Synthesis, gas permeability, and metal-induced gelation of poly(diphenylacetylene)s having p,m-dimethoxy and p,m-dihydroxy groups
Synthesis, gas permeability, and metal-induced gelation of poly(diphenylacetylene)s having p,m-dimethoxy and p,m-dihydroxy groups
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具有对，间二甲氧基和对，间二羟基的聚二苯乙炔的合成、透气性和金属诱导凝胶化
DOI：
10.1016/j.polymer.2014.03.007
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发表时间：
2014
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;T. Tsuzuki;T. Masuda;T. Hashimoto
具有三甲基甲硅烷基和两个甲氧基的二苯基乙炔[p-（CH 3）3 SiC 6 H 4 C三键CC 6 H 4-m，p-（OCH 3）2（1a）]用TaCl 5/n-Bu 4 Sn催化剂聚合，得到高分子量聚合物（2a）。相反，不含三甲基甲硅烷基的单体（1b）和具有二丁基二甲基甲硅烷氧基的单体（1c）几乎不聚合，因为所产生的聚合物2的溶解性差，具有1c的空间位阻。2a经CF 3COOH脱硅得到高分子量聚合物3a。用AlCl_3裂解3a膜中的甲氧基，合成了具有一定程度（4a：40%; 4 b：90%）的p，m-二羟基苯基的膜。膜4表现出较高的CO2选择透过性，而膜5a太脆。聚合物2a和3在CHCl 3和THF中完全溶解，加入TaCl 5、AlCl 3等金属氯化物后，溶液变成凝胶，加入少量甲醇后凝胶又恢复成溶液。这表明2a和3a通过金属-配体相互作用形成非共价分子间键。
Diphenylacetylene having a trimethylsilyl group and two methoxy groups [p-(CH3)3SiC6H4Ctriple bondCC6H4-m,p-(OCH3)2(1a)] polymerized with TaCl5/n-Bu4Sn catalyst to provide a high-molecular-weight polymer (2a). In contrast, monomers without trimethylsilyl group (1b) and having twot-butyldimethylsiloxy groups (1c) hardly polymerized because of poor solubility of the produced polymer2band steric hindrance of1c. Polymer3awith high molecular weight was obtained by desilylation of2ausing CF3COOH. Membranes havingp,m-dihydroxyphenyl groups to certain degrees (4a: 40%;4b90%) were synthesized by cleavage of methoxy groups in the membrane of3ausing AlCl3. Membrane4ashowed high CO2permselectivity, while membrane5awas too brittle. Polymers2aand3atotally dissolved in CHCl3and THF, and their solutions turned into gels upon addition of metal chlorides such as TaCl5, AlCl3, etc. The gels returned to solutions by adding a small amount of methanol. This indicates that2aand3aform non-covalent intermolecular bonds through metal–ligand interaction.