CATALYTIC POLYMERIZATION OF ANILINE AND ITS DERIVATIVES BY USING COPPER(II) SALTS AND OXYGEN - NEW-TYPE OF POLYANILINE WITH BRANCHED STRUCTURE
CATALYTIC POLYMERIZATION OF ANILINE AND ITS DERIVATIVES BY USING COPPER(II) SALTS AND OXYGEN - NEW-TYPE OF POLYANILINE WITH BRANCHED STRUCTURE
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DOI：
10.1246/bcsj.67.1947
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发表时间：
1994-07-01
影响因子：
4
通讯作者：
ISHIWATARI, M
中科院分区：
文献类型：
--
作者：
TOSHIMA, N;YAN, H;ISHIWATARI, M
将相应单体与铜(II)盐(50/5，mm o l/m o l)在乙腈-水(1/1，v/v)中室温氧气中搅拌24 h，催化苯胺及其衍生物的聚合，其中CuBr2和CuCl2活性较高。在每种情况下，铜盐都不是化学计量的氧化剂，而是催化剂，这一点可以根据翻转频率来证明。分离出的聚合物是具有祖母绿结构的聚苯胺的特征，尽管在邻位通过加成反应副产了少量的支化结构。因此，聚合物在284℃的热处理导致部分分解，以产生稳定的聚合物和苯胺。尽管合成的聚合物具有祖母绿类型的结构，但没有观察到强烈的掺杂对其导电性的影响，这可能是因为其无定形的形态。反应溶液的UV-Vis光谱表明，苯胺的催化聚合是通过苯胺的铜(II)络合物的形成进行的。
The catalytic polymerization of aniline and its derivatives was performed by stirring the solution of the corresponding monomer and copper(II) salts (50/5, mmol/mol) in acetonitrile and water (1/1, v/v) under oxygen at room temperature for 24 h. Among copper salts, CuBr2 and CuCl2 are more active than the others. In each case the copper salts do not work as a stoichiometrical oxidant but work as a catalyst, which can be proved on the basis of turn-over-frequency. The polymers isolated were characteristic of polyaniline with an Emeraldine structure, although a small amount of branched structures were by-produced by an addition reaction at ortho-position. Thus, heat treatment of the polymer at 284-degrees-C results in partial decomposition to produce the stable polymer and aniline. Although the resulting polymer had an Emeraldine type structure, a strong doping effect on its electroconductivity was not observed, probably because of the amorphous morphology. The UV-vis spectra of the reaction solution have suggested that the catalytic polymerization of aniline proceeds through the formation of the copper(II) complex of aniline.