Polyallene-based graft copolymer via 6-methyl-1,2-heptadien-4-ol and methyl methacrylate

A series of well-defined graft copolymers with a polyallene-based backbone and poly(methyl methacrylate) side chains were synthesized by the combination of living coordination polymerization of 6-methyl-1,2-heptadien-4-ol and atom transfer radical polymerization of methyl methacrylate. We first prepared poly(alcohol) with polyallene repeating units via 6-methyl-1,2-heptadien-4-ol by living coordination polymerization initiated by (η³-allyl)NiOCOCF₃]₂, followed by transforming the pendant hydroxyl groups into halogen-containing ATRP initiation groups. Next, grafting-from route was used for the synthesis of the well-defined graft copolymer with excellent solubility: poly(methyl methacrylate) was grafted to the backbone via ATRP of methyl methacrylate. This kind of graft copolymer is the first example of graft copolymer via allene derivative and methacrylic monomer.