Arm-first synthesis of star polymers with polywedge arms using ring-opening metathesis polymerization and bifunctional crosslinkers

Robert Learsch, Garret M. Miyake

Index: 10.1002/pola.28946

Full Text: HTML

Abstract

ABSTRACT This work presents a two-step, one-pot process to make star polymers with polywedge arms. In a one-pot reaction, after the polywedge arms are synthesized, crosslinker species are added to the reaction, rapidly forming star polymers. Crosslinker species with different degrees of conformational freedom were designed and synthesized and their capacity to generate star polymers was evaluated. Mass conversions up to 92% and stars with up to 17 arms were synthesized with the most rigid crosslinker. The effects of arm molecular weight and molar ratio of crosslinker to arm on mass conversion and arms per star were explored further. Finally, the size-molecular weight scaling relationship for polywedges with linear and star architectures was compared, corroborating theoretical results regarding star polymers with arms much larger than their core. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018. Crosslinkers with varying rigidity are synthesized and their ability to form star polymers from rigid, linear, high molecular weight polymer arms is investigated. The conformation of linear homopolymers and star polymers is analyzed and theoretical predictions are confirmed.