Stereospecific Radical Polymerization of a Side-Chain Transformable Bulky Acrylamide Monomer and Subsequent Post-Polymerization Modification for Syntheses of Isotactic Polyacrylate and Polyacrylamide |
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Authors: | Yuehang Pan Prof Makoto Ouchi |
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Institution: | Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510 Japan |
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Abstract: | We report syntheses of isotactic polyacrylate and polyacrylamide via a stereospecific radical polymerization of a pendant-transformable monomer, acrylamide carrying isopropyl-substituted ureidosulfonamide ( 1 ), followed by post-polymerization modification (PPM). The study in the alcoholysis and aminolysis reactions of the model compound ( 2 ) for evaluation of the transformation ability of the electron-withdrawing pendant group on the repeating unit 1 revealed the following points: the pendant of the polymer became more reactive than that of monomer; the pendant was active enough for aminolysis reaction affording the amide compound quantitatively without additive/catalyst; the addition of a lithium triflate Li(OTf)] and triethylamine (Et3N) was effective as for promotion of the alcoholysis reaction. Poly(methyl acrylate) (PMA) was quantitatively obtained via the radical polymerization of 1 in the presence of Li(OTf) at 60 °C and the subsequent addition of methanol along with Et3N. Thus-obtained PMA showed higher isotacticity m=74 %] than that directly obtained via radical polymerization of methyl acrylate (MA) (m=51 %). The isotacticity was further increased as the temperature and monomer concentration were lower, and eventually m was increased up to 93 %. The aminolysis PPM after the iso-specific radical polymerization of 1 gave various isotactic polyacrylamides carrying different alkyl pendant groups, including poly(N-isopropylacrylamide) (PNIPAM). |
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Keywords: | Acrylamide Isotactic Post-Polymerization Modification Radical Polymerization Tacticity |
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