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Primary and Secondary Structure Control of Polymer Brushes by Surface-initiated Living/ Controlled Polymerization

Abstract

High-density well-defined polymer brushes with predictable number-average molecular weight (Mn), narrow molecular weight dispersity (MWD) were prepared by surface-initiated controlled radical polymerization or living anionic polymerization. Ion-containing monomers, such as 3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate (MAPS), was polymerized by atom transfer radical polymerization in 2,2,2-trifluoroethanol in the presence of imidazolium chloride to give the polymer with greater Mn than 2 105 g mol-1 maintaining a narrower MWD than Mw/Mn < 1.2. Neutron reflectivity measurement of poly(MAPS) brush at water interface revealed that polymer brush with narrow MWD formed relatively sharp boundary at the solution interface, while the brush with broad MWD showed a gradient solution interface due to variety of chain length. Effect of MWD on swollen chain structure was described. This article also reviews surface-initiated streospecific polymerization. High density polymethyl methacrylate (PMMA) brush with well-controlled primary structure was prepared on flat and spherical substrates using surface-initiated living anionic polymerization in the presence of triethyl aluminum. The PMMA brush so obtained showed highly controlled stereoregularity (rr > 88%). Grazing incidence wide-angle X-ray diffraction (GIWAXD) measurements indicated that the stereoregular PMMA brushes formed helical structure with about 1 nm diameter and encapsulated fullerenes in the cavities.

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Publication details

The article was received on 09 Jun 2017, accepted on 14 Jul 2017 and first published on 14 Jul 2017


Article type: Review Article
DOI: 10.1039/C7PY00956A
Citation: Polym. Chem., 2017, Accepted Manuscript
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    Primary and Secondary Structure Control of Polymer Brushes by Surface-initiated Living/ Controlled Polymerization

    T. Hirai, M. Kobayashi and A. Takahara, Polym. Chem., 2017, Accepted Manuscript , DOI: 10.1039/C7PY00956A

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