A series of poly(diphenylacetylene)s bearing sulfonic acids : synthesis, characterization, and gas permeability
A series of poly(diphenylacetylene)s bearing sulfonic acids : synthesis, characterization, and gas permeability
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一系列含磺酸的聚（二苯乙炔）：合成、表征和透气性
DOI：
10.1016/j.polymer.2012.09.017
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发表时间：
2012
期刊：
影响因子：
4.6
通讯作者：
T. Hashimoto
中科院分区：
文献类型：
--
作者：
T. Sakaguchi;Y. Shinoda;T. Hashimoto
一系列二苯乙炔衍生物[(CH3)3SiC6H4CCC6H4R]；R = H(1)、甲基(1 b) n-C4H9 (1 c) n-C8H17 (1 d) PhC≡CC6H4R;合成R = CH3(2b), n-C4H9(2c), n-C8H17(2d), t-C4H9(2e)]，然后与TaCl5/n-Bu4Sn聚合得到相应的聚二苯乙炔s （3a-d和4b-e）。用乙酰硫酸酯磺化这些聚二苯乙炔，得到磺化聚二苯乙炔s （5a-d和6b-e）。除6b外，对磺化聚合物的甲醇溶液进行滴定，发现磺化度在1.0左右。磺化聚合物5a具有最低的透气性和最高的co2选择性。5b、5c、5d渗透率系数依次增大。烷基的存在会稀释磺酸的作用，并通过位阻减弱分子间的相互作用。具有正丁基和正丁基（6c和6e）的磺化聚（二苯乙炔）对co2的选择性几乎相同，但对co2的渗透性却大不相同。在含磺酸的聚二苯乙炔中，体积较大的球形t-丁基比线性正丁基更能有效地阻止分子间相互作用。
A series of diphenylacetylene derivatives [(CH3)3SiC6H4CCC6H4R; R=H (1a), CH3(1b), n-C4H9(1c), n-C8H17(1d), PhC≡CC6H4R; R = CH3(2b), n-C4H9(2c), n-C8H17(2d), t-C4H9(2e)] were synthesized and then polymerized with TaCl5/n-Bu4Sn to afford the corresponding poly(diphenylacetylene)s (3a–d and 4b–e). These poly(diphenylacetylene)s were sulfonated using acetyl sulfate, which gave the sulfonated poly(diphenylacetylene)s (5a–d and 6b–e). Except 6b, the degrees of sulfonation were found to be around 1.0 from the titration of methanol-solutions of sulfonated polymers. Sulfonated polymer 5a exhibited the lowest gas permeability and the highest CO2permselectivity among the present polymers. The gas permeability coefficients of 5b, 5c, and 5d became lager in this order. The presence of alkyl groups would dilute the effect of sulfonic acid and weak the intermolecular interaction by the steric hindrance. Sulfonated poly(diphenylacetylene)s having n-butyl and t-butyl groups (6c and 6e) showed almost the same CO2permselectivity, while they showed quite different CO2permeability. The spherical bulky t-butyl groups more effectively prevent the intermolecular interaction than the linear n-butyl groups in sulfonic acid-containing poly(diphenylacetylene)s.