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Model copolymerization reactions: determination of the relative rates of addition of styrene and acrylonitrile to the 1-cyanoethyl radical

Prementine, Glenn S. and Tirrell, David A. (1987) Model copolymerization reactions: determination of the relative rates of addition of styrene and acrylonitrile to the 1-cyanoethyl radical. Macromolecules, 20 (12). pp. 3034-3038. ISSN 0024-9297. https://resolver.caltech.edu/CaltechAUTHORS:PREm1987

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Abstract

2,2'-Azobis([2-^(13)C]propionitrile) (1) was prepared in 35% overall yield starting from [^(13)C]-acetaldehyde (99 atom %). Quantitative ^(13)C NMR analysis of end groups in styrene-acrylonitrile copolymers prepared with 1 as initiator allows determination of the relative rates of addition of these olefins to the 1-cyanoethyl radical. We have found k_A/k_s = 0.12 ± 0.03, a result consistent with the penultimate model treatment of this copolymerization system by Hill, O'Donnell, and O'Sullivan.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ma00178a015DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ma00178a015PublisherArticle
ORCID:
AuthorORCID
Tirrell, David A.0000-0003-3175-4596
Additional Information:© 1987 American Chemical Society. Received April 13, 1987. Acknowledgment is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this work. Support of our research by a Presidential Young Investigator Award of the National Science Foundation (to D.A.T.) is also acknowledged. NMR spectra were recorded in the University of Massachusetts NMR Laboratory, which is supported in part by the NSF Materials Research Laboratory at the University. Registry No. 1, 96837-18-2; (S))(A) (copolymer), 9003-54-7; PS, 9003-53-6; PA, 25014-41-9; S, 100-42-5; A, 107-13-1; (1-^(13)C)-H3CCHO, 2188-31-0; H2NNH2.H2SO4, 10034-93-2; 2,2'-hydrazobis([2-^(13)C]propionitrile), 110774-07-7.
Funders:
Funding AgencyGrant Number
American Chemical Society Petroleum Research FundUNSPECIFIED
NSFUNSPECIFIED
Issue or Number:12
Record Number:CaltechAUTHORS:PREm1987
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:PREm1987
Official Citation:Model copolymerization reactions: determination of the relative rates of addition of styrene and acrylonitrile to the 1-cyanoethyl radical Glenn S. Prementine and David A. Tirrell Macromolecules 1987 20 (12), 3034-3038
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:53595
Collection:CaltechAUTHORS
Deposited By: Anne Hormann
Deposited On:22 Jan 2015 21:23
Last Modified:03 Oct 2019 07:51

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