Employing a Two-Step Carbonylation and Condensation Approach to Expand the Scope of Hydroesterificative Polymerization

Abstract

Hydroesterificative polymerization is an atom-economical method for the synthesis of polyesters from alkenols. The implementation of hydroesterificative polymerization has predominantly focused on a single substrate, 10-undecen-1-ol, due to the multitude of potential side reactions with other substrates that prevent access to high molar mass polymers via the step-growth mechanism. This report uses a two-step carbonylation and condensation strategy to synthesize AB and AABB condensation polyesters from alkenols, alkenyl esters, and dienes. A broad range of commercially available and biobased monomers were investigated for hydroesterification by methanol. Turnover frequency (TOF) studies revealed that hydroesterification by methanol is at least twice as fast as hydroesterificative polymerization and typically leads to higher overall yields. The carbonylated monomers can be isolated via column chromatography and polymerized through condensation polymerization. In all cases, moderate to high molar mass (20–45 kDa) polyesters were isolated and characterized.