Strong Brønsted Acid as a Highly Efficient Promoter for Group Transfer Polymerization of Methyl Methacrylate
Strong Brønsted Acid as a Highly Efficient Promoter for Group Transfer Polymerization of Methyl Methacrylate
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DOI：
10.1021/ma902006d
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发表时间：
2009-10
期刊：
影响因子：
5.5
通讯作者：
R. Kakuchi;K. Chiba;Keita Fuchise;R. Sakai;T. Satoh;T. Kakuchi
中科院分区：
文献类型：
--
作者：
R. Kakuchi;K. Chiba;Keita Fuchise;R. Sakai;T. Satoh;T. Kakuchi
三氟甲磺酰亚胺（HNTf 2）是一种高效的甲基丙烯酸甲酯（MMA）基团转移聚合（GTP）活化剂。以1-甲氧基-1-三甲基硅氧基-2-甲基丙烯（MTS）为引发剂，HNTf 2催化的甲基丙烯酸甲酯（MMA）的GTP反应以活性方式进行，合成了分子量可控、分子量分布窄的聚甲基丙烯酸甲酯（PMMA）。动力学测试和后聚合实验进一步证实了聚合反应是以活性方式进行的。此外，从MALDI-TOF MS分析中，仅观察到一系列峰，这与具有MTS引发剂残基和脱甲硅烷基化链端的PMMA的分子量完全一致，表明HNTf 2催化的MMA的GTP在没有任何副反应的情况下进行。HNTf 2催化GTP合成的PMMA的间同立构规整度随聚合温度的降低而增加，间同立构规整度随聚合温度的降低而降低。
The Bronsted acid, trifluoromethanesulfonimide (HNTf2), was revealed to act as a highly efficient activator for group transfer polymerization (GTP) of methyl methacrylate (MMA) at ambient temperature. The HNTf2-catalyzed GTP of MMA initiated by 1-methoxy-1-trimethylsilyloxy-2-methyl-propene (MTS) proceeded in a living manner to produce poly(methyl methacrylate)s (PMMA) with controlled molecular weights and narrow molecular weight distributions. Kinetic measurement and postpolymerization experiment further supported that the polymerization proceeded in a living fashion. Furthermore, from the MALDI-TOF MS analysis, only one series of peaks was observed, which was in perfect agreement with the molecular weight of PMMA possessing the MTS initiator residue and the desilylated chain end, showing that the HNTf2-catalyzed GTP of MMA proceeded without any side reactions. The syndiotacticity of the PMMA obtained by the HNTf2-catalyzed GTP increased with the decreasing polymerization temperature; the syndiotactic (r...