Nature polymers, such as peptides and DNAs, are composed of repeating units (i.e., amino acids, nucleobases) carrying different side groups, and the order, i.e., sequence, is perfectly programmed to express sequence-oriented functions. On the other hand, vinyl polymers, which are typical synthetic polymers, are also constructed with repeating units (i.e., vinyl monomers) carrying various side groups. However, the chain-growth mechanism (typically radical polymerization) is totally unsuitable for sequence control due to the statistical propagation.<br/>In this work, we propose a new strategy to control sequence for vinyl polymers consisting same monomer derivatives by using metal-catalyzed living radical polymerization. Crucial is design of a bulky and cleavable pendant methacrylate (<b>I</b>) as the key monomer. The bulkiness would allow control of the single monomer addition to give the halogen-ended adduct. The bulky ester pendant in the adduct can be selectively transformed into less bulky pendant on demand via acidolysis and esterification. Thus, the cycle consisting of radical addition, acidolysis, and esterification could be repeated to give sequence-controlled polymers consisting of methacrylate units.

Sequence-controlled vinyl polymers with bulky and transformable vinyl monomer

254th National Meeting (2017)

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