【作者】 李春艳；

【导师】 姚琲；

【作者基本信息】 天津大学 ， 材料学， 2005， 博士

【摘要】 本文以提高导电聚苯胺的导电性、可加工性为目的,采用电化学、无机酸掺杂法和有机大分子酸乳液聚合法等多种方法,制备出高电导的掺杂态聚苯胺,研究了不同制备工艺和工艺参数对聚苯胺性能的影响。在此基础上,采用溶胶-凝胶的方法制备出同时具有耐水性和导电性的聚苯胺-TiO₂混合涂层,具有很高的实用价值。此外,设计并制作了聚苯胺图形薄膜微加工装置,可以实现导电高聚物薄膜在不同表面上的沉积,大大提高了聚苯胺的二维图形加工性能。采用恒电位法和循环伏安法,着重分析了苯胺单体浓度、质子酸浓度以及阴离子种类、扫描速度对电化学合成聚苯胺性能的影响。通过选择适当的工艺参数,不仅可以调节聚苯胺的聚合速度,还可以控制其导电性和结构形态。利用无机小分子酸对有机溶剂/水双组分聚合体系进行掺杂,发现聚苯胺的分子量是影响其溶解性的主要原因。当苯胺和过硫酸铵的配比为2:1左右,在低温下聚合约5小时,可以得到导电率和产率均较高的聚苯胺。此外,在无机酸掺杂的基础上,利用体积较大的有机酸进行二次掺杂,可以使聚苯胺分子链排列更加规整,进一步提高其电导率。通过对苯胺聚合过程的现场跟踪,证明了聚合过程的中间产物是高氧化态聚苯胺,综合分析了苯胺的聚合机理。系统探讨了有机功能质子磺酸对聚苯胺的各种掺杂方法,采用乳液聚合-萃取法制得了在氯仿中完全溶解的导电聚苯胺。研究了作为掺杂剂和乳化剂的DBSA用量、反应温度、引发剂浓度对导电聚苯胺性能的影响,确定了DBSA与苯胺的最佳摩尔比在0.83左右,最佳反应温度为15℃,引发剂APS的最佳浓度为0.055mol/l。为改善其耐水性和有机-无机的界面作用,将聚苯胺链通过溶胶-凝胶的方法固定在无机介质TiO₂中,制备出具有一定耐水性和导电性的涂层。为导电聚苯胺的实际应用提供了重要依据。在导电聚苯胺-TiO₂杂化材料中,导电聚苯胺的固含量应控制在30%wt～80%wt区间,并加入少量的硅烷偶联剂来改善材料的成膜性能,在低温下进行缓慢老化可得到较致密的网状结构的杂化材料。将导电高聚物的行打图形加工模式和电化学沉积的原理相结合,提出一种简单廉价、具有普适性的新沉积工艺。通过自制的微加工装置将聚苯胺应用于二维图形加工,并通过自制的聚苯胺微图形加工装置在不锈钢基片表面加工出了分布均匀的、大小可控的聚合物微图形。此外,尝试将聚苯胺直接沉积在粗化后的PCB基材上用于电镀铜,可以大大节约PCB板工艺中制备铜镀层的成本。更多还原

【Abstract】 In order to solve the machining problem and increase its conductivity, doped conducting Polyaniline was prepared by electrochemistry method, abio-acid doped method and emulsion polymerization doped with organic acid. The effects of the different preparation technics and technical parameters on the performance of Polyaniline were investigated. Then, blending Polyaniline-TiO₂ coat was prepared by the sol-gel method. Such coat had great practical value because it not only is water-proof but also has high conductivity. Moreover a new machining device was designed and fabricated to deposit the micro-pattern Polyaniline thin film onto concavo-convex surface. In this way the machining properties of two-dimensional pattern of conducting Polyaniline can be greatly improved.In electrochemistry, constant voltage and circle voltage-current methods were adopted. The influences of monomer concentration, protonic acid concentration, the kinds of anions and scanning speed on the properties of conducting Polyaniline were investigated. It was found that not only the polymerization speed, but also the conductivity and structure of Polyaniline can all be adjusted by choice of proper technical parameters.In bicomponent solvent system of organic solvent/H2O, Polyaniline was doped by abio-acid. It is found that the molecular weight of polyaniline is the main factor to affect its dissolution. Polyaniline with high conductivity and high product yield was obtained by polymerized at low temperature for 5h when aniline/APS is 2:1. In addition, the order of polyaniline chains can be improved by further doped with giant molecule organic acid, hence the conductivity of Polyaniline was also increased. Middle products were proved to be high-oxidation Polyaniline by on-line observation of Polyaniline-polymerization process. Theory about Polyaniline-polymerization was discussed systemically.Conducting Polyaniline that can be fully soluble in chloroform was prepared by emulsion polymerization and extraction method, doping with different dopants of macro-molecule functional protonic acids. Effects of DBSA content, which acted as dopants and emulsification APS, reacting temperature, solicitation concentration were studied. Optimization techniques is determined to be reacted at 15℃whenDBSA/aniline is about 0.83 and concentration of APS is 0.055mol/l simultaneity.In order to improve the water-proof performance and inorganic-organic interface action, a new hybrids coat with water-proof performance and high conductivity was prepared by confined Polyaniline chains into the inorganic media of TiO₂ by sol-gel methods. In such Polyaniline-TiO₂ hybrids material, conducting Polyaniline content should be about 30%wt～80%wt. The character of such polyaniline membrane material can be improved by a little GOTMS addition and dense hybrids material with net structure can be obtained by aging slowly at lower temperature.A new cheap, simple deposition technique that may be widely used was put forward on basis of the line-pattern and electrochemistry deposition principle of conducting polymer. Then Polyaniline can be applied in precision machining of two-dimensional patterns by a homemade micro-machining device. Such micro-machining device successfully prepared Polyaniline micro-patterns of variety shape, which can be uniformly distributed on stainless steel substrates. In addition, Polyaniline has also been deposited on roughened PCB board directly for the electro-deposition of Cu, through which the cost of Cu coats in PCB technique can be greatly reduced.更多还原