Atom Transfer Radical Polymerization of Poly(vinyl ether) Macromonomers

The present paper focuses on the atom transfer radical polymerization (ATRP) of vinyl ether (VE) based macromonomers with a methacryloyl group at the chain end. Living cationic polymerization of isobutyl VE (IBVE) initiated with the HCl adduct of a VE carrying a pendant methacryloyl group in conjunction with ZnI 2 yielded the macromonomer (MA-PIBVE) with a narrow molecular weight distribution (MWD) ( M̄ w / M̄ n < 1.1). The ATRP of MA−PIBVE was carried out using a halide initiator and the CuBr/4,4‘-di- n -heptyl-2,2‘-bipyridine catalytic system. The number-average molecular weight of the polymacromonomer increased in proportion to the monomer conversion, while the MWDs stayed fairly narrow ( M̄ w / M̄ n ∼ 1.2). Thus a novel type of polymacromonomers with controlled chain lengths for both the backbone and the side chain have been synthesized through a combination of living cationic polymerization and ATRP techniques.