SYNTHESIS OF (ACRYLOYLAMINO) ETHYL OLEATE FROM TRIGLYCERIDES OF OLIVE OIL AND ITS FREE-RADIAL HOMO- AND COPOLYMERIZATION

2018;
196-204
1
Lviv Polytechnic National University
2
Lviv Polytechnic National University
3
Lviv Polytechnic National University
4
Lviv Polytechnic National University
5
North Dakota State University
6
Lviv Polytechnic National University

In the last decade, attention to the synthesis of plant-based monomers has been grown, due to their biocompatibility, non-toxicity, also their renewal. Polymers based on them can be used as an alternative to conventional polymers of petrochemical origin, to produce composites, coatings and other materials especially those that are used to decorate the interiors of houses and offices. There is a growing interest in plant oil-based monomers. A range of the hydrophobic monomers that are used to obtain paints, adhesives, plasticizers, coatings etc. were synthesized.

The main aim of the work was to synthesize (acryloylamino) ethyl oleate ("olive" monomer, OM) from triglycerides of olive oil and study the kinetic peculiarities and the mechanism for the free radical homo- and copolymerization, compared with the monomer based on the triglycerides of soy oil -(acryloylamino) ethyl soyate ("soy" monomer, SM).

The chemical structure of OM and SM were confirmed using 1H NMR and FT-IR spectroscopy. The presence of the vinyl group in the molecule and the double bonds in the acyl moiety of fatty acid causes, at their radical polymerization, the simultaneous occurring of chain growth reactions and chain transfer reaction to the monomer with the participation of allyl hydrogen atoms in the α-position to the double bond in the fatty acid fragment. The kinetic peculiarities for the homopolymerization of OM, reactivity ratios (r1, r2) in copolymerization of OM with styrene, and vinyl acetate, as well as the Q−e parameters of OM, were determined. The differences between the structures of OM (the presence of only one double bond in the acyl moiety of fatty acid) compared with SM, which contains two double bonds, allow decrease the quantity of chain transfer reaction and formation of low-activity radicals, due to decrease amount of allylic hydrogens, also increase the rate of polymerization and polymer molecular weight.

The synthesized OM is a promising comonomer in the polymerization reactions. Even with low its content in finite macromolecules of copolymers, OM gives them unique properties. Resulting comonomers could be used as surface-active agents, emulsifiers, adhesives, interphase modifiers and polymer materials for drug delivery.

1. Havelka K. O., McCormick C. L. Specialty Monomers and Polymers: Synthesis, Properties, and
Applications. 1st ed.// American Chemical Society. – Washington, D. C. – 2000. – Р. 254. 2. Chen F. B.,
Bufkin G. Crosslinkable Emulsion Polymers by Autoxidation. I. Reactivity Ratios // J. Appl. Polym. Sci. –
1985. – No. 30. – Р. 4571−4582. 3. Yuan L., Wang Z., Trenor N. M., Tang C. Robust Amidation
Transformation of Plant Oils into Fatty Derivatives for Sustainable Monomers and Polymers //
Macromolecules. – 2015. – No. 48. – Р. 1320−1328. 4. Moreno M., Miranda J. I., Goikoetxea M.,
Barandiaran M. Sustainable polymer latexes based on linoleic acid for coatings applications// Prog. Org.
Coat. – 2014. – No. 77. – Р. 1709–1714. 5. Tarnavchyk I., Popadyuk A., Popadyuk N., Voronov
A. Synthesis and Free Radical Copolymerization of a Vinyl Monomer from Soybean Oil // ACS Sustainable
Chem. Eng. – 2015. – No. 3. – Р. 1618−1622. 6. Еркова Л. Н., Чечик О. С. Латексы. – Л.: Химия,
1983. – 224 с. 7. Final Report on the Safety Assessment of Oleic Acid, Laurie Acid, Palmitic Acid, Myristic
Acid, and Stearic Acid, journal of the American College of Toxicology // Mary and Liebert, Inc.,
Publishers. – 1987 – 6, No. 3. 8. Demchuk Z., Shevchuk O., Tarnavchyk I., Kirianchuk V., Kohut A.,
Voronov S., Voronov A. Free Radical Polymerization Behavior of the Vinyl Monomers from Plant Oil
Triglycerides // ACS Sustainable Chem. Eng. – 2016. – No. 4. – Р. 6974–6980. 9. Kirianchuk V.,
Demchuk Z., Shevchuk O., Kohut A., Tarnavchyk I., Voronov S., Voronov A. Free radical homo- and
copolymerization features of the new vinyl monomer based on olive oil // 19th JCF-Frühjahrssymposium
(spring symposium). Mainz, Germany. March – April 2017. – Р. 293. 10. Keith James Laidler Chemical
Kinetics. – New York: Harper & Row, 1987 – P. 531. 11. Бреслер С. Е., Ерусалимский Б. Л. Физика и
химия макромолекул – М.; Л.: Наука, 1965. – 509 с. 12. Emanuel N. M., Knorre D. G. Chemical
Kinetics: Homogeneous Reactions, 2nd ed., New York: Wiley, 1974. – P. 460. 13. Kukulj D., Davis T. P.,
Gilbert R. G. Chain Transfer to Monomer in the Free-Radical Polymerizations of Methyl Methacrylate,
Styrene, and α-Methylstyrene // Macromolecules. – 1998. – No. 31. – P. 994−999. 14. Samarth N.,
Mahanwar P. Modified Vegetable Oil Based Additives as a Future Polymeric Material–Review // Open
Journal of Organic Polymer Materials. – 2015. – No. 5. – P.1–22. 15. Odian G. Principles of
Polymerization, 4th ed. – New York: Wiley, 2004. – P. 832. 16. Vilela C., Rua R., Silvestre A. J. D.,
Gandini A. Polymers and copolymers from fatty acid-based monomers // Ind. Crops Prod. – 2010. – 32. –
Р. 97−104. 17. Carraher C. E. Introduction to Polymer Chemistry, 2nd ed. – Boca Raton, FL.: Taylor &
Francis, 2010. – P. 534. 18. Demchuk Z., Shevchuk O., Tarnavchyk I., Kirianchuk V., Lorenson M.,
Kohut A., Voronov S., Voronov A. Free Radical Copolymerization Behavior of Plant Oil-Based Vinyl
Monomers and Their Feasibility in Latex Synthesis // ACS Omega. – 2016. – No. 1. – P. 1374−1382.