Synthesis of π-conjugated polymers via regioregular organometallic polymers 2. Transformation of titanacyclopentadiene-containing polymer into poly(p-phenylene) derivative
Synthesis of π-conjugated polymers via regioregular organometallic polymers 2. Transformation of titanacyclopentadiene-containing polymer into poly(p-phenylene) derivative
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DOI：
10.1002/aoc.1593
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发表时间：
2010-08-01
影响因子：
3.9
通讯作者：
Tomita, Ikuyoshi
中科院分区：
文献类型：
--
作者：
Kino, Tomoko;Nishiyama, Hiroki;Tomita, Ikuyoshi
本文介绍了一种新型的聚合物反应方法，将含钛环戊二烯-2，5-二基单元的区域规整有机金属聚合物转化为聚对苯撑衍生物。通过1，4-二乙炔基-2，5-二辛氧基苯和低价钛络合物的聚合制备了有机钛聚合物，所述低价钛络合物由异丙醇钛（IV）和异丙基氯化镁原位生成，并与3-溴-1-丙炔反应，随后进行质子化。因此，可以高产率制备由取代的亚苯基-1，4-二基单元组成的聚合物，其可溶于有机溶剂如氯仿。聚合物的数均分子量和分子量分布估计分别为4800和1.8（GPC，聚苯乙烯）。该聚合物的紫外-可见吸收光谱在329 nm处有最大吸收，与模型化合物1，4-二（2-甲氧基苯基）-2-甲基苯（λ（max）= 276 nm）相比红移了53 nm。版权所有（C）2010约翰威利父子有限公司
The transformation of a regioregular organometallic polymer possessing titanacyclopentadiene-2,5-diyl units into a poly(p-phenylene) derivative by means of a novel polymer reaction method is described. The organotitianium polymer was prepared by the polymerization of 1,4-diethynyl-2,5-dioctyloxybenzene and a low-valent titanium complex, generated in situ from titanium(IV) isopropoxide and isopropylmagnesium chloride, and was subjected to the reaction with 3-bromo-1-propyne followed by the protonation. Consequently, a polymer consisting of the substituted phenylene-1,4-diyl units could be produced in a high yield, which is soluble in organic solvents such as chloroform. The number-average molecular weight and the molecular weight distribution of the polymer were estimated as 4800 and 1.8, respectively (GPC, polystyrene). The UV-vis absorption spectrum of the polymer exhibited the absorption maximum (lambda(max)) at 329 nm, which was bathochromically shifted by 53 nm compared with that of a model compound, 1,4-bis(2-methoxyphenyl)-2-methylbenzene (lambda(max) = 276 nm). Copyright (C) 2010 John Wiley & Sons, Ltd.