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Molecular Weight Control via Cross Metathesis in Photo‐Redox Mediated Ring‐Opening Metathesis Polymerization
Author(s) -
Kensy Victoria K.,
Tritt Rachel L.,
Haque Farihah M.,
Murphy Laura M.,
Knorr Daniel B.,
Grayson Scott M.,
Boydston Andrew J.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202000434
Subject(s) - romp , norbornene , polymerization , ring opening metathesis polymerisation , metathesis , redox , polymer chemistry , chemistry , copolymer , chain transfer , acyclic diene metathesis , ring opening polymerization , combinatorial chemistry , organic chemistry , radical polymerization , polymer
Photo‐redox mediated ring‐opening metathesis polymerization (photo‐ROMP) is an emerging ROMP technique that uses an organic redox mediator and a vinyl ether initiator, in contrast to metal‐based initiators traditionally used in ROMP. The reversibility of the redox‐mediated initiation and propagation steps enable spatiotemporal control over the polymerization. Herein, we explore a simple, inexpensive means of controlling molecular weight, using alpha olefins as chain transfer agents. This method enables access to low molecular weight oligomers, and molecular weights between 1 and 30 kDa can be targeted simply by altering the stoichiometry of the reaction. This method of molecular weight control was then used to synthesize a functionalized norbornene copolymer in a range of molecular weights for specific materials applications.