CATALYTIC SYNTHESES OF AROMATIC CONDUCTING POLYMERS

聚吡咯是一种稳定的耐热聚合物。研究了以分子氧为氧化剂，氯化铜(I) -氯化铝配合物为催化剂，从吡咯合成聚吡咯的新方法。然而，由于该催化剂对水敏感，由于分子氧的还原而产生的水眼会使催化剂失活。因此，在本项目中，我们开发了一种不含氯化铝的新型催化体系。在各种金属盐中，我们发现铁（III）盐如氯化铁（III）是有效的。此外，发现用于该反应的溶剂对反应产率和聚合物的导电性是有效的。事实上，在所有的溶剂中，碳酸丙烯酯被认为是最好的。在阴离子作为掺杂剂存在的情况下进行催化氧化聚合，以提高聚合物的导电性。2)氯化铜-氧体系对苯胺及其衍生物的氧化聚合具有较好的催化作用。然而，这样制备的聚苯胺有一个缺点，即加工性能差。为了弥补这一缺点，研究了一种由前驱体聚合物制备聚苯胺的新方法。聚邻氨基苯甲酸可溶于一些有机溶剂和碱性溶液，是前驱体聚合物的候选物之一。然而，用常规方法制备时，收率很低。研究了在碱性溶液中氧化聚合制备高收率聚邻氨基苯甲酸的新方法。对聚邻氨基苯甲酸进行热处理，得到的聚苯胺会损失二氧化碳。我们还开发了以氨基苯磺酸为原料制备磺化聚苯胺的新方法。

1) Polypyrrole is a stable and heat-resisting polymer. We have already developed a novel method to prepare polypyrrole from pyrrole by using molecular oxygen as an oxidant and copper (I) chloride-aluminum chloride complex as a catalyst, respectively. However, sine this catalyst is sensitive to water, the catalyst can be deactivate by the water bye-produced by the reduction of molecular oxygen. Thus, in this project, we have developed a new catalytic system which does not contain aluminum chloride. Among various metal salts, we found that iron (III) salts like iron (III) chloride are effective for this purpose. In addition, the solvent used for this reaction was found effective in the reaction yield and the conductivity of the polymer produced. In fact, propylene carbonate was found the best among the solvents examined. The catalytic oxidative polymerization was carried out in the presence of anions, which work as the dopant, to improve the conductivity of the produced polymer.2) The copper (II) chloride-oxygen system was found effective in the catalytic oxidative polymerization of aniline and its derivatives. However, the polyaniline thus prepared has a disadvantage, i.e., a bad processability. In order to cover this disadvantage, a novel method was investigated to prepare polyaniline from precursor polymers. Poly (o-aminobenzoic acid) is soluble in some organic solvents and alkaline solutions, being one of the candidates for the precursor polymer. However, the yield is very low when it is prepared by a conventional method. We have develop a new method to prepare poly (o-aminobenzoic acid) at high yield by oxidative polymerization in an alkaline solution. Heat treatment of poly (o-aminobenzoic acid) gives polyaniline with loss of carbon dioxide. We have also developed a new method to prepare sulfonated polyaniline from aminobezenesulfonic acid as a raw materials.