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Model copolymerization reactions. Direct observation of a "penultimate effect" in a model styrene-acrylonitrile copolymerization

Jones, Sharon A. and Prementine, Glenn S. and Tirrell, David A. (1985) Model copolymerization reactions. Direct observation of a "penultimate effect" in a model styrene-acrylonitrile copolymerization. Journal of the American Chemical Society, 107 (18). pp. 5275-5276. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:JONjacs9185

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Abstract

Forty years after the publication of the classical kinetic scheme for radical copolymerization, there is still debate concerning the factors that control composition and comonomer sequence in some copolymer chains. Interest in this problem arises not only from an intrinsic desire to understand the copolymerization process but also from the realization that alternative kinetic models of copolymerization predict very different copolymer chain structures. For example, Hill, O’Donnell, and O’Sullivan have shown in their analysis of styrene-acrylonitrile copolymerization that the best terminal, penultimate, and complex-participation models predict very similar copolymer compositions but very different comonomer sequences; in a copolymer prepared from an equimolar monomer mixture, the number fraction of styrene sequences which consist of an isolated styrene unit is predicted to be 0.74 for the terminal model, 0.61 for the penultimate model, and 0.18 for the unrestricted complex-participation model. Clearly the synthesis of well-defined copolymer structures requires a precise understanding of copolymerization mechanism.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja00304a042DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00304a042PublisherArticle
ORCID:
AuthorORCID
Tirrell, David A.0000-0003-3175-4596
Additional Information:© 1985 American Chemical Society. Received December 10, 1984. Acknowledgment is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for support of this research. This work was also supported by an Alfred P. Sloan Research Fellowship (D.A.T.) and a Presidential Young Investigator Award of the National Science Foundation (D.A.T.).
Funders:
Funding AgencyGrant Number
American Chemical Society Petroleum Research FundUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
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Record Number:CaltechAUTHORS:JONjacs9185
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:JONjacs9185
Official Citation:Model copolymerization reactions. Direct observation of a "penultimate effect" in a model styrene-acrylonitrile copolymerization Sharon A. Jones, Glenn S. Prementine, and David A. Tirrell Journal of the American Chemical Society 1985 107 (18), 5275-5276
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ID Code:53633
Collection:CaltechAUTHORS
Deposited By: Anne Hormann
Deposited On:20 Jan 2015 18:47
Last Modified:20 Jan 2015 18:47

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