Mechanism of free-radical copolymerization of styrene with acrylonitrile and methacrylonitrile mediated by 2,2,6,6-tetramethyl-1-piperidinyloxy |
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Authors: | M. Yu. Zaremski E. S. Garina A. V. Plutalova V. B. Golubev |
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Affiliation: | (1) Faculty of Chemistry, Moscow State University, Leninskie gory, Moscow, 119991, Russia |
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Abstract: | 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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