SULFONYL CHLORIDES - NOVEL SOURCE OF FREE RADICALS

Author:

Seleznev A. A.1,Radchenko D. P.2,Golubova S. I.1,Safronov S. A.1,Navrotskiy V. A.1

Affiliation:

1. Volgograd State Technical University

2. Volgograd State University

Abstract

Novel free radicals source based on sulfonyl chlorides is discovered. The radical mechanism is confirmed by 2,3-dimethyl-2,3-diphenylbutane formation under chlorosulfonated polyethylene heating in the isopropylbenzene solution. Concerted homolytic C-S and S-Cl bond scission of chlorosulfonated polyethylene thermal degradation mechanism proved by kinetic analysis. The proof of the two bonds simultaneous breaking is provided by the threefold activation energy reduction (83 kJ/mol) in comparison to the C-S and C-Cl bond dissociation energy (280 and 286 kJ/mol respectively), the 6 orders lower preexponential factor (2,46 ∙ 10 s) in Arrhenius equation in comparison to one bond cleavage (≈10-10 s) as well as the strongly negative activation entropy value (-134 J/mol∙K).

Funder

Russian Foundation for Basic Research

Publisher

Volgograd State Technical University

Subject

General Medicine

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