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

Creators: Prementine, Glenn S.; Tirrell, David A.

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.

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© 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.

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

Abstract

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