Synthesis of cyclopolyolefins via ruthenium catalyzed ring-expansion metathesis polymerization

Abstract

Polymers exhibiting cyclic topology have attracted great interest over the past 30 years. Macrocycles or cyclopolymers with more than 20 repeating monomer units are considered exceptional candidates for thermoplastic engineering application due to unique properties in comparison to their linear analogues including large hydrodynamic radii and functional group density, heat resistance, good insulating ability and low intrinsic viscosity. Cyclic polymers are thus expected to exhibit improved physical and mechanical properties for certain applications due to the absence of end groups. Although synthetic challenges have historically limited research on cyclic polymers, recent developments in ruthenium catalyzed ring-expansion metathesis polymerization (REMP) have enabled the synthesis and the preliminary investigation of structure-property relationships of high molecular weight macrocycles. In REMP reactions the polymer formation is proposed to proceed through a transient macrocyclic complex in which both ends of the growing polymer chain remain attached to the Ru center. This article summarizes the recent discoveries on the field of REMP assisted cyclopolymer based material development.