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Polymers 2017, 9(12), 723; https://doi.org/10.3390/polym9120723

Synthesis of Isotactic-block-Syndiotactic Poly(methyl Methacrylate) via Stereospecific Living Anionic Polymerizations in Combination with Metal-Halogen Exchange, Halogenation, and Click Reactions

1
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
2
Precursory Research for Embryonic Science and Technology, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
*
Authors to whom correspondence should be addressed.
Received: 23 November 2017 / Revised: 7 December 2017 / Accepted: 14 December 2017 / Published: 16 December 2017
(This article belongs to the Special Issue Living Polymerization)
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Abstract

Isotactic (it-) and syndiotactic (st-) poly(methyl methacrylate)s (PMMAs) form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b-st-) PMMAs via stereospecific living anionic polymerizations in combination with metal-halogen exchange, halogenation, and click reactions. The azide-capped it-PMMA was prepared by living anionic polymerization of MMA, which was initiated with t-BuMgBr in toluene at –78 °C, and was followed by termination using CCl4 as the halogenating agent in the presence of a strong Lewis base and subsequent azidation with NaN3. The alkyne-capped st-PMMA was obtained by living anionic polymerization of MMA, which was initiated via an in situ metal-halogen exchange reaction between 1,1-diphenylhexyl lithium and an α-bromoester bearing a pendent silyl-protected alkyne group. Finally, copper-catalyzed alkyne-azide cycloaddition (CuAAC) between these complimentary pairs of polymers resulted in a high yield of it-b-st-PMMAs, with controlled molecular weights and narrow molecular weight distributions. The stereocomplexation was evaluated in CH3CN and was affected by the block lengths and ratios. View Full-Text
Keywords: living polymerization; stereospecific polymerization; anionic polymerization; methyl methacrylate; PMMA; stereoblock polymer; stereocomplex; click reaction; isotactic polymer; syndiotactic polymer living polymerization; stereospecific polymerization; anionic polymerization; methyl methacrylate; PMMA; stereoblock polymer; stereocomplex; click reaction; isotactic polymer; syndiotactic polymer
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).
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Usuki, N.; Satoh, K.; Kamigaito, M. Synthesis of Isotactic-block-Syndiotactic Poly(methyl Methacrylate) via Stereospecific Living Anionic Polymerizations in Combination with Metal-Halogen Exchange, Halogenation, and Click Reactions. Polymers 2017, 9, 723.

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