Wicks, Douglas A. and Tirrell, David A. (1992) Structural Effects on Reactivity of Polymer-Bound Functional Groups. Kinetics of Nucleophilic Displacement Reactions on Chlorinated Polyethers. In: Catalysis in Polymer Synthesis. ACS Symposium Series. No.496. American Chemical Society , Washington, DC, pp. 136-148. ISBN 9780841224568. https://resolver.caltech.edu/CaltechAUTHORS:20150209-131329637
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Abstract
The reactions of chlorinated polyethers with tetrabutylammonium benzoate in N,N-dimethylacetamide have been examined. In all cases, the reactions are described by simple second-order kinetics at low conversion but exhibit retardation at extents of reaction greater than 60%. The magnitude of the retardation is a function of the length of the side chain that connects the polymer backbone and the reactive site, and the effect nearly vanishes for the C_4 side chain. Suppression of the reaction rate is proposed to arise from steric inhibition of attack by the relatively bulky benzoate ion.
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| Additional Information: | Copyright © 1992 American Chemical Society. Publication Date (Print): July 23, 2009. This work was supported by a Presidential Young Investigator Award of the National Science Foundation. 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. We thank Dr. Brian P. Devlin for the computer programs used to evaluate the kinetic parameters K, L and e. | |||||||||
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| Series Name: | ACS Symposium Series | |||||||||
| Issue or Number: | 496 | |||||||||
| DOI: | 10.1021/bk-1992-0496.ch010 | |||||||||
| Record Number: | CaltechAUTHORS:20150209-131329637 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20150209-131329637 | |||||||||
| Official Citation: | Structural Effects and Reactivity of Polymer-Bound Functional Groups Douglas A. Wicks and David A. Tirrell Catalysis in Polymer Synthesis. June 22, 1992, 136-148 Doi:10.1021/bk-1992-0496.ch010 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 54573 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Anne Hormann | |||||||||
| Deposited On: | 04 Mar 2015 16:43 | |||||||||
| Last Modified: | 10 Nov 2021 20:35 |
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