Suppression of Chain Transfer in Catalytic Acrylate Polymerization via Rapid and Selective Secondary Insertion

In catalytic copolymerization, undesired
chain transfer after incorporation
of a polar vinyl monomer is a fundamental problem. We show an approach
to overcome this problem by a fast consecutive insertion. The second
double bond of acrylic anhydride rapidly inserts intramolecularly
to regio- and stereoselectively form a cyclic repeat unit and a primary
alkyl favorable for chain growth (>96%). This results in significantly
enhanced copolymer molecular weights vs monofunctional acrylate monomers.