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Open AccessArticle

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

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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