The Intrinsic Mechanochemical Reactivity of Vinyl-Addition Polynorbornene

Daniel C Lee; Victoria K Kensy; Christopher R Maroon; Brian K Long; Andrew J Boydston

doi:10.1002/anie.201900467

The Intrinsic Mechanochemical Reactivity of Vinyl-Addition Polynorbornene

Angew Chem Int Ed Engl. 2019 Apr 16;58(17):5639-5642. doi: 10.1002/anie.201900467. Epub 2019 Mar 26.

Authors

Daniel C Lee¹, Victoria K Kensy², Christopher R Maroon³, Brian K Long³, Andrew J Boydston^{2

4}

Affiliations

¹ Molecular Engineering and Sciences, University of Washington, 3946 W Stevens Way NE, Seattle, WA, 98105, USA.
² Department of Chemistry, University of Washington, Box 351700, Seattle, WA, 98195-1700, USA.
³ Department of Chemistry, University of Tennessee, 320 Buehler Hall, Knoxville, TN, 37996-1600, USA.
⁴ Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI, 53706, USA.

PMID: 30753753
DOI: 10.1002/anie.201900467

Abstract

Herein we report the discovery of the intrinsic mechanochemical reactivity of vinyl-addition polynorbornene (VA-PNB), which has strained bicyclic ring repeat units along the polymer backbone. VA-PNBs with three different side chains were found to undergo ring-opening olefination upon sonication in dilute solutions. The sonicated polymers exhibited spectroscopic signatures consistent with conversion of the bicyclic norbornane repeat units into the ring-open isomer typical of polynorbornene made by ring-opening metathesis polymerization (ROMP-PNB). Thermal analysis and evaluation of chain-scission kinetics suggest that sonication of VA-PNB results in chain segments containing a statistical mixture of vinyl-added and ROMP-type repeat units.

Keywords: chain scission; cyclopolymers; mechanochemistry; mechanoresponsive polymers; olefination.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.
Research Support, Non-U.S. Gov't

Abstract

Publication types

Grants and funding