Synthesis and photoluminescence properties of heterocycle-containing poly(disubstituted acetylene)s
Synthesis and photoluminescence properties of heterocycle-containing poly(disubstituted acetylene)s
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DOI：
10.1016/j.polymer.2012.08.009
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发表时间：
2012-09
期刊：
影响因子：
4.6
通讯作者：
T. Muroga;T. Sakaguchi;T. Hashimoto
中科院分区：
文献类型：
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作者：
T. Muroga;T. Sakaguchi;T. Hashimoto
研究了含噻吩、呋喃、苯并[B]噻吩和苯并噻唑等杂环的二取代乙炔在NbCl 5、TaCl 5和WCl 6存在下的复分解聚合反应。含噻吩的单体聚合得到相对高分子量的聚合物，产率适中。含苯并[B]噻吩的单体也聚合得到具有相对高分子量的聚合物。另一方面，含呋喃和苯并噻唑的单体表现出低的复分解可聚合性，并且聚合不提供高分子量聚合物。具有杂环的聚（1-己基-2-芳基乙炔）[聚（1a）和聚（3a），方案1]发射蓝色光，并且发射最大值在480 nm附近。含杂环的聚（1-苯基-2-芳基乙炔）[poly（1b）]和聚（1-芴基-2-芳基乙炔）[poly（3d）]显示出绿色和黄色的发射，最大发射波长分别为520和540 nm。含杂环的聚二取代乙炔的发射波长与相应的不含杂环的聚二取代乙炔的发射波长几乎相同。然而，含杂环的聚合物显示出高的荧光量子产率相比，相应的聚合物没有杂环。二芳基乙炔聚合物的溶液和流延膜之间的发射红移，而在流延膜中的聚（1-己基-2-苯乙炔）[聚（1a）]的发射最大值几乎是相同的，在溶液中。含苯并[B]噻吩的聚（1-（4-三甲基硅基苯基）-2-苯乙炔）[poly（3B）]和聚（1-（9，9-二甲基-2-芴基）-2-苯乙炔）[poly（3d）]由于其高分子量而提供自支撑膜。聚（3b）的氧渗透系数（PO 2）高达1400巴。Poly（3d）具有较高的透气性，其PO 2为5300 barrers。
The metathesis polymerizations of disubstituted acetylenes containing heterocycles such as thiophene, furan, benzo[b]thiophene, and benzothiazole were examined using NbCl5, TaCl5, and WCl6. Thiophene-containing monomers polymerized to afford relatively high-molecular-weight polymers in moderate yields. Benzo[b]thiophene-containing monomers also polymerized to give polymers with relatively high molecular weights. On the other hand, furan- and benzothiazole-containing monomers exhibited low metathesis polymerizability, and the polymerizations did not provide high-molecular-weight polymers. Poly(1-hexyl-2-arylacetylene)s having heterocycles [poly(1a) and poly(3a), Scheme 1] emitted blue-colored lights, and the emission maxima were around 480 nm. Heterocycle-containing poly(1-phenyl-2-arylacetylene) [poly(1b)] and poly(1-fluorenyl-2-arylacetylene) [poly(3d)] showed green-colored and yellow-colored emissions, and the emission maxima were 520 and 540 nm, respectively. The emission wavelengths of poly(disubstituted acetylene)s having heterocycles were almost the same as those of the corresponding poly(disubstituted acetylene)s without heterocycles. However, heterocycle-containing polymers showed high fluorescence quantum yields compared to the corresponding polymers without heterocycles. Diarylacetylene polymers showed emission red-shifts between the solution and cast film, while the emission maximum of poly(1-hexyl-2-phenylacetylene) [poly(1a)] in the cast film was almost the same as that in the solution. Benzo[b]thiophene-containing poly(1-(4-trimethylsilylphenyl)-2-phenylacetylene) [poly(3b)] and poly(1-(9,9-dimethyl-2-fluorenyl)-2-phenylacetylene) [poly(3d)] afforded the free-standing membranes because of their high molecular weights. The oxygen permeability coefficient (PO2) of poly(3b) was as large as 1400 barrers. Poly(3d) showed higher gas permeability, and its PO2was 5300 barrers.