Block copolymerization of allene derivatives with 1,3-butadiene by living coordination polymerization with pi-allylnickel catalyst

The block copolymerization of allene derivatives (3A-3D) with 1,3-butadiene (2) by [(allyl)NiOCOCF3](2) (1) is described. For instance, the living coo rdination polymerization of phenylallene (3A, 50 equiv) starting From the l iving poly(2), which was prepared by the polymerization of 2 (160 equiv) by 1, successfully gave a block copolymer of 2 and 3A in high yield. The mole cular weight of the block copolymer (4A) in gel permeation chromatography s hifted clearly to the higher molecular weight region and kept a unimodal di stribution (M-n = 17,400, M-w/M-n = 1.23) in comparison with that of the st arting living poly(2) (M-n = 5,600, M-w/M-n = 1.67). The ratio of each segm ent and the molecular weight of the resulting copolymers could be controlle d by the feed ratio of each monomer. The block copolymerization also procee ded successfully by the inverse order of the monomer feeding (i.e., the pol ymerization of 3A followed by that of 2) to obtain the corresponding block copolymers in high yields. (C) 1999 John Wiley & Sons, Inc.