Synthesis of poly(diphenylacetylene)s bearing various polar groups and their gas permeability
Synthesis of poly(diphenylacetylene)s bearing various polar groups and their gas permeability
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带有不同极性基团的聚二苯乙炔的合成及其透气性
DOI：
10.1038/pj.2014.16
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发表时间：
2014
期刊：
影响因子：
--
通讯作者：
T. Hashimoto
中科院分区：
文献类型：
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作者：
T. Sakaguchi;T. Hashimoto
具有二异丙基苯氧基甲硅烷基、2-溴乙氧基、三甲基甲硅烷基和叔丁基的二苯基乙炔（p-PhOSi（i-Pr）2 C6 H4 C = C6H4-p-SiMe 3（1a），p-（BrCH2CH2O）C6H4C_（20）C6H4-p-SiMe 3（1b），PhC_（20）C6H4-p-SiMe 3（1c），PhC = C6 H4-p-t-Bu（1d））进行聚合，得到相应的聚（二苯基乙炔）（2a-d）。用n-Bu 4 N+ F−处理2a的膜，得到硅烷醇官能化的聚（二苯基乙炔）（3a）。傅立叶变换红外光谱分析表明，聚合物3a中的硅醇基团被消耗，通过硅氧烷键交联。3a的膜表现出非常高的气体渗透性，与极性硅烷醇基团的存在无关。将1-甲基咪唑取代到2b的膜上得到含咪唑盐的聚（二苯基乙炔）（3b（Br−））。用CF 3COOK和（CF 3SO 2）2NLi处理膜，可以交换3b（Br-）的抗衡阴离子，得到3b（TFAc-）和3b（Tf 2N-）膜. 1-甲基咪唑的引入显著提高了选择性（P CO_2/P N_2 = 31-44）。3b（Br−）、3b（TFAC−）和3b（Tf 2 N−）的P CO2值分别为11、23和53 barrers，表明CO2渗透性随着抗衡阴离子体积增大而增加。聚合物2c和2d使用乙酰基硫酸酯磺化以得到磺化聚（二苯基乙炔）（3c和3d）。聚合物3c具有较高的CO2选择透过性，其P CO2/P N2高达54。具有叔丁基的聚合物3d显示出180巴的相对大的P CO2和30的P CO2/P N2。
Diphenylacetylenes having a diisopropylphenoxysilyl, 2-bromoethoxy, trimethylsilyl and t-butyl groups (p-PhOSi (i-Pr) 2 C 6 H 4 C≡ CC 6 H 4-p-SiMe 3 (1a), p-(BrCH 2 CH 2 O) C 6 H 4 C≡ CC 6 H 4-p-SiMe 3 (1b), PhC≡ CC 6 H 4-p-SiMe 3 (1c), PhC≡ CC 6 H 4-p-t-Bu (1d)) were polymerized to provide the corresponding poly (diphenylacetylene) s (2a–d). Treatment of the membrane of 2a with n-Bu 4 N+ F− gave silanol-functionalized poly (diphenylacetylene)(3a). Fourier transform-infrared spectroscopy spectrum of 3a revealed that some silanol groups were consumed and the polymer was crosslinked via siloxane bond. The membrane of 3a exhibited very high gas permeability irrespective of the presence of polar silanol groups. Substitution of 1-methylimidazole to the membrane of 2b afforded an imidazolium salt-containing poly (diphenylacetylene)(3b (Br−)). Counteranions of 3b (Br−) could be exchanged by the treatment of the membrane with CF 3 COOK and (CF 3 SO 2) 2 NLi, and membranes of 3b (TFAc−) and 3b (Tf 2 N−) were obtained. Introduction of 1-methylimidazole remarkably increased the selectivity (P CO2/P N2= 31–44). The P CO2 values of 3b (Br−), 3b (TFAc−) and 3b (Tf 2 N−) were 11, 23 and 53 barrers, respectively, indicating that the CO 2 permeability increased as the counteranion became bulkier. Polymers 2c and 2d were sulfonated using acetyl sulfate to give sulfonated poly (diphenylacetylene) s (3c and 3d). Polymer 3c exhibited high CO 2 permselectivity, and the P CO2/P N2 was as large as 54. Polymer 3d with t-butyl groups showed relatively large P CO2 of 180 barrers and P CO2/P N2 of 30.