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Determination of the relative rates of addition of styrene and acrylonitrile to the 1-(1,3-diphenyl)propyl and 1-(3-cyano-1-phenyl)propyl radicals. Evidence for a penultimate effect in radical copolymerization

Cywar, Douglas A. and Tirrell, David A. (1989) Determination of the relative rates of addition of styrene and acrylonitrile to the 1-(1,3-diphenyl)propyl and 1-(3-cyano-1-phenyl)propyl radicals. Evidence for a penultimate effect in radical copolymerization. Journal of the American Chemical Society, 111 (19). pp. 7544-7553. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:CYWjacs1989

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Abstract

1,1’-Azobis( 1,3-[ 1-^(13)C]diphenylpropane) (1b) and 4,4’-azobis(4-phenyl[4-^(13)C]butyronitrile) (1C) were prepared in overall yields of 10% and 1.2%, respectively, both starting from Ba^(13)CO_3 (99 atom %). Analysis of end-group concentrations in styrene-acrylonitrile (SAN) copolymers prepared with 1b as initiator allows accurate determination of the relative rates of addition of these monomers (k_s/k_A) to the 1-( 1,3-diphenylpropyl) radical (2b); similarly, analysis of SAN copolymers prepared with IC allows determination of k_s/k_A for the 1-(3-cyano-l-phenylpropyl) radical (2c). Significantly different preferences of the radicals for addition of styrene and acrylonitrile were observed; we obtain k_s/k_A = 0.21 f±0.01 for 2b and k_s/k_A = 0.52 ± 0.03 for 2c. These results show that k_s/k_A for 1-(1-phenylalkyl) radicals is sensitive to substitution y to the radical center and provide strong support for the existence of a penultimate unit effect in SAN copolymerization. The results are consistent with the penultimate model analysis of SAN copolymerization by Hill, O’Donnell, and OSullivan.


Item Type:Article
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http://dx.doi.org/10.1021/ja00201a041DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00201a041PublisherArticle
ORCID:
AuthorORCID
Tirrell, David A.0000-0003-3175-4596
Additional Information:© 1989 American Chemical Society. Received March 14, 1989. 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 gratefully 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. The authors thank Dr. Douglas A. Wicks for advice and assistance.
Funders:
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American Chemical Society Petroleum Research FundUNSPECIFIED
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Record Number:CaltechAUTHORS:CYWjacs1989
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:CYWjacs1989
Official Citation:Determination of the relative rates of addition of styrene and acrylonitrile to the 1-(1,3-diphenyl)propyl and 1-(3-cyano-1-phenyl)propyl radicals. Evidence for a penultimate effect in radical copolymerization Douglas A. Cywar and David A. Tirrell Journal of the American Chemical Society 1989 111 (19), 7544-7553
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:53530
Collection:CaltechAUTHORS
Deposited By: Anne Hormann
Deposited On:11 Jan 2015 03:56
Last Modified:11 Jan 2015 03:56

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