Mechanism of free-radical copolymerization of styrene with acrylonitrile and methacrylonitrile mediated by 2,2,6,6-tetramethyl-1-piperidinyloxy

By the examples of chemically similar styrene-acrylonitrile and styrene-methacrylonitrile systems, substantially different mechanisms of TEMPO-mediated copolymerization have been theoretically predicted and experimentally verified. Living copolymer-TEMPO adducts capable of thermal decomposition and...

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Bibliographic Details
Published in:Polymer science. Series A, Chemistry, physics Chemistry, physics, 2008-04, Vol.50 (4), p.365-373
Main Authors: Zaremski, M. Yu, Garina, E. S., Plutalova, A. V., Golubev, V. B.
Format: Article
Language:eng ; rus
Subjects:
Chemistry
Chemistry and Materials Science
Polymer Sciences
Polymerization
Synthesis
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Summary:By the examples of chemically similar styrene-acrylonitrile and styrene-methacrylonitrile systems, substantially different mechanisms of TEMPO-mediated copolymerization have been theoretically predicted and experimentally verified. Living copolymer-TEMPO adducts capable of thermal decomposition and polymerization reinitiation via the pseudoliving mechanism predominantly form in the first system. The reaction proceeds under the steady-state regime and is characterized by the living growth of M n of the copolymer with conversion. In the second system, the probabilities of formation of living and dead macromolecules are equal. Therefore, the living growth of M n of the copolymer ceases and the reaction passes to the conventional copolymerization regime.
ISSN:0965-545X
1757-1820
1555-6107
DOI:10.1134/S0965545X08040020