We report recent advances in the synthesis, characterization, and functions of functional star and single-chain polymers via living radical polymerization, especially focusing on the precision space/chain design for unique functions.(A) Functional microgel star polymers were synthesized by arm-linking reactions with functional linkers and monomers: 1) star polymers with multi-functional (fluorous/amine) microgels for selective/efficient capture and stimuli-responsive release of polyfluorinated surfactants via cooperative recognition in water; 2) star polymers with self-assembly linkers for the creation of higher-order supramolecular structures within microgels; 3) arm-cleavable star polymers for the isolation and characterization of microgels.Macromolecules 2011  , 44, 4574; ACS symposium series 2012  , 1101, 65(B) Single-chain folding polymers  were obtained from amphiphilic random copolymers that undergo self-folding in water via intramolecular hydrophobic/hydrogen-bonding interaction. Similarly, single-chain patched polymers were obtained from these random copolymers but with pendent olefins by crosslinking on self-folded precursors. Folding properties and structures were investigated in detail to create precision functional spaces.J. Am. Chem. Soc. 2011  , 133, 4742; Macromolecules 2014  , 47, 589(C) Functional gradient copolymers were obtained in one-pot via a tandem catalysis that synchronized ruthenium-catalyzed living radical polymerization and metal alkoxide-mediated transesterification of methacrylates with alcohols. The high controllability and versatility of the catalysis led to functionalized gradient copolymers of complex sequence (random gradient, gradient block) exhibiting unique physical properties.J. Am. Chem. Soc. 2012  , 134, 4373; ACS Macro Lett. 2013  , 2, 985 

Functional star and single-chain polymers via living radical polymerization: From precision space/chain design to functions

248th National Meeting (2014)

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