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Mechanism of the controlled radical polymerization of styrene and methyl methacrylate in the presence of dicyclopentadienyltitanium dichloride
Author(s) -
Grishin Dmitry F.,
Ignatov Stanislav K.,
Shchepalov Alexander A.,
Razuvaev Alexey G.
Publication year - 2004
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.631
Subject(s) - chemistry , polymerization , methyl methacrylate , polymer chemistry , radical polymerization , styrene , photochemistry , monomer , chain termination , living free radical polymerization , copolymer , organic chemistry , polymer
The mechanism of the controlled radical polymerization of styrene and methyl methacrylate in the presence of dicyclopentadienyltitanium dichloride (Cp 2 TiCl 2 ) was studied using quantum chemical calculations and electron spin resonance spectroscopy. It was established that the reduction of Cp 2 TiCl 2 to Cp 2 TiCl during the macromolecule synthesis occurs through the living polymerization mechanism, which adjusts the growth of a polymeric chain. The geometrical structures of the molecular complexes between a growing macroradical and Cp 2 TiCl 2 and transition states of radical inhibition steps were optimized and the thermodynamic and kinetic parameters of the elementary reactions were estimated for several feasible directions of the process. On this basis, the observed kinetic features of vinylic monomer polymerization with participation of organic compounds of titanium are discussed. Copyright © 2004 John Wiley & Sons, Ltd.