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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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Published in: | Polymer science. Series A, Chemistry, physics Chemistry, physics, 2008-04, Vol.50 (4), p.365-373 |
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Main Authors: | , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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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. |
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ISSN: | 0965-545X 1757-1820 1555-6107 |
DOI: | 10.1134/S0965545X08040020 |