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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.
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 4. FTIR absorbance spectra of the cationic samples Lin30 and Lin40.
Figure 5. FTIR absorbance spectra of the cationic samples Lin50 and Lin60.
bonds of the fatty acid chain. The presence of a similar peak in peaks for the oil and styrene-divinylbenzene in the polymer.
DVB is due to the presence of methylene protons in ethylvi- In thermal samples, the selected peak at 1744 cm-1 is for ester
nylbenzene, which is present to the extent of about 20% in DVB. linkage in the oil, the second at 1711 cm-1 is for the carbonyl
The peaks for the vinylic (CdCsH _ ) protons of the linseed oil, stretch in the acrylic acid, and the third at 1530 cm-1 is for
AcA, and DVB are present at 5.1-6.8 ppm. The peaks at aromatic -CdC- linkage in divinylbenzene. The selected
4.1-4.5 ppm in the soluble extract (CLin0 to CLin60) (sample absorbance peaks are shown in Figures 4, 5, and 6. The
CLin50 is shown in Figure 3) and in conjugated linseed oil are regression calibration curves of various contents (weight percent)
due to the methylene protons (CH _ 2) of the glyceride unit. This against absorbance are obtained from the absorbance of the
is a characteristic peak for the linseed oil. It is used in calculating samples at different peaks (Figure 7). The data from the
the oil content in the soluble extract of the polymeric material. calibration curve are used to calculate the linseed oil content
The aromatic protons of the DVB and the oligomeric portion (weight percent) in the insoluble portion and are reported in
of the material are observed between 7.1 and 7.9 ppm. These Tables 2 and 3. The content of linseed oil (weight percent)
aromatic peaks are distinctive and are used to calculate the DVB through 1H NMR and FTIR analysis is shown in Figure 8. It is
content in the soluble extracts. However, the solvent (CDCl3) observed from Figure 8 that the content (weight percent) of
peak, which occurs in the same region at 7.26 ppm, has been linseed oil in the polymer is almost equal for both 1H NMR
excluded from all calculations. The peak at 11.9 ppm in acrylic and FTIR analysis. It is also observed that the cationic polymer
acid is due to the -OH _ of the carboxylic group present in the samples have higher contents of bound linseed oil than the
acid, which shifted downward to 9.8 ppm in the polymeric thermal samples. The cationic polymer samples contain 3-5
samples. The acids generally exist in dimeric form due to the times more polymerized linseed oil than the thermal samples.
presence of intermolecular hydrogen bonding (Scheme 1),42 and Conjugated linseed oil is also studied for cationic polymer-
when polymerization occurs, the dimeric form becomes non- ization by using boron trifluoride diethyl etherate. The catalyst
existent. The cleavage of intermolecular hydrogen bonding leads used is very reactive, and it is not possible to control the reaction
to the shifting of the signal downfield. This peak is the even at low temperature. The addition of the boron trifluoride
characteristic peak of acrylic acid. The solvent removed from diethyl etherate into the reaction mixture results in phase-
the soluble portion by vacuum evaporation is free from any separated agglomerates in the mixture immediately.
oligomers. and the peak is shown in Figure 3. The peak is the
same as for pure solvent. 5. Conclusions
The contents of the conjugated linseed oil, acrylic acid, and
Linseed oil based polymers from cationic and thermal
divinylbenzene (weight percent) for different polymeric samples
polymerizations have been investigated quantitatively through
are reported in Table 3. The content of the linseed oil (weight 1
H NMR and FTIR spectroscopic analysis. The solubilities of
percent) in the soluble extract varies from 0 to 97%, and the
the samples through Soxhlet extraction range from 22 to 37%
content of acrylic-DVB components varies from 100 to 3%. and from 4.23 to 53% for cationic and thermal samples,
The content of conjugated linseed oil in the soluble extract and respectively. The content of grafted linseed oil obtained through
insoluble portion increases with an increase in the oil content 1
H NMR ranges from 22.9 to 43.0% and from 0 to 10% for
in the samples. The linseed oil used for thermal polymerization cationic and thermal samples, and that from FTIR is 18.2-45.4%
is 87% conjugated and is more reactive. Therefore, more linseed and 0-10.7% for cationic and thermal samples. The values
oil is grafted to the matrix. When the reactivity of conjugated obtained through quantitative 1H NMR and FTIR spectroscopic
linseed oil is compared with other monomers, it is less reactive. analysis methods are consistent and can be applied to other
By conjugating the carbon-carbon double bonds, the reactivity polymers also.
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,
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