TY - JOUR
T1 - Control of the primary and secondary structure of polymer brushes by surface-initiated living/controlled polymerization
AU - Hirai, Tomoyasu
AU - Kobayashi, Motoyasu
AU - Takahara, Atsushi
N1 - Funding Information:
The neutron reflectivity measurements were performed under the S-type research project (proposal no. 2008S) of the High Energy Accelerator Research Organization (KEK) and M. K. appreciates Dr N. L. Yamada for technical support and improvement in the operation system for the Sofia reflectometer. This work was also supported by the Photon and Quantum Basic Research Coordinated Development Program from the Ministry of Education, Culture, Sports, Science and Technology, Japan. We also acknowledge support from the World Premier International Research Center Initiative (WPI) MEXT, Japan, and the Cooperative Research Program of “Network Joint Research Center for Materials and Devices”. Part of this work was supported by the Impulsing Paradigm Change through Disruptive Technologies (ImPACT) Program. The GIWAXD measurements were performed at the BL40B2 beamline of SPring-8 under proposals 2013B1171, 2014A1222, 2014B1286, 2015A1584, 2015B2288, 2016A1272, and 2016B1227.
Publisher Copyright:
© The Royal Society of Chemistry 2017.
PY - 2017/9/28
Y1 - 2017/9/28
N2 - Characterization of the molecular structure of high-density well-defined polymer brushes with predictable number-average molecular weight (Mn), narrow molecular weight dispersity (MWD), and highly ordered tacticity, prepared by surface-initiated controlled radical polymerization or living anionic polymerization, is described. Ionic monomers, such as 3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate (MAPS), were polymerized by atom transfer radical polymerization in 2,2,2-trifluoroethanol in the presence of imidazolium chloride to give a polymer with Mn greater than 2 × 105 g mol-1 maintaining a narrower MWD (Mw/Mn < 1.2). Neutron reflectivity measurement of poly(MAPS) (PMAPS) brushes at the water interface revealed that polymer brushes with narrow MWD form a relatively sharp boundary at the solution interface, while brushes with a broad MWD show a gradient solution interface due to the variety of chain length. The effect of MWD on swollen chain structure is described. This article also reviews surface-initiated stereospecific polymerization. High density poly(methyl methacrylate) (PMMA) brushes with well-controlled primary structures were prepared on flat and spherical substrates using surface-initiated living anionic polymerization in the presence of triethyl aluminum. The PMMA brushes 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 structures with about 1 nm diameter and encapsulated fullerenes in the cavities.
AB - Characterization of the molecular structure of high-density well-defined polymer brushes with predictable number-average molecular weight (Mn), narrow molecular weight dispersity (MWD), and highly ordered tacticity, prepared by surface-initiated controlled radical polymerization or living anionic polymerization, is described. Ionic monomers, such as 3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate (MAPS), were polymerized by atom transfer radical polymerization in 2,2,2-trifluoroethanol in the presence of imidazolium chloride to give a polymer with Mn greater than 2 × 105 g mol-1 maintaining a narrower MWD (Mw/Mn < 1.2). Neutron reflectivity measurement of poly(MAPS) (PMAPS) brushes at the water interface revealed that polymer brushes with narrow MWD form a relatively sharp boundary at the solution interface, while brushes with a broad MWD show a gradient solution interface due to the variety of chain length. The effect of MWD on swollen chain structure is described. This article also reviews surface-initiated stereospecific polymerization. High density poly(methyl methacrylate) (PMMA) brushes with well-controlled primary structures were prepared on flat and spherical substrates using surface-initiated living anionic polymerization in the presence of triethyl aluminum. The PMMA brushes 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 structures with about 1 nm diameter and encapsulated fullerenes in the cavities.
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U2 - 10.1039/c7py00956a
DO - 10.1039/c7py00956a
M3 - Review article
AN - SCOPUS:85029747514
SN - 1759-9954
VL - 8
SP - 5456
EP - 5468
JO - Polymer Chemistry
JF - Polymer Chemistry
IS - 36
ER -