2018 (1) 7

Hydrogen peroxide as a chain transfer agent in the radical diene polymerization

Vitaly Boiko, Vladimir Grishchenko

Institute of Macromolecular Chemistry NAS of Ukraine

48, Kharkivske shose, Kyiv, 02160, Ukraine

Polym. J., 2018, 40, no. 1: 46-50

Section: Synthesis polymers.

Language: English.

Abstract:

Analysis of chain termination in the radical polymerization of dienes in solutions of alcohols initiated by hydrogen peroxide has shown that chain termination is accomplished by chain transfer to initiator, rather than by recombination of macroradicals. This conclusion is made on the basis of calculations of the rates of chain termination by both paths, carried out using our own and published data on the rate constants of macroradical reactions and comparing them with data on the functionality of oligodienes by hydroxyl groups. The problem of reactivity of hydroxyl radicals formed in the chain transfer on hydrogen peroxide molecule is discussed. The reaction rate of the hydroxyl radical with double bond of the oligomer, which proceeds with the formation of allylic radical in the chain, is estimated from the rate constants of similar reactions in methyl methacrylate and a-methyl styrene. The peculiarity of this reaction is determined by the high activity of hydroxyl radicals and nonselectivity of their interactions in the system, which leads to the chain transfer to the oligomer. Thus, in this system, hydrogen peroxide acts simultaneously as a polymerization initiator and a chain transfer agent, which leads to the termination of macroradicals with forming a terminal hydroxyl group.

Keywords: diene radical polymerization, HTPB; hydrogen peroxide, chain termination, chain transfer.

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