Synthesis and properties of polyacetylenes carrying N-phenylcarbazole and triphenylamine moieties
Synthesis and properties of polyacetylenes carrying N-phenylcarbazole and triphenylamine moieties
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DOI：
10.1016/j.polymer.2006.07.064
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发表时间：
2006-09
期刊：
影响因子：
4.6
通讯作者：
Jinqing Qu;Ritsuya Kawasaki;M. Shiotsuki;F. Sanda;T. Masuda
中科院分区：
文献类型：
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作者：
Jinqing Qu;Ritsuya Kawasaki;M. Shiotsuki;F. Sanda;T. Masuda
合成了含有 N-苯基取代咔唑 (Cz) 和三苯胺 (TPA) 基团的新型乙炔单体，即 3-乙炔基-9-苯基咔唑 (1) 和对(N,N-二苯氨基)苯乙炔 (2)，并用几种 Rh、W 和 Mo 基催化剂进行聚合。当使用 [(nbd)RhCl]2–Et3N (nbd=降冰片二烯) 作为催化剂时，可以以良好的产率 (77–97%) 获得高数均分子量 (15 500–974 000) 的 Poly(1) 和 Poly(2)。该聚合物在 250-350 nm 处显示出源自 Cz 和 TPA 部分的紫外-可见吸收峰，在 350 nm 以上显示出聚乙炔主链。聚合物的紫外可见吸收带边缘波长比相应单体的吸收带边缘波长长。 Poly(2) 在比 Poly(1) 更长的波长处表现出紫外可见吸收峰，这表明 Poly(2) 的主链共轭长度比 Poly(1) 的主链共轭长度长。使用[(nbd)RhCl]2-Et3N聚合获得的聚合物的分子量和光致发光量子产率大于Rh+(nbd)[η6-C6H5B−(C6H5)3]基聚合物的分子量和光致发光量子产率。聚合物的循环伏安图表明它们具有清晰的电化学性能； Poly(1) 的起始氧化电压高于 N-烷基取代的 Cz 衍生物。这些聚合物表现出电致变色现象，并通过施加电压将颜色从浅黄色变为蓝色，这可能是由于 Cz 和 TPA 部分形成带电极化子所致。聚合物在空气中失重 5% 的温度约为 350-420°C，表明其具有较高的热稳定性。
Novel acetylene monomers containing N-phenyl-substituted carbazole (Cz) and triphenylamine (TPA) groups, namely, 3-ethynyl-9-phenylcarbazole (1) and p-(N,N-diphenylamino)phenylacetylene (2) were synthesized, and polymerized with several Rh-, W-, and Mo-based catalysts. Poly(1) and poly(2) with high number-average molecular weights (15 500–974 000) were obtained in good yields (77–97%), when [(nbd)RhCl]2–Et3N (nbd=norbornadiene) was used as a catalyst. The polymers exhibited UV–vis absorption peaks derived from the Cz and TPA moieties at 250–350nm and polyacetylene backbone above 350nm. The UV–vis absorption band edge wavelengths of the polymers were longer than those of the corresponding monomers. Poly(2) exhibited a UV–vis absorption peak at a longer wavelength than poly(1) did, which indicates that poly(2) has main chain conjugation longer than that of poly(1). The molecular weights and photoluminescence quantum yields of the polymers obtained by the polymerization using [(nbd)RhCl]2–Et3N were larger than those of the Rh+(nbd)[η6-C6H5B−(C6H5)3]-based counterparts. The cyclic voltammograms of the polymers indicated that they had clear electrochemical properties; the onset oxidation voltage of poly(1) was higher than those of N-alkyl-substituted Cz derivatives. The polymers showed electrochromism and changed the color from pale yellow to blue by application of voltage, presumably caused by the formation of charged polaron at the Cz and TPA moieties. The temperatures for 5% weight loss of the polymers were around 350–420°C under air, indicating the high thermal stability.