聚苯胺:一类新型导电聚合物

A. MacDiarmid, A. Epstein
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引用次数: 899

摘要

聚苯胺是一类聚合物,其基本形式具有通式[图略],含有y还原和(1 -y)氧化重复基团。原则上,Y可以连续变化,从1(完全还原的材料)到0(完全氧化的聚合物)。翡翠氧化态(y= 0.5)由交替还原和氧化基团组成。它可以被质子化,即被水酸掺杂,同时电导率增加了近10个数量级(最大电导率为101-102 S cm-1),形成一个多聚二醌自由基阳离子,如[图省略],其中包含离域半填充的宽极化子能带。聚合物很容易被溶液加工成可以机械排列的薄膜和纤维,其掺杂形式具有平行于排列方向的电导率明显大于非排列材料。x射线研究表明,掺杂和未掺杂的聚合物以几种不同的晶体形式存在。通过在环上或氮上进行取代,可以合成各种各样的衍生物。
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Polyanilines: a novel class of conducting polymers
The polyanilines are a class of polymers the base form of which has the general formula [graphic omitted] containing y reduced and (1 –y) oxidized repeat groups. y can in principle be varied continuously from one, the completely reduced material, to zero to give the completely oxidized polymer. The emeraldine oxidation state (y= 0.5) consists of alternating reduced and oxidized groups. It can be protonated, i.e. doped, by aqueous acids with a concomitant increase in conductivity of almost 10 orders of magnitude (to a maximum conductivity of 101–102 S cm–1), forming a polysemiquinone radical cation such as [graphic omitted] which contains a delocalized half-filled broad polaron energy band. The polymer is readily solution-processed into films and fibres which can be mechanically aligned, the doped forms of which have a conductivity parallel to the direction of alignment significantly greater than that of non-aligned material. X-Ray studies show that the doped and undoped polymer exist in several different crystalline forms. A wide variety of derivatives can be synthesized by substitution on the ring or on the nitrogen.
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