Synthesis and properties of various poly(diphenylacetylenes) containing tert-amine moieties

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• 作者：Toru Katsumata ; Masaki Maitani ; Ching-Cheng Huang ; Masashi Shiotsuki ; Toshio Masuda
• 关键词：Substituted polyacetylene ; Transition metal catalyst ; Gas permeability
• 刊名：Polymer
• 出版年：2008
• 期刊代码：83_00323861
• 类别：ms
• 出版时间：10 June 2008
• 卷：49
• 期：12
• 页码：2808-2816
• 文件大小：1170 K

摘要

The polymerization of diphenylacetylene derivatives possessing tert-amine moieties, such as triphenylamine, N-substituted carbazole and indole, was examined in the presence of TaCl₅–n-Bu₄Sn (1:2) catalyst. A polymer with high molecular weight (M_w = 570 × 10³) was obtained in good yield by the polymerization of diphenylamine-containing monomer 1b, whereas the isopropylphenylamine derivative (1c) gave a polymer with relatively low molecular weight (M_w = 2.4 × 10³). The polymerization of monomer 1d containing cyclohexylphenylamine group did not proceed; however, carbazolyl- and indolyl-containing monomers also produced polymers. Poly(1b), poly(2f) and poly(4b) could be fabricated into free-standing membranes by casting toluene solutions of these polymers. The gas permeability of poly(1b) was too low to be evaluated accurately whereas poly(4b) possessing two chlorine atoms in the repeating unit showed higher gas permeability than that of poly(1b); furthermore, poly(2f) having trimethylsilyl and 3-methylindolyl groups exhibited relatively high gas permeability (). In the cyclic voltammograms of diphenylamino group-containing polymers, poly(1b) and poly(2b), the intensities of oxidation and reduction peaks decreased more than those of carbazolyl-containing poly(2a). The molar absorptivity () of poly(1b) at 700 nm increased with increasing applied voltage in the UV–vis spectrum.