TY - JOUR
T1 - Free Radical Polymerization Behavior of the Vinyl Monomers from Plant Oil Triglycerides
AU - Demchuk, Zoriana
AU - Shevchuk, Oleg
AU - Tarnavchyk, Ihor
AU - Kirianchuk, Vasylyna
AU - Kohut, Ananiy
AU - Voronov, Stanislav
AU - Voronov, Andriy
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/12/5
Y1 - 2016/12/5
N2 - A one-step method of plant oil direct transesterification was used to synthesize new vinyl monomers from sunflower (SFM), linseed (LSM), soybean (SBM), and olive (OVM) oils. The degree of unsaturation in plant oil fatty acids was used as a criterion to compare the free radical polymerization behavior of new monomers. The number-average molecular weight of plant oil-based homopolymers synthesized in toluene in the presence of AIBN at 75 °C varies at 11 000-25 000 and decreases as follows: poly(OVM) > poly(SFM) > poly(SBM) > poly(LSM), corresponding to increasing degree of unsaturation in the monomers. Rate of polymerization depends noticeably on the degree of unsaturation in monomers. Due to the allylic termination, chain propagation coexists with effective chain transfer during polymerization. The obtained values of CM (ratio of chain transfer and propagation rate constants) depends on monomer structure as follows: CM(LSM) > CM(SBM) > CM(SFM) > CM(OVM). 1H NMR spectroscopy shows that the fraction of the reacting allylic atoms does not vary significantly for the synthesized monomers (7-12%) and is determined entirely by plant oil degree of unsaturation. The glass transition temperature of homopolymers [Tg = 4.2 °C for poly(SFM), Tg = −6 °C for poly(SBM)] from new monomers indicates that varying biobased fragments in copolymers might considerably change the intermolecular interactions of macromolecules and their physicochemical properties.
AB - A one-step method of plant oil direct transesterification was used to synthesize new vinyl monomers from sunflower (SFM), linseed (LSM), soybean (SBM), and olive (OVM) oils. The degree of unsaturation in plant oil fatty acids was used as a criterion to compare the free radical polymerization behavior of new monomers. The number-average molecular weight of plant oil-based homopolymers synthesized in toluene in the presence of AIBN at 75 °C varies at 11 000-25 000 and decreases as follows: poly(OVM) > poly(SFM) > poly(SBM) > poly(LSM), corresponding to increasing degree of unsaturation in the monomers. Rate of polymerization depends noticeably on the degree of unsaturation in monomers. Due to the allylic termination, chain propagation coexists with effective chain transfer during polymerization. The obtained values of CM (ratio of chain transfer and propagation rate constants) depends on monomer structure as follows: CM(LSM) > CM(SBM) > CM(SFM) > CM(OVM). 1H NMR spectroscopy shows that the fraction of the reacting allylic atoms does not vary significantly for the synthesized monomers (7-12%) and is determined entirely by plant oil degree of unsaturation. The glass transition temperature of homopolymers [Tg = 4.2 °C for poly(SFM), Tg = −6 °C for poly(SBM)] from new monomers indicates that varying biobased fragments in copolymers might considerably change the intermolecular interactions of macromolecules and their physicochemical properties.
KW - Free radical polymerization
KW - Plant oil-based monomers
KW - Renewable polymers
UR - http://www.scopus.com/inward/record.url?scp=85001975405&partnerID=8YFLogxK
U2 - 10.1021/acssuschemeng.6b01890
DO - 10.1021/acssuschemeng.6b01890
M3 - Article
AN - SCOPUS:85001975405
SN - 2168-0485
VL - 4
SP - 6974
EP - 6980
JO - ACS Sustainable Chemistry and Engineering
JF - ACS Sustainable Chemistry and Engineering
IS - 12
ER -