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Structural Effects on Reactivity of Polymer-Bound Functional Groups. Kinetics of Nucleophilic Displacement Reactions on Chlorinated Polyethers

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. http://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.


Item Type:Book Section
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/bk-1992-0496.ch010DOIBook chapter
http://pubs.acs.org/doi/abs/10.1021/bk-1992-0496.ch010PublisherBook chapter
ORCID:
AuthorORCID
Tirrell, David A.0000-0003-3175-4596
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.
Funders:
Funding AgencyGrant Number
NSF Presidential Young Investigator AwardUNSPECIFIED
NSF Materials Research Laboratory at the University of MassachusettsUNSPECIFIED
Record Number:CaltechAUTHORS:20150209-131329637
Persistent URL:http://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:04 Mar 2015 16:43

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