物理化学学报 >> 2002, Vol. 18 >> Issue (03): 237-242.doi: 10.3866/PKU.WHXB20020310

研究论文 上一篇    下一篇

取代聚苯胺的聚集态结构

戴李宗;许一婷;Jean-Yves GAL;吴辉煌   

  1. 厦门大学化学化工学院,固体表面物理化学国家重点实验室,厦门 361005;UMR Laboratoire Hydrosciences (CNRS, UMII, IRD), Maison des Sciences de l′Eau de Montpellier, Universite Montpellier II, 34095 Montpellier Cedex 05, France
  • 收稿日期:2001-08-20 修回日期:2001-11-20 发布日期:2002-03-15
  • 通讯作者: 戴李宗 E-mail:lzdai@xmu.edu.cn

Studies on the Structure of the Aggregated State of Ringsubstituted Polyaniline

Dai Li-Zong;Xu Yi-Ting;Jean-Yves Gal;Wu Hui-Huang   

  1. College of Chemistry and Chemical Engineering, Xiamen University,State Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen 361005;UMR Laboratoire Hydrosciences (CNRS, UMII, IRD), Maison des Sciences de l′Eau de Montpellier, Universite Montpellier II, 34095 Montpellier Cedex 05, France
  • Received:2001-08-20 Revised:2001-11-20 Published:2002-03-15
  • Contact: Dai Li-Zong E-mail:lzdai@xmu.edu.cn

摘要: 环取代基及掺杂对聚苯胺分子链结构产生影响的同时也对大分子聚集态结构产生影响.通过对聚合物膜的XRD、SEM研究,表明在所合成的环取代聚苯胺衍生物中,聚合物的结晶性依POT(聚邻甲苯胺)、PDMAn(聚2,5二甲氧基苯胺)、PmClAn(聚间氯苯胺)顺序增加;与本征态的比较,质子酸掺杂后聚合物的结晶性有所提高.POT基本上表现出了非晶聚合物的性质; PDMAn具有同质多晶的结构特征,但结晶度较低; PmClAn表现出了典型高分子晶体性质,符合单斜晶系的特征(晶胞参数为a=0.679 nm, b=2.304 nm, c=0.5734 nm, α=90°, β=100.9°, γ=90°).采用HyperChem程序包中的MM+分子力学方法对1HNMR和XRD实验结果进行结构优化,确定了苯式结构/醌式结构为3/2的PmClAn大分子链的构象.

关键词: 环取代聚苯胺衍生物, 结晶性, 聚集态结构, 大分子链构象

Abstract: Ringsubstituted groups and doping not only have a great effect on the chain structure of polyanilines, but also on their aggregated state due to its electronic and steric effect. When steric hindrance increases, the crystallinity declines. Within the same molecular chain or between different molecular chains, the forming of hydrogen bond contributes to increasing crystallinity. From SEM and XRD experiments of polymer films it was found that the crystallinity of the ringsubstituted polyanilines synthesized increases in the order of polyotoluidide(POT), poly2,5dimethoxyaniline (PDMAn) and polymchloroaniline(PmClAn). In comparison to their corresponding undoping polymers, it was concluded that proton doping of polyanilines renders their crystallinity increased. POT basically showed amorphous, while PDMAn allomorphous with low crystallinity. On the other hand, PmClAn is characterized by its molecular crystalline, being monoclinic with crystallcell parameters of a=0.679 nm, b=2.304 nm, c=0.5734 nm,α=90°, β=100.9°, and γ=90°. By using MM+ molecular mechanics methode in HyperChem program,1HNMR and Xray diffraction data were analyzed, thereby the configuration of PmClAn chain was determined and optimized, the results show that in the macromolecular chain of PmClAn the ratio of benzoid to quinoid units is 3:2.

Key words: Ringsubstituted polyanilines, Crystallinity, Aggregatedstate structure, Macromolecular chain configuration