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.