Kinetics of macroradicals propagation and decay in polymeric matrix of 1,6-hexanediol diacrylate

Authors: 

Yuriy Medvedevskikh, Galyna Khovanets’, Andriy Kytsya and Iryna Yevchuk

Dependence of acrylate macroradicals concentration in polymeric matrix of 1,6-hexanediol diacrylate on time within temperature range of 45-80С has been investigated by means of ESR-spectroscopy. It has been established that experimental data do not linearize in coordinates of equation of the second order reaction, what coordinates with bimolecular mechanism of macroradicals decay. It has been suggested, that the effect of decreasing of the rate constant of bimolecular macroradicals decay in time is related with their propagation in chain propagation reaction. Kinetic equation obtained on this basis satisfactorily describes experimental data, what allowed to estimate quantitatively such parameters as the rate constants of chain propagation an termination in polymeric matrix, diffusion coefficient of macroradicals and characteristic time of segmental movement.

[1] Russel G., Nappel P., Gilbert R.: Macromolecules, 1988, 21, 2133.
[2] Brun E.V., Ivanov V..А., Каminskiy V.А.: Vysokomol. soyed. (А), 1992, 34(4), 40.
[3] Kurdikar D., Peppas N.: Macromolecules, 1994, 27, 4084.
[4] Litvinenko G.L., Lachinov М.V., Sarkisova E.V.: Vysokomol. soyed. (А), 1994, 36(2), 327.
[5] Andrzejewska E.: Progr. Polymer Science, 2001, 26, 605.
[6] Wertz J.E., Bolton J.R.: Electron Spin Resonance. Elementary Theory and Practical Application, McGraw-Hill Book Company, New York, 1972.
[7] Medvedevskikh Yu.G., Kytsya A.R., Holdak O.S., at al.: J Appl Polymer Sci, 2007, 106(6), 4047.
[8] Conformation of Macromolecules: Thermodynamic and Kinetic Demonstrations (ed. by Medvedevskikh Yu.G., Voronov S.A., Zaikov G.E.), Nova Science Publishers, 2007.