T. Yokozawa, I. Adachi, Ryo Miyakoshi
Oct 1, 2007
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Journal
High Performance Polymers
Abstract
Chain-growth condensation polymerization of 2-bromo-5-chloromagnesio-3-[2-(2-metho-xyethoxy)ethoxy]methylthiophene (2) with Ni catalysts was studied, and the block copolymer of poly2 and poly(3-hexylthiophene) was synthesized by this polymerization method. The polymerization of 2 depended on the ligands of the Ni catalyst, and poly2 with the lowest polydispersity was obtained when 1,2-bis(diphenylphosphino)ethane (dppe) was used as the ligand. The linear relationships between the conversion of 2 and Mn of the polymer and between the feed ratio of 2 to the Ni catalyst and Mn of the polymer indicate that this polymerization proceeds in a chain-growth polymerization manner via a catalyst-transfer condensation polymerization mechanism. The block copolymerization of 2 and 2-bromo-5-chloromagnesio-3-hexylthiophene (1) was then carried out in four ways by changing the order of polymerization of the two monomers and the catalysts. It turned out that the block copolymer was obtained without the formation of the homopolymers by the polymerization of 1 with Ni(dppe)Cl2 or Ni(dppp)Cl2 (dppp = 1,2-bis(diphenylphosphino)propane), followed by the postpolymerization of 2. Of the two catalysts, Ni(dppe)Cl2 resulted in narrower polydispersity of the block copolymer.