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Updated: Sep 22, 2025

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes
Published on: February 27, 2017
Living Vinyl Addition Polymerization of Substituted Norbornenes by a t-Bu3P-Ligated Methylpalladium Complex
Dong-Gyun Kim1, Andrew Bell2, Richard A Register1
1Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, United States.
Abstract:
The vinyl addition polymerization of substituted norbornene (NB) monomers, via (t-Bu3P)PdMeCl activated by [Li(OEt2)2.5]B(C6F5)4, is investigated. NB monomers bearing alkyl, aryl, fluoroaryl, and even hexafluoroisopropanol substituents yield polymers exhibiting monomodal and narrow molecular weight distributions, with molecular weight controlled by reaction time and monomer to initiator ratio, demonstrating the living nature of these polymerizations. These polymers are soluble in common organic solvents and possess excellent thermal stability. Block copolymers are also prepared via sequential monomer addition; these are the first examples of well-defined block copolymers of substituted NB monomers enchained by vinyl addition polymerization.
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