolymers. The copolymer with The structure of PHA with unsaturated side chains
50% AESO showed a very sharp loss tangent peak, soybean fatty acids is shown in Fig. 12. After cross-
which broadened with the increasing contents of linking, the biopolyester became a smooth and less
AESO. sticky elastomeric film. The cross-linked biopoly-
Baki Hazer and co-workers [24] reported that the ester, obtained thermally at 60 1C with benzoyl
soybean fatty acid and poly(hydroxy alkanoate) peroxide initiation, exhibited the highest cross-
(PHA) reacted under UV irradiation to form a linking density. The cross-linking was determined
cross-linked biopolyester. It is believed that in the by sol–gel analysis. The swelling properties of these
ARTICLE IN PRESS
994 V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 983–1008

biopolyesters were studied and the number average side chain [26]. Fish oils find use in industry in the
molecular weights were also calculated using the production of protective coatings, lubricants, sea-
Flory-Rehner equation [25]. The cross-link density lants, inks, animal feed and surfactants [27].
can be increased by irradiation with shorter Regular and conjugated fish oils prove to be
wavelength. It was also reported that while poly- cationically polymerizable monomers [26]. Polymers
merization of the soybean oil is difficult, the from fish oil have been prepared with divinylben-
biopolyester from soybean oil fatty acids is more zene, dicyclopentadiene and norbornadiene como-
reactive than the relative oil for polymerization. nomers [26]. The polymers obtained from fish oil
were found to be typical thermosetting materials
[26]. Three distinct decomposition states were found
2.2. Fish oil polymers
by TGA, corresponding to the evaporation of
unsaturated free oil present in the bulk polymer,
Fish oil is biodegradable and is readily available
carbonization of the cross-linked polymer and
as a byproduct in the production of fishmeal. Fish
subsequent oxidation of the carbons [26].
oils have a triglyceride structure with a high
Both regular oil and conjugated fish oils can be
percentage of polyunsaturated omega 3 fatty acid
used to produce hard and stiff polymers having
side chains, which can contain as many as 5–6 non-
moduli comparable to those of the conventional
conjugated carbon–carbon double bonds per ester
plastics [28]. In Fig. 13, fish oil polymers are
compared with commercially available polymers.
0.9
100% AESO The glass transition temperature of the conjugated
80% AESO
0.8
60% AESO
fish oil (CFO) polymer is nearly 110 1C, which is
0.7 50% AESO higher than Tg for polystyrene. The thermosetting
0.6
nature of the fish oil polymers results in an
improvement in thermal stability at higher tempera-
Tan δ

0.5
tures (T4200 1C) as compared to the thermoplastic
0.4 polymers. The conjugated fish oil resulted in
0.3 polymeric materials with better thermal stability
0.2
and mechanical properties as compared to the
regular fish oil polymers. However, regular fish oil
0.1
-150 -100 -50 0 50 100 150 200 polymers were observed to have relatively good
Temperature (°C) creep resistance properties [28]. These polymers
were found to have high cross-linking densities. The
Fig. 11. Plot of dynamic mechanical properties of AESO–styrene
bulk polymer was mainly composed of insoluble
copolymers against temperature using different compositions
(AESO 50–100%) of the copolymers. Reprinted with the substances (65–80 wt%). The homopolymerization
permission from J Appl Polym Sci 2001; 82: 714 r John Wiley of regular fish oil ethyl ester initiated by boron
and Sons, Inc. [1]. trifluoride diethyl etherate (BFE) resulted in a

CH3 Saturated units:


x = 2 for hexanoate.
CH x = 4 for octanoate.
x = 6 for decanoate.
HC
Z Unsaturated units:
CH2 y = 0 for -ene.
y = 1 for -diene.
HC
CH3 y = 2 for -triene.
CH
O y z = 1-3.
CH2 O
x CH2

O CH CH2 C O CH CH2 C

PHA-Soybean

Fig. 12. The structure of poly(hydroxy alkanoate) (PHA) containing unsaturated side chains of fatty acids, PHA–soybean. Reprinted with
the permission from Polymer Bulletin 2001; 46: 391 r Springer-Verlag, Inc. [24].
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1.0 diethyl etherate proved to be the most effective


1e+10 initiator for copolymerization.
Polystyrene
Epoxy A number of fish oils have also been polymerized
0.8
with styrene and divinylbenzene cationically in the
Storage Modulus (Pa)

1e+9 presence of boron trifluoride diethyl etherate as


0.6 initiator [30]. In addition to the good thermal
CFO-DVB-38 stability, and physical and mechanical properties,

Tan δ
1e+8 Polyethylene the polymeric products also showed even more
0.4
Polystyrene promising and valuable properties, such as good
Polyethylene
damping and shape-memory properties. The tensile
1e+7
0.2 fractured surfaces of the fish oil polymers have been
Epoxy
studied to obtain SEM micrographs of the fractured
surfaces of fish oil polymers such as those shown in
CFO-DVB-38
1e+6 0.0 Fig. 14. It is observed that Norway fish oil (NFO)
50 100 150 200 250 polymers have smooth surfaces even at higher
Temperature (°°C)
magnifications, whereas triglyceride fish oil (TFO)
Fig. 13. The comparison of the storage modulus (E0 ) and loss polymer results in rough surfaces.
factor (tan d) for conjugated fish oil (CFO-DVB-38) and some
commercially available polymers. Reprinted with the permission 2.3. Corn oil polymers
from Polymer 2000; 41: 7935 r Elsevier Science Ltd., [25].

Corn oil is one of the cheapest commercially


available vegetable oils and finds use in food and
viscous oil and they did not gel at all at room livestock feed as well as in the production of
temperature or above. However, conjugated fish oil ethanol, which is utilized as a fuel. It has a
is more reactive than regular fish oil and the simple triglyceride structure, with approximately 4.1 car-
homopolymerization of conjugated fish oil results in bon–carbon double bonds per molecule in fatty acid
a soft and solid material. The addition of alkene side chains [31]. The fairly high degree of unsatura-
comonomers, such as divinylbenzene, norborna- tion present in corn oil makes it possible to
diene, dicyclopentadiene, etc., facilitated gelation of copolymerize this oil with other monomers. Other-
regular fish oil ester system. The gel time varies from wise, corn and soybean oils have similar chemical
1 min to a few hours at room temperature depend- structures, with three fatty acid chains composed of
ing upon the oil and comonomer contents. Regular oleic acid, linoleic acid and linolenic acid [32].
and conjugated fish oil ethyl ester form polymers Polymers have been prepared by cationic poly-
with divinylbenzene in the presence of BFE. merization of corn oil, styrene and divinylbenzene in
Regular fish oil resulted in soft to hard thermosets the presence of boron trifluoride diethyl etherate
depending upon the amount of divinylbenzene, [31]. Corn oil and conjugated corn oil were
whereas conjugated fish oil resulted in very hard effectively copolymerized with comonomers. The
thermosets. copolymers obtained with conjugated corn oil
Many other alkene comonomers, such as furfural, showed better mechanical properties and thermal
benzoquinone, p-mentha-1, 8-diene, furan, vinyl stability than the corresponding simple corn oil
acetate, etc., were also examined in BFE-initiated polymers. The polymers possess a wide variety of
copolymerizations [29]. Copolymerization of these mechanical properties, such as tensile, flexural and
alkene comonomers with fish oil or conjugated fish compressive strengths, ranging from elastomers to
oil generated soft to hard polymers in the presence tough and rigid plastics. The dynamic mechanical
of divinylbenzene, norbornadiene or dicyclopenta- properties of several corn oil polymers are shown in
diene comonomers. A wide range of alkene como- Fig. 15.
nomers resulted in viable solid plastic materials, but Fig. 16 shows the dependence of the weight
neither copolymerizing fish oil nor conjugated fish percent of cross-linked polymers on the cure time
oil could be copolymerized with p-mentha-1, 8- and the corn oil contents in the copolymers.
diene, methyl methacrylate, isoprene, methyl croto- Fig. 16(a) shows that the conjugated corn oil
nate, phenol, linalool, furfural, bisphenol A, etc. resulted in polymers with higher cross-linked con-
Among various Lewis acids, boron trifluoride tents in comparison to the polymers from regular
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996 V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 983–1008

Fig. 14. The SEM micrograph of the mechanically fractured surfaces of samples NFO49ST33-DVB15-BFE3, CFO49ST33-DVB15-BFE3
and TFO49ST33-DVB15-BFE3. Reprinted with the permission from Polymer 2001; 42: 10144 r Elsevier Science Ltd. [29].

1.0E+10
COR35-ST39-DVB18-(NFO5-BFE3) corn oil. Fig. 16(b) indicates that the system
COR45-ST32-DVB15-(NFO5-BFE3)
COR55-ST25-DVB12-(NFO5-BFE3) underwent a slow increase in the yield of cross-
1.0E+9
Storage Modulus (Pa)

linked polymer after gelation. It is also observed


1.0E+8
that with the same curing time, only a 5 1C increase
in the cure temperature made an appreciable
1.0E+7 difference in the yields of cross-linked polymers
(shown in Fig. 16(b)). A plot of the shape recovery
1.0E+6 properties of the conjugated and regular corn oil
copolymers at different temperatures is reported in
1.0E+5 Fig. 17. It is observed that 50% shape recovery of
deformations was reached at 42 and 44 1C for
0.6 conjugated and regular corn oil polymers, respec-
Loss Factor (tan δ)

tively, and attained complete recovery for conju-


0.4
gated corn oil polymer at 75 1C and 96% recovery
for regular corn oil polymer at the same tempera-
ture. Regular corn oil copolymer is found to possess
0.2
superior damping characteristics when compared to
conjugated corn oil copolymer. This is attributed to
0 the high reactivity of conjugated oil, leading to
-50 0 50 100 150 200
densely cross-linked polymers.
Temperature (°C)

Fig. 15. The temperature dependence of the storage modulus (E0 ) 2.4. Tung oil polymers
and loss factor (tan d) for corn oil polymers prepared from
different concentrations of corn oil, keeping the styrene and
divinylbenzene contents in same ratio (3:2). Reprinted with the
Tung oil is one of the oldest known drying oils
permission from J Appl Polym Sci 2003; 90: 1833 r Wiley and finds numerous applications in the paint
Periodicals, Inc. [30]. industry. It is extracted from the seeds of the tung
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V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 983–1008 997

100 100

Wt % of cross-linked polymer
35°C

80 40°C 80

60 60

40 40

20 20 COR-ST-DVB
CCOR-ST-DVB
0 0
0 100 200 300 400 0 20 40 60 80 100
(a) Cure Time (min) (b) Corn Oil Contents (%)

Fig. 16. (a) show the dependence of the weight percent of the cross-linked polymer obtained from COR45ST32-DVB15-(NFO5-BFE3) on
cure time at 35 and 45 1C and; (b) the weight percentage of cross-linked polymers prepared from conjugated and simple corn oil versus
corn oil contents. Reprinted with the permission from J Appl Polym Sci 2003; 90: 1833 r Wiley Periodicals, Inc. [30].

100

80
Recovery (%)

60
Fig. 18. The structure of a-elaeostearic acid. Reprinted with the
40 permission from Biomacromolecules 2003; 4: 1018 r American
Chemical Society [34].

20
COR45-ST32-DVB15-(NFO5-BFE3)
CCOR45-ST32-DVB15-(NFO5-BFE3)

0 and forms an irregular polymeric solid within a few


20 40 60 80 100 seconds after the addition of this initiator at room
Temperature (°°C) temperature. The gel time ranged from a few
seconds to 1 min depending, on the oil and other
Fig. 17. The study of the shape-recovery results for the polymer
monomer compositions. The addition of a less
from conjugated and regular corn oil for sample with composi-
tion OIL45ST32-DVB15-(NFO5-BFE3) at different tempera- reactive oil, such as soybean oil, increases the gel
tures. Reprinted with the permission from J Appl Polym Sci 2003; time from second to minutes or hours, again
90: 1836 r Wiley Periodicals, Inc. [30]. depending upon the oil and other monomer
compositions. The level of conversion of the starting
material into a cross-linked product depends on the
tree, with its main constituent a glyceride of composition of the material. Tung oil polymers
elaeostearic acid with a conjugated triene structure possess very good dynamic mechanical properties as
(Fig. 18). This highly unsaturated, conjugated well as thermal stability at room temperature. These
system is largely responsible for the rapid polymer- are thermally stable upto 200 1C and 10% weight
ization and outstanding drying properties of the oil loss was recorded at around 400 1C.
[33]. Tung oil has been polymerized by both free Tung oil can also be copolymerized with styrene
radical and cationic polymerizations. Larock and and divinylbenzene by thermal polymerization [35].
coworkers [34,35] studied the cationic and thermal The 1H NMR spectra of the tung oil, styrene,
polymerization of tung oil in detail. Tung oil is divinylbenzene and extracted soluble contents from
cationically copolymerized with divinylbenzene in the sample with 50% tung oil is reported in Fig. 19
the presence of boron trifluoride diethyl etherate, [35]. These results are used to calculate the oil
resulting in hard plastics [34]. The cationic copoly- content in a particular sample. The thermal poly-
merization of tung oil is found to be very reactive. It merization of tung oil was reported to involve
was observed that tung oil is very sensitive to the primarily the dimerization of the elaeostearic acid,
cationic initiator boron trifluoride diethyl etherate, producing monocyclic dimeric fatty acid groups at
ARTICLE IN PRESS
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2.5. Linseed oil polymers

2.5.1. Natural linseed oil polymers


Linseed oil, obtained from the linseed seed, is a
fatty acid ester triglyceride and is composed of about
53% linolenic acid, 18% oleic acid, 15% linoleic acid,
6% palmitic acid and 6% stearic acid [39]. It is
traditionally used as a drying oil for surface-coating
applications. To make it a superior drying oil in
terms of film properties, different olefinic monomers,
such as styrene have been copolymerized with linseed
oil [40–42]. Linseed oil is polymerized by cationic,
thermal, free radical polymerization, as well as by
oxidative polymerization [43]. The process of auto-
oxidative curing of linseed oil with initiation,
propagation and termination steps is shown in
Scheme 3. It is observed that in the initiation step,
Fig. 19. The 1H NMR spectra of (a) tung oil (TUN), (b) styrene
(ST), (c) divinylbenzene (DVB) and (d) the extracted soluble naturally occurring hydroperoxides decompose to
substances from the sample TUN50ST20-DVB30 bulk polymer. form free radicals. This step can be catalyzed either
Reprinted with the permission from Biomacromolecules 2003; 4: by the inclusion of driers (pigments used as catalysts)
1021 r American Chemical Society [34]. or the application of heat. These free radicals react
with antioxidants and after consuming the antiox-
idants, react with the fatty acid chains of the drying
200 1C or above [36–37]. When polymerized at high oil. The propagation then proceeds by the abstrac-
temperatures (in a range of 200–300 1C), the resulting tion of the hydrogen atoms present between double
products ranged from viscous oils to weak rubbery bonds of the methylene groups, which result in the
films. Aromatic comonomers have been introduced free radical 1. Radical 1 is resonance stabilized, and
to produce viable polymeric materials. A wide can react with oxygen to form radical 2, as shown in
variety of viable transparent polymeric materials Scheme 3. The peroxy free radical may be conjugated
ranging from elastomers to tough and rigid plastics or non-conjugated. This can regenerate free radical 1
have been prepared from thermal copolymerization by abstracting hydrogen from methylene groups.
of the tung oil, styrene and divinylbenzene [35]. The After this termination, cross-linking proceeds.
stoichiometry and the addition of catalysts greatly The termination results in the formation of structures
affected the thermophysical and mechanical proper- 3, 4 and 5. Cobalt, lead and zirconium-2-ethylhex-
ties of the polymers. The addition of metallic anoates are generally used as catalysts for oxidative
catalysts proved to be a very effective means to polymerization of linseed oil. It is found that
accelerate the thermal copolymerization leading to cobalt-2-ethylhexanoate was active during the oxida-
high cross-link densities and improved properties of tive step and lead and zirconium catalysts acted
the bulk polymers. However, varying the oxygen during the polymerization step. Cobalt–zirconium
uptake and the addition of various peroxides had no complex gave the best results, and under specified
effect on the resulting polymers. conditions, zirconium catalyst was more efficient
Trumbo and Mote [38] reported the synthesis of than lead.
copolymers from tung oil and diacrylate by Diels- Soucek et al. [44] used DSC to study the auto-
Alder reaction and studied the properties of the oxidative curing of linseed oil, catalyzed by various
films produced from these copolymers using 1,6- metal catalysts. A manganese drier was used to
hexanediol diacrylate and 1,4-butanediol diacrylate. catalyze the reaction at the coating surface (top
The copolymers produced were completely soluble. drier) and a zirconium drier was used to catalyze the
The molecular weight distributions of the copoly- reaction throughout the entire film thickness
mers were broad and multimodal. The films of the (through drier). It is a common practice to use a
copolymers were readily prepared and when cured, combination of top and through driers. Fig. 20
exhibited good solvent resistance, high hardness and shows the DSC scans for linseed oil using different
good gloss. drier systems at 130 1C.
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Scheme 3. The autoxidation process for the curing of linseed oil showing initiation, propagation and termination steps of the reaction.
Reprinted with the permission from Prog Org Coat 1998; 33: 220 r Elsevier Science S. A. [42].

Linseed oil has been styrenated for use in picted in Scheme 4, showing the process of
polymerizations to obtain some desired film proper- styrenation of linseed oil and castor oil. The oils
ties [45]. There are two methods of styrenation of are first interesterified and then the macromer is
oils, dependent on the mode of generation of free prepared from the reaction of interesterified product
radicals: the classical method and the macromer and acrylic acid. Finally, the macromers are reacted
method. In the classical method, free radicals are with styrene. The macromonomers of linseed oil
formed by thermolysis, either in the absence (for were prepared by transesterification of methyl-
conjugated oils) or in the presence (for non- methacrylate (MMA) with partial glycerides [46].
conjugated oils) of an initiator, such as benzoylper- Styrenation was achieved via a free radical mechan-
oxide. The degree of conjugation and unsaturation ism using benzoylperoxide as the initiator. Scheme 5
has a crucial effect on the formation of free radicals shows the detailed mechanism for the preparation
on the oil molecules. The process of styrenation of of partial glycerides and their styrenation. In the
linseed oil proceeds through different stages, de- macromer method, the macromer was obtained
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through reaction of hydroxyl-containing oil speci-


LIN-Mn (0.1) @ 130°C
LIN-TIA (0.5) @ 130°C
mens with vinyl monomer and then this macromer
LIN-TIP (0.5) @ 130°C was homopolymerized or copolymerized with styr-
Exotherm
ene [47]. Semidrying and non-conjugated oils were
mixed with conjugated drying oils to produce
homogeneous styrenated products [48]. When clas-
sical and macromer methods were compared, it was
found that macromer technique resulted in homo-
geneous products in high yield.
The effect of cobalt-2-ethylhexanoate drier on the
oxidative polymerization of linseed oil was investi-
0 20 40 60 80 100 gated [49]. It was found that the cobalt catalysts
Time (min) accelerated all of the oxidation reactions involved in
the process, and improved the formation of a solid
Fig. 20. Differential scanning calorimetric isothermal exotherms
for linseed oil cured with three different metal catalysts,
film at the surface, but a viscous oil remained under
manganese drier, titanium (di-isopropoxide) bis (acetyl-aceto- this surface film. The addition of cobalt drier only
nate) (TIA) and titanium (IV) isopropoxide (TIP) at 130 1C. influenced the kinetics, but did not alter the reaction
Reprinted with the permission from Progress in Organic Coatings products.
1996; 28: 254 r Elsevier Science S. A. [43].

O OH
O
O O
O O OH
O O
+
O O
O O OH
Linseed Oil Castor Oil

Interesterification

OH O
O O O O
O O
O O
O O OH
O O +
+ O
O O O
O OH O OH OH
O

OH O
O
O
O
O Other possible isomers
+ OH
+
OH O
+
OH
OH
Interesterification Product (IP)

Acrylic Acid (CH2=CH-COOH)


-H2O
O O
O O O O
O O
O OH O OH
O O
Styrene
O O
O O OH O O
O CH CH CH2 CH
n
Macromer Styrenated Oil

Scheme 4. Styrenation of the linseed oil and castor oil through interesterification of oils which react with acrylic acid and finally with
styrene to form styrenated oil. Reprinted with the permission from Macromol Mater Eng 2000; 283: 17 r Wiley–VCH Verlag GmbH [44].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 983–1008 1001

O
OH OH
O OH O
O O
O + OH O + O

O OH O OH

O O
Glycerol Mixture of Partial Glyceride
Triglyceride Oil

OH OH
O O
O O
+
O OH
O
CH3
-CH3OH H2C C C O
O CH3
O CH3 CH3
O
O C C CH2
O C C CH2
O O
O + O
O O C C CH2
O
O CH3

O CH3 H3C
O C C CH2 H2C HC C CH2 CH2 CH
O O n
O O
O
Benzoyl peroxide O
O
O O
O
H3C
O H3C C CH2 CH2 CH
O CH2 H2C HC n
C C O
O O O
O O
Benzoyl peroxide O
O C C CH2 O
CH3 C CH2 CH2 CH
O n
H3C
Styrenated Oil

Scheme 5. The process of preparation of the partial glyceride and then the styrenation of the partial glyceride through free radical
mechanism in presence of benzoylperoxide. Reprinted with the permission from J Appl Polym Sci 2003; 88: 2374–75 r Wiley Periodicals,
Inc. [45].

For films cured with the cobalt drier, the factor and storage modulus with temperature for
quantification of the oxidation product shows lower epoxidized linseed oil—cis-1,2,3,6-tetrahydrophtha-
concentrations of carboxylic acids, ketones and lic anhydride (ELO—THPA) system is depicted in
alcohols [49]. The efficiency of peroxide decomposi- Fig. 21. A wide range of temperature from 140 to
tion by the cobalt, zirconium and calcium/zirco- +220 1C was used for the study. On using imidazole
nium drier was compared by measuring the catalysts, the epoxidized linseed oil was cured to a
variations of peroxide value as a function of maximum extent, leading to high conversion of
oxidation time. The influence of different catalysts anhydrides (nearly double) and increased stiffness.
and anhydride hardeners on the curing of polymer By using tertiary amine as a catalyst, lower stiffness
networks based on epoxidized linseed oil has been was observed in comparison to that with the
studied [50]. Generally, tertiary amines and imida- imidazole catalyst. When the catalyst content
zoles were used as catalysts. The variation of loss was increased, the conversion of anhydride was
ARTICLE IN PRESS
1002 V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 983–1008

observed to be low due to the fast gelling of the of analysis, such as FTIR, NMR, etc. [51]. The
system. On decreasing the catalyst concentration, it cationic photopolymerization of epoxynorbornane
was observed that the anhydride conversion is linseed oil and epoxidized linseed oil was studied by
maximum leading to good thermal stability and various methods of characterization. The prepara-
mechanical properties, such as flexural and Young’s tion of epoxynorbornane linseed oil and norbor-
moduli, Tg, etc. nane linseed oil is detailed in Scheme 6. The 1H
NMR spectra of linseed oil, norbornane linseed oil
and epoxynorbornane linseed oil are shown in Fig.
2.5.2. Epoxidized linseed oil polymers 22. Figs. 23 and 24 show the effect of the reactive
A series of epoxynorbornane-modified linseed oils and non-reactive diluents on the rate of polymeriza-
were prepared as a function of the norbornane tion [51]. The addition of reactive or non-reactive
content and were characterized by various methods diluents reduced the viscosity of the formulations
and was found to have significant effect on epoxy
10000 0.4 conversion and the rate of polymerization of
0.35 epoxidized norbornane linseed oil. It was reported
1000 0.3 that the photopolymerization of epoxides was
0.25 accelerated due to the presence of vinyl ether
E’ (MPa)

Tan δ

100 0.2 [52,53]. This was attributed to the generation of a


0.15 large number of propagating cationic species via a
10 0.1 redox reaction between the vinyl ether and the
0.05 photoinitiator diaryliodonium salt. The mechanism
1 0
for the photoinitiated cationic polymerization
-140 - 80 20 40 100 160 of epoxynorbornane linseed oil is depicted in
Temperature (°C) Scheme 7.
Soucek and coworkers [54] have studied the
Fig. 21. The temperature dependence of loss factor (tan d) and
properties of UV-curable hybrid films derived from
storage modulus (E0 ) at a frequency of 1 Hz for an epoxidized
linseed oil—cis-1,2,3,6-tetrahydrophthalic anhydride (ELO– epoxynorbornane linseed oil. Different levels of
THPA) system. Reprinted with the permission from Polymer epoxynorbornane linseed oil and tetraethylortho-
2000; 41: 8609 r Elsevier Science Ltd., [49]. silane (TEOS) were used in the study. The organic–

O
O
O O 7
7
O O O
O O 7 7
+ 7 O
4 O
7 O
7 4
0.76-0. 90 MPa NLO--25 7
NLO--50
250 °C NLO--100

H2O2 /Tungstate

60 °C
O O

O O 7 7
O O
O O O O
7 O
4 O
O 7 7
7
NLO--25 O
O O
[a] 4 7
NLO--50
NLO--100 7
ENLO--25 O O
[b] ENLO--50
ENLO--100

Scheme 6. The reaction process of the preparation of the norbornane linseed oil (NLO) and epoxynorbornane linseed oil (ENLO).
Reprinted with the permission from J Polym Sci: Part A: Polym Chem 2003; 41: 3444 r Wiley Periodicals, Inc. [50].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 983–1008 1003

Fig. 22. The 1H NMR spectra of (a) linseed oil, (b) norbornane linseed oil and (c) epoxynorbornane linseed oil. Reprinted with the
permission from J Polym Sci: Part A: Polym Chem 2003; 41: 3446 r Wiley Periodicals, Inc. [50].

inorganic hybrid films are formed either from the of 72–90% at 493–500 1C. The thermogravimetric
inorganic phase formation within the organic film behavior of some samples is shown in Fig. 25. All of
or a simultaneous polymerization of both organic the samples exhibited stability up to 100 1C, and the
and inorganic reactive groups. It was also observed degradation of the samples usually started around
that the incorporation of TEOS oligomers improved 350 1C, with the whole mass degraded to char at
the performance of films and enhanced tensile 500 1C and completely burned off at 650 1C.
strength, fracture toughness, thermal stability and
general coating properties of epoxynorbornane
linseed oil. 2.6. Castor oil polymers
Turri et al. [55] studied the polymerization of
linseed oil via calorimetry. They observed that all of Epoxidized castor oil has been used for the
the pigments such as minium (Pb3O4), chromium preparation of interpenetrating polymer networks
yellow (PbCrO3) and red earth (based on iron (IPN), and these were characterized for their
oxides) accelerate the polymerization reaction of dynamic mechanical behavior [57]. It was observed
linseed oil and therefore have a catalytic action. that the cross-linked IPNs from the epoxidized oil
Kundu and Larock prepared a variety of new and adducts of tung oil with maleic anhydride had
polymers from conjugated linseed oil, styrene and very good compatibility. The hydroxyl groups of
divinylbenzene by thermal polymerization [56]. The epoxidized castor oil form hydrogen bonds with the
resulting polymeric material was opaque and con- carbonyl groups in tung oil. These hydroxyls are
tained 35–85% of cross-linked materials. These more reactive towards tung oil adducts than
copolymers exhibited a major thermal degradation epoxidized cottonseed oil. Yagci and coworkers
ARTICLE IN PRESS
1004 V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 983–1008

70 ate fatty acid ester into esters of dimer and oligomer


acids. A fixed bed reactor was used for the
60
oligomerization of dehydrated methylricinoleate.
50 The product was characterized by infrared, 1H-
Epoxy Conversion (%)

NMR and mass spectroscopy. The kinetics of the


40 oligomerization of methyl ester of dehydrated
castor oil fatty acid was compared with the thermal
30
oligomerization process [59]. The catalytic reaction
20 followed second-order kinetics, whereas the thermal
process followed first-order kinetics.
10 Neat ENLO-100 Schwank et al. [60] reported the copolymerization
1% DEGDVE in ENLO-100 of dehydrated castor oil with styrene. The poly-
0 5% DEGDVE in ENLO-100
20% DEGDVE in ENLO-100 merization was carried out in benzene and the
-10 product was isolated for characterization. It was
0 50 100 150 200 250 300 observed that the copolymerization was very
Irradiation Time (sec.) difficult when the concentration of dehydrated
castor oil is more than 20%. Ashraf and coworkers
Fig. 23. The effect of the reactive diluents, diethylene glycol
divinyl ether (DEGDVE), on the epoxy ring-opening polymer- [61] prepared a blend of dehydrated castor oil and
ization of sample ENLO-100 in the presence of 4 weight percent epoxy resin. The miscibility of the two components
(4-octyloxyphenyl) phenyl iodonium hexafluoroantimonate was examined by viscometric and ultrasonic techni-
(OPPI) as a function of the irradiation time. Reprinted with the ques. Ashraf and coworkers [62] also studied the
permission from J Polym Sci: Part A: Polym Chem 2003; 41: 3451
miscibility of the blends of epoxidized dehydrated
r Wiley Periodicals, Inc. [50].
castor oil and poly (methyl methacrylate). The
compatibility was investigated by differential scan-
70 ning calorimetry and SEM.
60
2.7. Polymers from other oils
50
Epoxy Conversion (%)

Drying and semidrying oils such as sesame,


40
sunflower, safflower, walnut oil have also been
30 investigated for the preparation of polymer by
different methods. Homopolymerization is not
20 Neat ENLO-100
favored due to the steric hindrance of the bulky
2 % DEGDEE in ENLO-100
10 6 % DEGDEE in ENLO-100
oil moieties. Triglyceride oil-based macromers of
20 % DEGDEE in ENLO-100 sunflower oil were prepared in two successive steps
0 [46]. First, a partial glyceride was prepared by
-10
glycerolysis of sunflower oil in the presence of
0 50 100 150 200 250 300 calcium oxide (CaO). Subsequently, a macromer
Irradiation Time (sec.) was prepared by transesterification of the partial
glyceride with methylmethacrylate in the presence of
Fig. 24. The effect of non-reactive diluents, di-(ethylene glycol) the same catalyst. The prepared macromer was
diethyl ether (DEGDEE), on the epoxy ring-opening polymeriza-
tion of sample ENLO-100 in the presence of 4 weight percent
copolymerized with styrene in the presence of
(4-octyloxyphenyl) phenyl iodonium hexafluoroantimonate benzoyl peroxide, yielding a styrenated product. In
(OPPI) as a function of the irradiation time. Reprinted with the this case, a product with longer polystyrene
permission from J Polym Sci: Part A: Polym Chem 2003; 41: 3451 segments was obtained.
r Wiley Periodicals, Inc. [50]. Kusefoglu and coworkers [63] studied the poly-
merization of high oleic sunflower oil with different
prepared styrenated castor oil and linseed oil by the comonomers. The effect of simultaneous addition of
macromer technique [45]. bromine and acrylate to the fatty acid triglycerides
Kumar and co-workers [58] oligomerized castor was studied. The yield for bromoacrylation of
oil over molybdenum oxide on a silica–alumina sunflower oil was 55%. The copolymers of sun-
support. They directly converted the methylricinole- flower oil and styrene were formed via free radical
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 983–1008 1005

Photolysis of Photoinitiator
+
[a] Ar 2 I + X + [Ar 2 I + X + ] + ArI* X*

+
[b] ArI* X* ArI + R + H*X*

Initiation
O H O+
[c] H+ +

H
O
[d] H+ + O+

Propagation

[e] O + H O+
H O
O+

O
[f] O O O Homopolymer (I)
O H [g]
H
+
O
[h] O + H O
O+

O H
[i]
O O+

O H
[j]
O

O Homopolymer (II)
O O [L]

Scheme 7. The mechanism for the photoinitiated cationic polymerization of the epoxynorbornane linseed oil (ENLO). Reprinted with the
permission from J Polym Sci: Part A: Polym Chem 2003; 41: 3454 r Wiley Periodicals, Inc. [50].

mechanism. They also studied the polymerization of alternate route, which has the potential to augment
acrylamide derivatives of fatty acid compounds [64]. the use of petroleum-based polymers. These trigly-
The acrylamide functionality on the triglyceride of ceride oils mostly comprise unsaturated fatty acids,
sunflower oil was introduced by the Ritter reaction. and provide a wide scope for polymerization using a
variety of techniques. The unsaturation present in
3. Conclusion these oils makes them ideal for the preparation of
bio-based polymers. Polymers prepared from
In recent years, natural oils have become the soybean oil have properties comparable with those
center of attraction for their potential use as starting of conventional polymers. The mechanical proper-
materials for the preparation of polymers. This is an ties of these polymers depend on the degree of
ARTICLE IN PRESS
1006 V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 983–1008

Acknowledgements
100

The authors are thankful to the chief editors of


80 C87LIN30-ST28-DVB42 (S1)
this journal for their kind suggestions and editorial
Weight loss (%)

C87LIN40-ST24-DVB36 (S2)
C87LIN50-ST20-DVB30 (S3)
corrections.
60
C87LIN60-ST12-DVB28 (S4)
C87LIN70-ST08-DVB22 (S5)
40
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