Electropolymerization rates of polythiophene/polypyrrole composite polymer with some dopant ions
Electropolymerization rates of polythiophene/polypyrrole composite polymer with some dopant ions
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DOI：
10.1002/(sici)1099-0488(19970115)35:1
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发表时间：
1997-01
期刊：
影响因子：
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通讯作者：
Seong-Keuck Cha
中科院分区：
文献类型：
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作者：
Seong-Keuck Cha
通过电化学聚合吡咯、噻吩及其混合单体，研究了聚合速率和聚合物基体形貌的变化，并改善了聚合物的老化和循环伏安行为。通过两步反应在铂电极的光滑表面上聚合了噻吩。第一步由双电层处的电子转移控制，另一步由在由预涂覆的噻吩聚合物组成的固定化层上反应的单体的扩散控制。第二步的电聚合速率为1.85 × 10−4 cm 3 mol−1 s−1，比第一步快8.63 × 102倍。一些支持电解质，如KPF 6，LiClO 4，TBAP和TBABF 4被用于聚合反应，以观察掺杂剂阴离子对聚合速率的影响，KPF 6是最快的，为2.41 × 10−6 cm s−1。然而，由于其对氧的敏感性，LiClO 4用于聚合，其在空气中相当稳定并且与KPF 6具有相同的速率。对于两种单体的竞争聚合反应，发现噻吩的速率比单独的噻吩慢约11倍。当噻吩单体的起始浓度比吡咯高五倍时，发现其在复合聚合物中的部分仅为8- 10%。然而，该水平在氧化还原性质和老化方面给出了期望的结果。其抗老化性能主要是由于孔隙率大幅度收缩而引起的形貌变化。John Wiley & Sons，Inc.
Pyrrole, thiophene, and a mixture of the two monomers were electrochemically polymerized to investigate polymerization rates and the morphology change of the polymer matrix, and to improve the aging and cyclic voltammetric behaviors of the polymers. Thiophene was polymerized on a smooth surface of Pt electrode by two steps. The first step was controlled by electron transfer at the electrical double layer and the other by diffusion of the monomer reacting on the immobilized layer consisting of the precoated thiophene polymer. The electropolymerization rate of the second step was 1.85 × 10−4 cm3 mol−1 s−1, which is faster by 8.63 × 102 times than the first step. Some supporting electrolytes such as KPF6, LiClO4, TBAP, and TBABF4 were employed in the polymerization reaction to see the effects of dopant anions on the polymerization rate, and KPF6 was the fastest one at 2.41 × 10−6 cm s−1. However, owing to its sensitivity to oxygen, LiClO4 was used for the polymerization that is fairly stable in air and the same rate as KPF6. For the competitive polymerization reaction of the two monomers the rate of thiophene was found to be about 11 times slower than that of thiophene alone. When the starting concentration of the thiophene monomer was higher than pyrrole by five times, its portion in the composite polymer was found to be only 8–10%. However, this level gave desirable results in terms of redox properties and aging. The resistance against aging was explained by the morphology change, which came from great shrinking of its porosity. © 1997 John Wiley & Sons, Inc.