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Reactivities of conjugated dienes towards the 1-cyano-1-methylethyl and 1-phenylethyl radicals

Bevington, J. C. and Bowden, B. F. and Cywar, D. A. and Lyons, R. A. and Senogles, E. and Tirrell, D. A. (1991) Reactivities of conjugated dienes towards the 1-cyano-1-methylethyl and 1-phenylethyl radicals. European Polymer Journal, 27 (11). pp. 1239-1249. ISSN 0014-3057. https://resolver.caltech.edu/CaltechAUTHORS:BEVepj1991b

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Abstract

Study of the reactions of monomers with the 1-cyano-1-methylethyl and 1-phenylethyl radicals, derived from azobisisobutyronitrile and 1,1′-azobis(1-phenylethane) respectively, has been extended to the cases of isoprene, 2,3-dimethyl-1,3-butadiene and 2,3-diphenyl-1,3-butadiene. The procedure involves examination by ^(13)C-NMR of end-groups in binary copolymers of the dienes with methyl methacrylate, made using ^(13)C-enriched samples of the azo compounds as initiators. Selectivity in the reactions of the initiating radicals with monomers is compared with that in the reactions of the monomers with polymethacrylonitrile and polystyrene radicals, as deduced from consideration of appropriate copolymerizations. The 1-phenylethyl radical models the polystyrene radical rather more satisfactorily than the 1-cyano-1-methylethyl radical models the polymethacrylonitrile radical. There is further discussion of the effects of penultimate monomeric units on selectivity in the reactions of growing polymer radicals with monomers.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1016/0014-3057(91)90061-RDOIArticle
http://www.sciencedirect.com/science/article/pii/001430579190061RPublisherArticle
ORCID:
AuthorORCID
Tirrell, D. A.0000-0003-3175-4596
Additional Information:Copyright © 1991 Elsevier. (Received 25 March 1991)
Issue or Number:11
Record Number:CaltechAUTHORS:BEVepj1991b
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:BEVepj1991b
Official Citation:J.C. Bevington, B.F. Bowden, D.A. Cywar, R.A. Lyons, E. Senogles, D.A. Tirrell, Reactivities of conjugated dienes towards the 1-cyano-1-methylethyl and 1-phenylethyl radicals, European Polymer Journal, Volume 27, Issue 11, 1991, Pages 1239-1249, ISSN 0014-3057, http://dx.doi.org/10.1016/0014-3057(91)90061-R. (http://www.sciencedirect.com/science/article/pii/001430579190061R)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:53509
Collection:CaltechAUTHORS
Deposited By: Anne Hormann
Deposited On:23 Jan 2015 23:32
Last Modified:03 Oct 2019 07:50

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