Radical polymerization, a representative chain-growth polymerization with vinyl monomers, is used for many industrial applications, and most of the products are related to copolymers rather than homopolymers.  In such copolymers, the �averaged� composition ratio of co-monomers is statistically dependent on their monomer reactive ratios, and the sequence is ill-defined or totally random except alternating copolymerization of specific combinations.  Now that control of simple primary structural factors (i.e., chain length, terminal, etc.) is achieved with living polymerization techniques, �sequence� is a next structural factor to be controlled. Thus, we have designed �template� for molecules in metal-catalyzed living radical polymerization to control propagation-order independently of reactive ratios.1-5  In addition, our efforts were directed to how to control single monomer addition in living polymerization toward control of aperiodic sequences via the iterative cycle. (1) J. Am. Chem. Soc. 2009 , 131, 10808. (2) J. Am. Chem. Soc. 2010 , 132, 14748. (3) Macromol. Rapid Comm. 2011 , 32, 209. (3) Angew. Chem. Int. Edit. 2011 , 50, 7434. (4) Polym. Chem. 2011 , 2, 341.

Sequence-controlled vinyl polymers by chain growth control of radical species

246th National Meeting (2013)

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