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• W2080496042 endingPage "4148" @default.
• W2080496042 startingPage "4140" @default.
• W2080496042 abstract "Radical coupling reactions have been widely used for preparation of symmetrical macromolecules. In previous studies of atom transfer radical coupling (ATRC), coupling efficiency above 90% has been generally attained at high temperature (T = 70–110 °C) by using Mn < 5000 precursors. From the mechanistic viewpoint, we designed a strategy for styrene-assisted ATRC from methacrylic macroradicals at low temperature (St/PMMA–Br/CuIBr/Cu0/Me6TREN). Analysis of the products (1H NMR, H–H COSY, MALDI–TOF mass spectra and gel permeation chromatography) indicated that this provides an efficient “convergent” or coupling approach, if a high degree of chain-end functionality is preserved. We then applied this concept in combination with chain-growth condensation polymerization (CGCP), which usually affords quantitative chain-end functionality. Couplings of high-molecular-weight AB-type diblock polybenzamide, 2-bromoisobutyryl-terminated poly(N-octyloxybenzyl-m-benzamide)-block-poly(N-octyl-m-benzamide) (Mn = 9300, Mw/Mn = 1.09), were conducted to yield ABA-type triblock polybenzamides with high coupling efficiency (>94%). The molecular weight (Mn ∼ 18000) was doubled and a narrow molecular weight distribution (Mw/Mn < 1.18) was maintained. Selective removal of the octyloxybenzyl groups was achieved, resulting in a poly(N-H-m-benzamide) segment (i.e., A block). Thermal transitions of the diblock and triblock polybenzamides were examined by DSC. In the case of triblock polybenzamides, the Tg value shifted from 45 to 62 °C after removal of the octyloxybenzyl groups; this might be ascribed to a confinement effect of the segments at the extremities via strong intermolecular hydrogen-bonding interaction." @default.
• W2080496042 created "2016-06-24" @default.
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• W2080496042 date "2011-05-12" @default.
• W2080496042 modified "2023-10-18" @default.
• W2080496042 title "Efficient Low-Temperature Atom Transfer Radical Coupling and Its Application to Synthesis of Well-Defined Symmetrical Polybenzamides" @default.
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• W2080496042 doi "https://doi.org/10.1021/ma200494m" @default.
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