Controlled polymerization of methyl acrylate for high-molecular-weight polymers by pentafluorophenylbis(triflyl)methane-promoted group transfer polymerization using triisopropylsilyl-ketene acetal
Controlled polymerization of methyl acrylate for high-molecular-weight polymers by pentafluorophenylbis(triflyl)methane-promoted group transfer polymerization using triisopropylsilyl-ketene acetal
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使用三异丙基甲硅烷基乙烯酮乙缩醛通过五氟苯基双(三氟甲基)甲烷促进的基团转移聚合控制丙烯酸甲酯聚合以获得高分子量聚合物
DOI：
10.1002/pola.26140
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发表时间：
2012
期刊：
影响因子：
--
通讯作者：
高田健司
中科院分区：
文献类型：
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作者：
角本貴進;寺島俊雄;吉川知志;高田健司
以五氟苯基双（三氟甲磺酰基）甲烷（C6 F5 CHTf 2）为催化剂，以1-三甲基硅氧基-、1-三乙基硅氧基-和1-三异丙基硅氧基-1-甲氧基-2-甲基-1-丙烯（MTSMe、MTSEt和MTSiPr）为引发剂，研究了丙烯酸甲酯（MA）的基团转移聚合（GTP）.使用MTSiPr的C6 F5 CHTf 2促进的MA的GTP在活性性质下进行以产生具有受控分子量和窄分子量分布的聚（丙烯酸甲酯）（PMA），这允许合成具有高达108，000的数均分子量（Mn（SEC））和1.07的多分散性（Mw/Mn）的高分子量PMA。基质辅助激光解吸/电离飞行时间质谱测量显示，所获得的PMA具有源自MTSiPr的链端结构，表明C6 F5 CHTf 2促进的MA的GTP在没有任何副反应的情况下进行。此外，动力学研究和后聚合实验支持了聚合的活性方式。此外，MA和丙烯酸正丁酯（nBA）的嵌段共聚顺利进行，得到了结构明确的PMA-嵌段-聚（丙烯酸正丁酯）（PnBA）。© 2012 Wiley Periodicals，Inc. J Polym Sci Part A：Polym Chem，2012
The group transfer polymerization (GTP) of methyl acrylate (MA) was studied using pentafluorophenylbis(triflyl)methane (C6F5CHTf2) as the organocatalyst and 1‐trimethylsiloxy‐, 1‐triethylsiloxy‐, and 1‐triisopropylsiloxy‐1‐methoxy‐2‐methyl‐1‐propene (MTSMe, MTSEt, and MTSiPr, respectively) as the initiators. The C6F5CHTf2‐promoted GTP of MA using MTSiPrproceeded in a living nature to produce poly(methyl acrylate)s (PMAs) with controlled molecular weights and narrow molecular weight distributions, which allowed the synthesis of high‐molecular‐weight PMA with the number‐average molecular weight (Mn(SEC)) of up to 108,000 and the polydispersity (Mw/Mn) of 1.07. The matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry measurement revealed that the obtained PMA possessed the chain end structure that originated from MTSiPr, showing that the C6F5CHTf2‐promoted GTP of MA proceeded without any side reactions. In addition, the kinetic study and the postpolymerization experiment supported the living manner of the polymerization. Moreover, the block copolymerization of MA andn‐butyl acrylate (nBA) smoothly proceeded to afford the well‐defined PMA‐block‐poly(n‐butyl acrylate) (PnBA). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012