8566 Ind. Eng. Chem. Res.

2008, 47, 8566–8571

Spectroscopic Characterization of Linseed Oil Based Polymers

Vinay Sharma,†,‡ J. S. Banait,‡ and P. P. Kundu*,†
Department of Chemical Technology, Sant Longowal Institute of Engineering & Technology,
Sangrur, Punjab 148106, India, and Faculty of Physical Sciences, Punjabi UniVersity,
Patiala, Punjab 147002, India

Linseed oil based polymers from cationic and thermal polymerizations have been investigated quantitatively
through 1H NMR and FTIR spectroscopic analysis. The solubility of the samples ranges from 22 to 37% for
cationic samples and from 4.23 to 53% for thermal samples. The content of the grafted linseed oil calculated
from 1H NMR results ranges from 22.9 to 43.0% and from 0 to 10% for cationic and thermal samples. The
grafted linseed oil contents from FTIR are 18.2-45.4% and 0-10.7% for cationic and thermal samples. The
values obtained through quantitative 1H NMR and FTIR spectroscopic analysis methods are consistent and
can be applied to other polymers also.

1. Introduction 2.2. Sample Preparation. 2.2.1. Cationic Sample Pre-

The spectroscopic techniques are one of the important paration. Polymeric materials have been prepared by heating
parameters for characterizing different polymers.1-3 These desired concentrations of linseed oil, styrene, and divinyl-
techniques are powerful tools for the characterization of poly- benzene in glass molds.41 In these experiments, the styrene
mers both qualitatively4 and quantitatively.5 A lot of research to divinylbenzene ratio is kept constant at 2:1, respectively.
work is already published on the quantitative analysis of Desired amounts of styrene and divinylbenzene are added to
different polymers by NMR and Fourier transform infrared the linseed oil, and the mixture is vigorously stirred. Then,
(FTIR) spectroscopies.6-9 Hazer et al.10 used FTIR and NMR the mixture is cooled and the initiator is added with constant
to calculate poly(ethylene glycol) contents in cross-linked stirring at low temperature and the whole mass is transferred
poly(ethylene glycol)-block-polybutadiene block copolymers. to the glass mold. The sealed glass mold is kept at room
Natural oils are always a center of attraction as an alternative temperature for 12 h and then heated sequentially at different
source for the production of useful polymers.11,12 Larock et temperatures, such as for 12 h at 60 °C and for 24 h at 110
al.13-17 have done remarkable work on the polymerization of °C, and is finally postcured at 120 °C for 3 h. The
various natural oils. They directly polymerized oils with other nomenclature used in this work is based on the original
monomers. Wool and co-workers18-22 used these oils for the compositions of the reactants (reported in Table 1).
production of polymers by modifying the oil moieties, and 2.2.2. Thermal Sample Preparation. Polymeric materials
subsequently polymerizing them with other monomers. Soucek have been prepared by heating desired concentrations of
et al.23-29 have used epoxidized linseed and soybean oils for conjugated linseed oil, acrylic acid, and divinylbenzene in glass
polymerization. Baki et al.30-34 have done work on poly(hy- vials. Desired amounts of acrylic acid and divinylbenzene are
droxyalkanoate) (PHA) based on natural oils for the preparation added to the conjugated linseed oil, and the mixture is vigorously
of unsaturated bacterial polyester. stirred. The glass vial is heated sequentially at different
In the present work, linseed oil based polymers have been temperatures, such as for 6 h at 80 °C, for 12 h at 100 °C, and
synthesized and studied quantitatively by 1H NMR and FTIR. for 12 h at 120 °C, and is finally postcured at 140 °C for 12 h.
In the literature, Larock et al.13,35-37 have quantitatively studied The nomenclature used in this work is based on the original
the soluble portions of the oil based polymers through 1H NMR, compositions of the reactants (reported in Table 1).
but the insoluble portions have not been analyzed. In this work,
the insoluble portion is also quantitatively analyzed through 3. Characterization
FTIR. There is a lot of published work on the quatitification of 3.1. Soxhlet Extraction. The polymeric materials as reported
polymers through FTIR.38-40 The present work reports the in Table 1 are Soxhlet extracted for their soluble and insoluble
complete quantitative analysis of linseed oil polymers through
1 Table 1. Detailed Feed Compositions of Different Linseed Oil
H NMR and FTIR. Polymers
sample linseed styrene divinylbenzene acrylic initiator
2. Experimental Section IDa oil (%) (%) (%) acid (%) (%)
2.1. Materials. Linseed oil of commercial grade was pro- Lin30 30 46 15.5 8
cured from a local market (Punjab, India), and conjugated Lin40 40 39 13 8
linseed oil (87% conjugation) was purchased from Alnor Oil Lin50 50 31.5 10.5 8
Lin60 60 24 8 8
Company, Alnor, NY. Styrene (ST), acrylic acid (AcA),
CLin0 0 10 90
tetrahydrofuran, and boron trifluoride diethyl etherate complex Clin10 10 10 80
were purchased from Merck Chemical Co., Germany. Divinyl- CLin20 20 10 70
benzene (DVB) was purchased from Fluka Chemie. CLin30 30 10 60
CLin40 40 10 50
* To whom correspondence should be addressed. E-mail: ppk923@ CLin50 50 10 40
yahoo.com. CLin60 60 10 30
†
Sant Longowal Institute of Engineering & Technology.
‡ a
Punjabi University. CLin samples contain 87% conjugated linseed oil.

10.1021/ie800415z CCC: $40.75  2008 American Chemical Society

Published on Web 10/21/2008
 Ind. Eng. Chem. Res., Vol. 47, No. 22, 2008 8567
Table 2. Detailed Compositions of Cationically Cross-Linked Linseed Oil, Styrene, and Divinylbenzene Copolymers from Soxhlet Extraction,
and 1H NMR and FTIR Spectroscopic Results
sample soluble extractible compositiona Soxhlet results
linseed oil
wt % ST solubleb insolublec content (wt %)
ID composition wt % oil and DVB (wt %) (wt %) by FTIRd
Lin30 Lin30 + ST46.5 + DVB15.5 + In8 64.68 35.32 22.50 (7.9; 14.6) 77.50 (54.1;23.4) 18.16
Lin40 Lin40 + ST39 + DVB13 + In8 89.72 10.28 28.00 (2.9; 25.1) 72.00 (49.1;22.9) 24.56
Lin50 Lin50 + ST31.5 + DVB10.5 + In8 78.99 21.01 33.33 (7.00; 26.33) 66.67 (28.00;38.67) 36.89
Lin60 Lin 60 + ST24 + DVB8 + In8 87.76 12.24 36.67 (4.49; 32.18) 63.33 (20.27;43.06) 45.39
a
Microcomposition of the extracted soluble materials calculated from the 1H NMR integrals of the glyceride peak at 4.1 ppm and aryl CH peak at 7
ppm. b The data in parentheses have been calculated directly from the weight percent oil and weight percent aromatic content in the soluble extract. The
first value in the parentheses represents the percent aromatic content, and the second value represents the percent oil content. c The data in the
parentheses have been calculated indirectly from the weight percent of the oil and aromatic content in the soluble extract, as the total mass of the
soluble and insoluble parts was held constant. The first value in the parentheses represents the percent aromatic content and the second value represents
the percent oil content. d The data are calculated from absorbance peaks at 1744 and 1601 cm-1 for carbonyl stretching of ester in oil and aromatic
stretching for styrene-divinylbenzene, respectively.

Table 3. Detailed Compositions of Thermally Cross-Linked Conjugated Linseed Oil, Acrylic Acid, And Divinylbenzene Copolymers from
Soxhlet Extraction, and 1H NMR and FTIR Spectroscopic Results
sample soluble extractible compositiona Soxhlet results
linseed oil content
ID composition wt % oil wt % AcA and DVB solubleb (wt %) insolublec (wt %) (wt %) by FTIRd
CLin0 CLin0 + AcA90 + DVB10 0 100 4.23 (4.23; 0) 95.77 (95.77; 0) 0
CLin10 CLin10 + AcA80 + DVB10 91.75 8.25 9.47 (0.78; 8.69) 90.53 (89.22; 1.31) 1.75
CLin20 CLin20 + AcA70 + DVB10 93.94 6.06 19.49 (1.18; 18.31) 80.51 (78.82; 1.69) 1.83
CLin30 CLin30 + AcA60 + DVB10 96.74 3.26 30.03 (0.98; 29.05) 69.97 (69.02; 0.95) 1.70
CLin40 CLin40 + AcA50 + DVB10 96.86 3.14 38.95 (1.22; 37.73) 61.05 (58.78; 2.27) 2.87
CLin50 CLin50 + AcA40 + DVB10 95.82 4.18 44.85 (1.87; 42.98) 55.15 (48.13; 7.02) 6.84
CLin60 CLin60 + AcA30 + DVB10 95.12 4.88 52.53 (2.56; 49.97) 47.47 (37.44; 10.03) 10.73
a
Microcomposition of the extracted soluble materials calculated from the 1H NMR integrals of the glyceride peak at 4.1 ppm, acrylic OH peak at 9.8
ppm, and aryl CH peak at 7 ppm. b The data in parentheses have been calculated directly from the weight percent oil and weight percent acrylic-DVB
content in the soluble extract. The first value in the parentheses represents the percent acrylic-DVB content, and the second value represents the percent
oil content. c The data in the parentheses have been calculated indirectly from the weight percent of the oil and acrylic-DVB content in the soluble
extract, as the total mass of the soluble and insoluble parts was held constant. The first value in the parentheses represents the percent acrylic-DVB
content, and the second value represents the percent oil content. d The data are calculated from absorbance peaks at 1744, 1711, and 1530 cm-1 for
carbonyl stretching of ester in the oil, carbonyl stretching of acrylic acid, and aromatic stretching for divinylbenzene, respectively.

Figure 1. Variation in soluble contents of the linseed oil polymers (wt %)

with increasing linseed oil content (wt %) for cationic and thermal samples. Figure 2. 1H NMR spectra of divinylbenzene, extract of the sample Lin50
(Lin50-ST29-DVB13-In8), linseed oil, styrene, and solvent for extraction
and solvent collected from extracts.

3.2. 1H Nuclear Magnetic Resonance (1H NMR). The

contents. A sample ranging from 2 to 3 g of the bulk polymer
is extracted for 24 h with 150 mL of refluxing tetrahydrofuran
using a Soxhlet extractor. After extraction, the resulting solution
is concentrated by rotary evaporation and subsequent vacuum
drying. The insoluble solid is dried under vacuum for several
hours before weighing.
extracted soluble part of the polymeric material as well as the
linseed oil, styrene, and divinylbenzene are dissolved in CDCl3.
Tetramethylsilane (TMS) is used as reference compound. The
solution is scanned with a multinuclear FT-NMR spectrometer
(Bruker AC-300 F) at 300 MHz. A total of 30 scans are averaged
to obtain the final data.
8568 Ind. Eng. Chem. Res., Vol. 47, No. 22, 2008
Figure 3. 1H NMR spectra of divinylbenzene, extract of the sample CLin50
(CLin50-AcA40-DVB10), conjugated linseed oil, acrylic acid, and solvent
for extraction and solvent collected from extracts.
Scheme 1. Intermolecular Hydrogen Bonding Cleavage in the
Acrylic Acid Dimer during Polymerization Reaction
3.3. Fourier Transform Infrared Spectroscopy. The dried
insoluble part after Soxhlet extraction is analyzed by FTIR
spectrometry. The samples are analyzed by a Perkin-Elmer RX-I
spectrophotometer. Samples are prepared by mixing a weighed
amount of polymer with KBr. Specifically, 1 mg of finely
powdered polymer sample is mixed with 100 mg of KBr powder
in a mortar and pestle. The mixture is then pressed in a die at
about 100 MPa for 3 min to get a transparent disk. This disk is
then placed in a sample holder, and the peak is recorded in
absorbance. A total of 32 scans at 4 cm-1 resolution are
collected to get average spectra.
4. Results and Discussion
4.1. Soxhlet Extraction. Polymeric samples were extracted
for their insoluble contents, and these results are reported in
Tables 2 and 3. For the cationic samples, with an increase in
linseed oil content in the polymeric samples from 30 to 40%,
the insoluble contents in the samples decreased from 78 to 63%,
while the soluble part increased from 22 to 37%. The plot
between the content of the linseed oil and soluble contents of
the copolymer sample is shown in Figure 1. These results
indicate that, with the increase of linseed oil content, the cross-
Figure 4. FTIR absorbance spectra of the cationic samples Lin30 and Lin40.
Figure 5. FTIR absorbance spectra of the cationic samples Lin50 and Lin60.
linking densities of the polymeric samples decrease. In the
thermal samples, an increase in the conjugated linseed oil
content results in an increase in the soluble portion of copolymer.
It is observed that the soluble portion increases from 4.23 to
52.53% with an increase in the oil content from 0 to 60. Figure
1 also shows that the cationic samples have higher cross-link
densities than the thermal samples, as cationic samples have
less soluble portion in tetrahydrofuran. This is why the cationic
samples are superior to the thermal samples, because cationic
samples were prepared by using boron trifluoride diethyl etherate
(BFE).
4.2. 1H NMR of Cationic and Thermal Polymers. The 1H
NMR spectra of ST, DVB, linseed oil, solvent collected from
extractable portion of the polymer (vacuum rotary evaporator),
and the soluble extract from the cationic polymeric sample
(Lin50) are shown in Figure 2. The extracts from Lin50 are
representative of the soluble extracts obtained from all other
cationic samples (Lin30 to Lin60). The peaks at 2.8 ppm are
due to the methylene (CH _ 2) protons present between the two
unsaturated CdC double bonds of the fatty acid chain. The
presence of a similar peak in DVB is due to the presence of
methylene protons in the ethylvinylbenzene, which is present
to the extent of about 20% in the DVB. The peaks for the vinylic
(CdCsH _ ) protons of the linseed oil, ST, and DVB are present

Figure 6. FTIR absorbance spectra of the thermal samples CLin0 and
CLin60.
Figure 7. Regression calibration curves for cationic and thermal samples.
at 5.1-5.8 ppm. The peaks at 4.1-4.5 ppm in the soluble extract
(Lin30 to Lin60) (sample Lin50 is shown in Figure 2) and in
linseed oil are due to the methylene protons (CH _ 2) of the
glyceride unit. This is a particularly characteristic peak for the
linseed oil. It is used in calculating the oil content in the soluble
Ind. Eng. Chem. Res., Vol. 47, No. 22, 2008 8569
Figure 8. Variation of insoluble contents of linseed oil (wt %) versus linseed
oil contents (wt %) in polymer sample obtained through 1H NMR and FTIR
analysis.
extract of the polymeric material. The aromatic protons of ST,
DVB, and the oligomeric portion of these materials are observed
between 7.1 and 7.9 ppm. These aromatic peaks are distinctive
and are used to calculate the ST and DVB contents in the soluble
extracts. The initiator used in the copolymerization of linseed
oil with other monomers is modified by linseed oil, and the
contents of initiator mixture are taken as linseed oil content.
However, the peak due to the solvent CDCl3 that occurs in the
same region at 7.26 ppm has been excluded from all calcula-
tions. The solvent collected from the soluble portion by vacuum
evaporation is checked for the presence of any oligomer. It is
found that the peak appears at the same point as for pure solvent
(peak shown in Figure 2).
The contents of oil and aromatic components (weight percent)
of the different samples are reported in Table 2. The linseed oil
content (weight percent) in the soluble extract varies from 64
to 90%, whereas the aromatic contents (ST-DVB) vary from
36 to 10%. The values in parentheses in the Soxhlet results of
Table 2 indicate the detailed microcomposition of the polymeric
samples. The soluble portion present in the samples helps in
plasticization of the cross-linked insoluble materials. Thus, the
insoluble materials mainly determine the properties of the
polymeric material. For the samples Lin30 to Lin60 in Table
2, the amount of oil increases in the insoluble fraction. This
fact is consistent with our hypothesis that the linseed is grafted
into the polymer chain of the ST and DVB copolymer during
prolonged heating. This is calculated from the FTIR studies of
the insoluble extract in the next section.
In the thermal polymerization of conjugated linseed oil,
acrylic acid, and divinylbenzene, the maximum amount of
linseed oil is present in the soluble fraction. In comparison to
the cationic samples, there is improvement in the quantity of
linseed oil in the insoluble portion also due to the conjugation
in the linseed oil. The 1H NMR spectra of AcA, DVB, CLin,
solvent collected on vacuum evaporation of the soluble extract,
and the soluble extract from the polymeric sample CLin50 are
shown in Figure 3. The extracts from CLin50 are representative
of the soluble extracts obtained from all other samples (CLin0
to CLin60). The peaks at 2.8 ppm are due to the methylene
(CH_ 2) protons present between the two unsaturated CdC double
8570 Ind. Eng. Chem. Res., Vol. 47, No. 22, 2008
bonds of the fatty acid chain. The presence of a similar peak in
DVB is due to the presence of methylene protons in ethylvi-
nylbenzene, which is present to the extent of about 20% in DVB.
The peaks for the vinylic (CdCsH _ ) protons of the linseed oil,
AcA, and DVB are present at 5.1-6.8 ppm. The peaks at
4.1-4.5 ppm in the soluble extract (CLin0 to CLin60) (sample
CLin50 is shown in Figure 3) and in conjugated linseed oil are
due to the methylene protons (CH _ 2) of the glyceride unit. This
is a characteristic peak for the linseed oil. It is used in calculating
the oil content in the soluble extract of the polymeric material.
The aromatic protons of the DVB and the oligomeric portion
of the material are observed between 7.1 and 7.9 ppm. These
aromatic peaks are distinctive and are used to calculate the DVB
content in the soluble extracts. However, the solvent (CDCl3)
peak, which occurs in the same region at 7.26 ppm, has been
excluded from all calculations. The peak at 11.9 ppm in acrylic
acid is due to the -OH _ of the carboxylic group present in the
acid, which shifted downward to 9.8 ppm in the polymeric
samples. The acids generally exist in dimeric form due to the
presence of intermolecular hydrogen bonding (Scheme 1),42 and
when polymerization occurs, the dimeric form becomes non-
existent. The cleavage of intermolecular hydrogen bonding leads
to the shifting of the signal downfield. This peak is the
characteristic peak of acrylic acid. The solvent removed from
the soluble portion by vacuum evaporation is free from any
oligomers. and the peak is shown in Figure 3. The peak is the
same as for pure solvent.
The contents of the conjugated linseed oil, acrylic acid, and
divinylbenzene (weight percent) for different polymeric samples
are reported in Table 3. The content of the linseed oil (weight
percent) in the soluble extract varies from 0 to 97%, and the
content of acrylic-DVB components varies from 100 to 3%.
The content of conjugated linseed oil in the soluble extract and
insoluble portion increases with an increase in the oil content
in the samples. The linseed oil used for thermal polymerization
is 87% conjugated and is more reactive. Therefore, more linseed
oil is grafted to the matrix. When the reactivity of conjugated
linseed oil is compared with other monomers, it is less reactive.
By conjugating the carbon-carbon double bonds, the reactivity
of the oils can be improved.43 The peaks at 2.76 ppm, which
are due to CH2 groups present between two C-C double bonds,
disappear. The decrease in the rigid part in the polymer with
increasing oil content results in the higher solubility of the
polymer in the solvent. From the results it is observed that the
reactivity of monomers has a greater impact on the properties
of resulting polymers. Although conjugated linseed oil is
reactive, the branching in the oil and the low mobility of the
oil results in the low oil content in the cross-linked polymer.
4.3. FTIR Analysis of Linseed Polymers. The quantitative
analysis of a component in solution can be successfully carried
out, provided there is a suitable characteristic band in the
spectrum of the component of the interest. The simple solid
mixture can be easily analyzed quantitatively, but a component
in a complex mixture presents special problems. The mixture
of linseed oil, styrene, and divinylbenzene is also a complex
mixture. The selection of the characteristic peaks solves the
complexity of this copolymer. To quantify the unknown amount
of linseed oil grafted to styrene-divinylbenzene copolymer and
the percentage of grafting, two absorbance peaks at 1744 and
1601 cm-1 for the cationic samples and three absorbance peaks
at 1744, 1711, and 1530 cm-1 for the thermal samples are
selected. In cationic samples, the peak at 1742 cm-1 is for the
ester linkage in oil and the second at 1601 cm-1 is for the
aromatic -CdC- linkage. These peaks are the characteristic
peaks for the oil and styrene-divinylbenzene in the polymer.
In thermal samples, the selected peak at 1744 cm-1 is for ester
linkage in the oil, the second at 1711 cm-1 is for the carbonyl
stretch in the acrylic acid, and the third at 1530 cm-1 is for
aromatic -CdC- linkage in divinylbenzene. The selected
absorbance peaks are shown in Figures 4, 5, and 6. The
regression calibration curves of various contents (weight percent)
against absorbance are obtained from the absorbance of the
samples at different peaks (Figure 7). The data from the
calibration curve are used to calculate the linseed oil content
(weight percent) in the insoluble portion and are reported in
Tables 2 and 3. The content of linseed oil (weight percent)
through 1H NMR and FTIR analysis is shown in Figure 8. It is
observed from Figure 8 that the content (weight percent) of
linseed oil in the polymer is almost equal for both 1H NMR
and FTIR analysis. It is also observed that the cationic polymer
samples have higher contents of bound linseed oil than the
thermal samples. The cationic polymer samples contain 3-5
times more polymerized linseed oil than the thermal samples.
Conjugated linseed oil is also studied for cationic polymer-
ization by using boron trifluoride diethyl etherate. The catalyst
used is very reactive, and it is not possible to control the reaction
even at low temperature. The addition of the boron trifluoride
diethyl etherate into the reaction mixture results in phase-
separated agglomerates in the mixture immediately.
5. Conclusions
Linseed oil based polymers from cationic and thermal
polymerizations have been investigated quantitatively through
1
H NMR and FTIR spectroscopic analysis. The solubilities of
the samples through Soxhlet extraction range from 22 to 37%
and from 4.23 to 53% for cationic and thermal samples,
respectively. The content of grafted linseed oil obtained through
1
H NMR ranges from 22.9 to 43.0% and from 0 to 10% for
cationic and thermal samples, and that from FTIR is 18.2-45.4%
and 0-10.7% for cationic and thermal samples. The values
obtained through quantitative 1H NMR and FTIR spectroscopic
analysis methods are consistent and can be applied to other
polymers also.
Literature Cited
(1) Koenig, J. L. Spectroscopy of Polymers, 2nd ed.; Elsevier: New York,
1999.
(2) Eidelman, N.; Simon, C. G., Jr. Characterization of combinatorial
polymer blend composition gradients by FTIR microspectroscopy. J. Res.
Natl. Inst. Stand. Technol. 2004, 109, 219–231.
(3) Everall, N.; Griffiths, P. R.; Chalmers, J. M. Vibrational Spectroscopy
of Polymers: Principles and Practice; Wiley: New York, 2007.
(4) Boccaleri, E.; Arrais, A.; Frache, A.; Gianelli, W.; Fino, P.; Camino,
G. Comprehensive spectral and instrumental approaches for the easy
monitoring of features and purity of different carbon nanostructures for
nanocomposite applications. Mater. Sci. Eng., B 2006, 131, 72–82.
(5) Smith, B. C. Multiple components II: Chemometric methods and
factor analysis in QuantitatiVe spectroscopy: Theory and practice. Academic
Press: San Diego, CA, 2002.
(6) Henrichs, P. M.; Hewitt, J. M.; Schwartz, L. J.; Bailey, D. B.
Quantitative NMR measurements in copolymers of vinylidene chloride and
acrylonitrile: The effect of saturation and varying nuclear Overhauser
enhancements. J. Polym. Sci., Part A: Polym. Chem. 1982, 20, 775–782.
(7) Cheng, H. N. NMR characterization of copolymers that exhibit
nonsymmetric compositional heterogeneity. Macromolecules 1997, 30,
4117–4125.
(8) Jamaludin, S. M. S.; Nor Azlan, M. R.; Fuad, M. Y. A.; Ishak,
Z. A. M.; Ishiaku, U. S. Quantitative analysis on the grafting of an aromatic
group on polypropylene in melt by FTIR technique. Polym. Test. 2000, 19,
635–642.

(9) Canto, L. B.; Pessan, L. A. Determination of the composition of
styrene-glycidyl methacrylate copolymers by FTIR and titration. Polym.
Test. 2002, 21, 35–38.
(10) Hazer, B. Grafting on polybutadiene with macro or macromonomer
initiators containing poly(ethylene glycol) units. Macromol. Chem. Phys.
1995, 196, 1945–1952.
(11) Sharma, V.; Kundu, P. P. Addition polymers from natural oilssA
review. Prog. Polym. Sci. 2006, 31, 983–1008.
(12) Sharma, V.; Kundu, P. P. Condensation polymers from natural oils.
Prog. Polym. Sci. 2008, in press. DOI: 10.1016/j.progpolymsci.2008.07.004.
(13) Li, F.; Hanson, M. V.; Larock, R. C. Soybean oil-divinylbenzene
thermosetting polymers: synthesis, structure, properties and their relation-
ships. Polymer 2001, 42, 1567–1579.
(14) Li, F.; Larock, R. C. New soybean oil-styrene-divinylbenzene
thermosetting copolymers. I. Synthesis and characterization. J. Appl. Polym.
Sci. 2001, 80, 658–670.
(15) Li, F.; Larock, R. C. New soybean oil-styrene-divinylbenzene
thermosetting copolymers II: dynamic mechanical properties. J Polym. Sci.,
Part B: Polym. Phys. 2000, 38, 2721–2738.
(16) Li, F.; Larock, R. C. New soybean oil-styrene-divinylbenzene
thermosetting copolymers III: tensile stress-strain behavior. J. Polym. Sci.,
Part B: Polym. Phys. 2001, 39, 60–77.
(17) Li, F.; Larock, R. C. New soybean oil-styrene-divinylbenzene
thermosetting copolymers IV: good damping properties. Polym. AdV.
Technol. 2002, 13, 436–449.
(18) Wool, R. P.; Kusefoglu, S. H.; Palmese, G. R.; Zhao, R.; Khot,
S. N. High modulus polymers and composites from plant oils. U.S. Patent
6,121,398, 2000.
(19) Khot, S. N.; Lascala, J. J.; Can, E.; Morye, S. S.; Williams, G. I.;
Palmese, G. R.; Kusefoglu, S. H.; Wool, R. P. Development and application
of triglyceride-based polymers and composites. J. Appl. Polym. Sci. 2001,
82, 703–723.
(20) Can, E.; Kusefoglu, S.; Wool, R. P. Rigid thermosetting liquid
molding resins from renewable resources: (1) copolymers of soyoil
monoglycerides with maleic anhydride. J. Appl. Polym. Sci. 2001, 81, 69–
77.
(21) Lorenz, C. D.; Stevens, M. J.; Wool, R. P. Fracture behavior of
triglyceride-based adhesives. J. Polym. Sci., Part B: Polym. Phys. 2004,
42, 3333–3343.
(22) Lu, J.; Hong, C. K.; Wool, R. P. Bio-based nanocomposites from
functionalized plant oils and layered silicate. J. Polym. Sci., Part B: Polym.
Phys. 2004, 42, 1441–1450.
(23) Zou, K.; Soucek, M. D. UV-curable organic-inorganic hybrid film
coatings based on epoxidized cyclohexene derivatized linseed oil. Macromol.
Chem. Phys. 2004, 204, 2032–2039.
(24) Zong, Z.; Soucek, M. D.; Liu, Y.; Hu, J. Cationic photopolymer-
ization of epoxynorborane linseed oils: The effect of diluents. J. Polym.
Sci., Part A: Polym. Chem. 2003, 41, 3440–3456.
(25) Teng, G.; Soucek, M. D. Blown soybean oil ceramer coatings for
corrosion protection. Macromol. Mater. Eng. 2003, 288, 844–851.
(26) Teng, G.; Soucek, M. D.; Vick, B. A.; Simonsick, W. J.; Sen, A.
Spectroscopic investigation of the blowing process of soybean oil. Surf.
Coat. Int. Part B: Coat. Trans. 2003, 86, 221–229.
Ind. Eng. Chem. Res., Vol. 47, No. 22, 2008 8571
(27) Chen, J.; Soucek, M. D.; Simonsick, W. J.; Celikay, R. W.
Preparation and photopolymerization of norbornyl epoxidized linseed oil.
Polymer 2002, 40, 5379–5389.
(28) Wold, C. R.; Ni, H.; Soucek, M. D. Model reaction study on the
interaction between the inorganic and organic phases in drying oil based
ceramer coatings. Chem. Mater. 2001, 13, 3032–3037.
(29) Wold, C. R.; Soucek, M. D. Viscoelastic and thermal properties of
linseed oil-based ceramer coatings. Macromol. Chem. Phys. 2000, 201, 382–
392.
(30) Hazer, B.; Demirel, S. I.; Borcakli, M.; Eroglu, M. S.; Cakmak,
M.; Erman, B. Free radical crosslinking of unsaturated bacterial polyesters
obtained from soybean oily acids. Polym. Bull. 2001, 46, 389–394.
(31) Cakmakli, B.; Hazer, B.; Borcakli, M. Poly (styrene peroxide) and
poly (methyl methacrylate peroxide) for grafting on unsaturated bacterial
polyesters. Macromol. Biosci. 2001, 1, 348–354.
(32) Ilter, S.; Hazer, B.; Borcakli, M.; Atici, O. Graft copolymerization
of methyl methacrylate onto a bacterial polyester containing unsaturated
side chains. Macromol. Chem. Phys. 2001, 202, 2281–2286.
(33) Arkin, A. H.; Hazer, B. Chemical modification of chlorinated
microbial polyesters. Biomacromolecules 2002, 3, 1327–1335.
(34) Cakmakli, B.; Hazer, B.; Tekin, I. O.; Acıkgoz, S.; Can, M.
Polymeric linoleic acid-polyolefin conjugates: Cell adhesion and biocom-
patibility. J. Am. Oil Chem. Soc. 2007, 84, 73–81.
(35) Li, F.; Perrenoud, A.; Larock, R. C. Thermophysical and mechanical
properties of novel polymers prepared by the cationic copolymerization of
fish oils, styrene and divinylbenzene. Polymer 2001, 42, 10133–10145.
(36) Li, F.; Larock, R. C.; Otaigbe, J. U. Fish oil thermosetting polymers:
creep and recovery behavior. Polymer 2000, 41, 4849–4862.
(37) Li, F.; Larock, R. C. Synthesis, structure and properties of new
tung oil-styrene-divinylbenzene copolymers prepared by thermal polym-
erization. Biomacromolecules 2003, 4, 1018–1025.
(38) Zhang, P.; He, J.; Zhou, X. An FTIR standard addition method for
quantification of bound styrene in its copolymers. Polym. Test. 2008, 27,
153–157.
(39) Chakraborty, S.; Bandyopadhyay, S.; Ameta, R.; Mukhopadhyay,
R.; Deuri, A. S. Application of FTIR in characterization of acrylonitrile-
butadiene rubber (nitrile rubber). Polym. Test. 2007, 26, 38–41.
(40) Sadeghi, G. M. M.; Morshedian, J.; Barikani, M. Determination of
OH-number and functionality of polybutadiene-ol by FTIR and NMR
spectroscopy. Polym. Test. 2003, 22, 165–168.
(41) Li, F.; Larock, R. C. New soybean oil-styrene-divinylbenzene
thermosetting copolymers. I: Synthesis and characterization. J. Appl. Polym.
Sci. 2001, 80, 658–670.
(42) Sharma, Y. R. Elementary Organic Spectroscopy: Principles and
Chemical Applications; S. Chand and Company Ltd.: New Delhi, India,
2002.
(43) Marc, L. G. Organic Chemistry; Addison-Wesley: Reading, MA,
1984.
ReceiVed for reView March 12, 2008
ReVised manuscript receiVed July 10, 2008
Accepted September 1, 2008
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