Polyolefins Derived from 5-Vinyl-2-norbornene as Platforms for Functional Polymers

Abstract 5-Vinyl-2-norbornene (VNB) is a cyclic olefin monomer containing a norbornenyl double bond and a vinyl double bond. Selective insertion of the norbornenyl double bond during the Ziegler–Natta homopolymerization and copolymerization of VNB produces polyolefins bearing pendant vinyl groups available for subsequent chemical transformation. This review surveys previous studies on the synthesis and postpolymerization modification of VNB-derived polyolefins. Particular attention is given to the relationships between synthetic methodologies and polymer molecular structures, including molar mass, molar mass distribution, copolymer composition, preservation of pendant vinyl groups, and postpolymerization modification efficiency. On the basis of these findings, key synthetic requirements for developing model polymers that are capable of revealing intrinsic structure–property relationships are discussed. These include living polymerization with complete chemoselectivity, programmable control of monomer sequence distribution, and expanded functionalization methodologies. These capabilities would provide independent control of molar mass, topology, composition, and chemical functionality. This review is intended to highlight the potential of VNB-derived polyolefins as platforms for the development of model polymers that contribute to the understanding of polymer structure–property relationships and the rational design of high-performance applied polymer materials.