导电聚苯胺的合成、结构、性能和应用

概述了中国科学院长春应用化学研究所对导电聚苯胺合成、结构、性能和应用的研究.从合成可溶性的聚苯胺入手,阐明了聚苯胺的若干基本化学和结构问题,提出并证明了掺杂态聚苯胺的结构模型和掺杂机理;除了质子酸掺杂外,发现了聚苯胺的碘氧化掺杂、光助氧化掺杂和K+注入还原掺杂;开发了分别以环氧树脂和聚氨酯为载体的聚苯胺防腐涂料;运用掺杂剂诱导的溶解性,通过合成带聚乙二醇链的膦酸掺杂剂,实现了导电态聚苯胺的水体系加工.其中的聚苯胺树脂及防腐涂料的生产技术,已经完成中试,正在走向产业化.     

多金属氧酸盐掺杂聚苯胺电子聚合物——多金属氧酸盐与HCl共掺杂聚苯胺HCl-SiW11Co/Pan的合成及其性质

多金属氧酸盐掺杂聚苯胺电子聚合物——多金属氧酸盐与HCl共掺杂聚苯胺HCl-SiW11Co/Pan的合成及其性质;聚苯胺;多金属氧酸盐;掺杂;光电磁性质     

XPS研究聚苯胺的竞争掺杂行为

采用X射线光电子能谱（XPS）方法对不同反应体系下化学合成的聚苯胺（PANI）的结构和掺杂状况进行了研究。发现盐酸（HCl）掺杂的聚苯胺在样品后处理过程中易发生脱掺杂行为;在十二烷基苯磺酸钠（SDBS）和盐酸共存体系下合成聚苯胺时,对阴离子DBS-和Cl-发生竞争掺杂行为。结果表明DBS-与带正电荷聚苯胺链结合,起到了掺杂和诱导聚苯胺可溶性的作用,它的N1s和S2p谱图与单独采用十二烷基苯磺酸（DBSA）掺杂聚苯胺的谱图相似。但SDBS-HCl复合体系比单独采用DBSA体系更为有利。     

掺杂态聚苯胺的性能及其防腐应用研究进展

聚苯胺具有良好的导电性和独特的掺杂-解掺杂特性,成为近年来备受关注的导电高分子材料,其特有的抗划伤、抗点蚀和钝化性能使其在金属防腐领域拥有巨大的应用前景。聚苯胺结构中苯环的存在,使得其分子链具有较大刚性,而分子间氢键又导致其难溶、难熔、可加工性能较差,严重制约了聚苯胺的应用。掺杂过程能有效改善聚苯胺的某些性能,或赋予其新的功能,扩展聚苯胺的应用。本文综述了聚苯胺的掺杂方式、掺杂机理、聚苯胺防腐材料的制备方法,以及其在金属防腐领域的应用,展望了聚苯胺的研究和应用前景。     

复合酸掺杂导电聚苯胺的性能研究

以苯胺为单体、过硫酸胺为氧化剂,由化学氧化聚合法在磺基水杨酸和硫酸的复合酸的水溶液中合成导电聚苯胺,并通过压片法、激光粒度分析、扫描电镜、差热分析及红外光谱对掺杂态聚苯胺的电导率、表面形貌及结构进行了研究.结果表明,复合酸掺杂聚苯胺的热稳定性比仅用硫酸掺杂聚苯胺的有了很大的提高;所得导电聚苯胺的粒度分布比较均匀(平均粒径约15.4μm);复合酸掺杂使聚苯胺分子链上的电荷呈离域化,掺杂程度提高.     

新型质子酸掺杂聚苯胺的合成及其电化学电容行为

用化学氧化聚合法制得了草酸掺杂聚苯胺(H2C2O4-PANI)和柠檬酸掺杂聚苯胺(C6H8O7-PANI),并与盐酸掺杂聚苯胺(HCl-PANI)做了对比研究.用红外光谱(FT-IR)、X射线衍射(XRD)和透射电镜(TEM)对掺杂聚苯胺的结构和形貌进行了表征.用循环伏安,恒流充放电和交流阻抗测试对材料在1 mol/L HCl溶液中的电化学电容行为进行了研究.结果表明:3种酸掺杂的聚苯胺具有不同的空间结构,电化学性能也有差异.与盐酸和柠檬酸掺杂的聚苯胺相比,草酸掺杂制备的聚苯胺表现出更优良的电化学电容行为,单电极比电容可达670 F/g.     

固相反应法制备磷钼酸(H3PMo12O40)掺杂聚苯胺对其电化学活性的影响

利用固相反应法制备了磷钼酸(H3PMo12O40,简称PMA)掺杂聚苯胺,并以红外光谱(FT-IR)、X-射线衍射(XRD)、循环伏安(cyclic voltamm ogram)等测试方法对聚苯胺进行了表征。结果表明,无论是液相法还是固相法,磷钼酸掺杂于聚苯胺中,仍保持自身结构特征,与传统液相合成的磷钼酸掺杂聚苯胺相比,固相反应法合成的磷钼酸掺杂聚苯胺的晶化率和电活性略差。固相反应法制备的磷钼酸掺杂聚苯胺在对抗坏血酸(AH2)电催化氧化中,表现出比液相合成更好的电催化活性。     

盐酸掺杂聚苯胺的制备及性能研究

本文用溶液聚合法制备盐酸掺杂聚苯胺,测定了体系酸度对聚苯胺电导率的影响,及盐酸掺杂聚苯胺在不同条件下经过热处理后的电导率,采用TGA、XRD等方法,研究了热处理过程对聚苯胺结构的影响。结果表明,当热处理温度为90℃时,电导率高于初始值,当热处理温度高于100℃时,电导率开始下降,到达220℃时,电导率下降了约4个数量级。在氮气中聚苯胺电导率的衰减比空气中小,聚苯胺经热处理后在浓硫酸中的溶解性会明显降低。本文还探讨了去掺杂、氧化和化学交联等盐酸掺杂聚苯胺的热降解机理。     

FeCl3掺杂聚苯胺催化合成苯甲醛1，2-丙二醇缩醛

FeCl3掺杂聚苯胺催化合成苯甲醛1;2-丙二醇缩醛;缩醛;三氯化铁;聚苯胺;掺杂     

聚苯胺水基胶体分散液及其复合物的研究 Ⅱ紫外光谱及导电性能

利用紫外可见光谱研究了聚苯胺（ＰＡｎ）在水基胶体分散液中掺杂与脱掺杂过程，证实了ＰＡｎ的掺杂与脱掺杂是完全可逆的过程．当ｐＨ＝３５时，开始脱掺杂，当ｐＨ＝６０时，脱掺杂已基本结束．ＰＡｎ颗粒的大小也对紫外光谱有影响．当聚苯胺颗粒尺寸达到纳米量级时（１００ｎｍ），复合膜光谱吸收峰明显兰移，表现出了表面效应和量子尺寸效应．聚苯胺／聚乙烯醇复合膜的电导率不仅受聚苯胺含量的影响，同时也受复合膜中聚苯胺颗粒聚集状态的影响．较小的聚苯胺颗粒，使复合膜具有较低的渗滤阈值．     

Polyaniline thin film optical waveguides for integrated optics and VLSI prepared by vacuum evaporation technique

Polyaniline is emerging as an important polymer material which offers challenging opportunities for both fundamental research and new technological applications in waveguides. Metal doped polyaniline has been prepared initially in the form of powder by a solution growth technique. The emeraldine salt with doped metal was also prepared by solution growth technique. This powder was used for vacuum evaporation on optically flat glass substrate. The dark green doped (Fe, Al) polyaniline thin films were prepared by vacuum evaporation technique (10^?4 torr). Deposited waveguide thin films have been characterized structurally, using X‐ray diffraction (XRD), optically etc. Effective refractive index of the thin film waveguide was also calculated theoretically and experimentally. Waveguide parameters, namely refractive index, propagation loss and depth of vacuum deposited polyaniline thin films optical waveguide have been determined. The optical spectra and structure and waveguide parameters of vacuum deposited polyaniline thin films are strongly affected by the type of doping. It is possible to reduce the losses by addition of Fe to the vacuum deposited polyanine thin film and modify the effective refractive index (O_eff) according to particular requirements. Results are compared with the results in the literature. Copyright © 2002 John Wiley & Sons, Ltd.     

Molecular properties of sulfonated polyaniline

The molecular characteristics of internally doped sulfonated polyaniline with a sulfonation degree of ∼1 are studied by the methods of viscometry and dynamic light scattering. In diluted aqueous-saline solutions, the molecules of sulfonated polyaniline are individual entities; they do not form intermolecular associates and do not dissociate into separate components. An increase in the concentration of NaCl in solution from 0 to 1 mol/l brings about a sharp gain in the intrinsic viscosity of the polymer and in the hydrodynamic radius of molecules. This effect results from the decomposition of zwitterion pairs responsible for the compact conformation of polymer molecules in water. The equilibrium rigidity of sulfonated polyaniline molecules is calculated from the hydrodynamic characteristics determined in a 1 M NaCl solution, where the electrostatic interaction may be considered to be suppressed. A length of the Kuhn segment of 1.46 nm is higher by a factor of 1.5 than the corresponding length for the initial polyaniline.     

CuCl2掺杂聚苯胺催化合成苯甲醛1,2-丙二醇缩醛

缩醛是一类重要化合物,具有原料来源丰富、生产工艺简单、化学性质稳定等优点,近20年来作为新型香料在日用香精和食品香精中均有广泛应用[1-2]。根据酸催化机理,Lewis酸可增强羰基碳的正电性,有利亲核试剂的进攻。研究表明,不少无机盐都是这类反应的高效、高选择性的催化剂,又因为无机盐价廉、易得等优点,所以用其作为催化剂具有更加重要的实际意义。聚苯胺(PAn)以其独特的掺杂现象及良好的稳定性为催化载体的选择提供了新的途径[3-4]。若以PAn为载体,将具有催化活性的路易斯酸掺杂其中,可降低路易斯酸的流失量,并克服其易潮解、腐蚀设备…     

A suitable model for emeraldine salt

A new mechanism for the formation of doped polyaniline is presented. Besides providing suitable structural and spectroscopic parameters, the new mechanism allows for the rationalization of the experimentally observed equilibrium between polaron and bipolaron defects in emeraldine salt. The magnetic behavior and the "metallic island" model for conduction in doped polyaniline are also theoretically supported by the new proposal.     

β-萘磺酸掺杂聚苯胺纳米粒子的固相反应法制备及其表征

利用固相反应法制备了 β 萘磺酸掺杂的聚苯胺纳米粒子 ,并以红外光谱 (FTIR) ,扫描电子显微镜(SEM) ,透射电镜 (TEM) ,X 射线衍射 (XRD)以及粉末微电极等测试方法对其进行了表征 .结果表明 ,固相反应法合成的 β 萘磺酸掺杂聚苯胺粒子直径为 30～ 5 0nm ,聚苯胺分子链排列有序 ,晶化率较好 .粉末微电极的循环伏安测试表明 ,β 萘磺酸掺杂聚苯胺有较好的电化学活性 .     

Synthesis and Characterization of Conducting Polyaniline Doped with Polymeric Acids

Conducting polyaniline doped with polymeric acids was synthesized by a in situ chemical polymerization method. The synthesized polymers were characterized by using UV‐Visible, FT‐IR spectroscopy and SEM analysis. Thermal stability of these polymers was evaluated by using TGA/DSC analysis. Among the three polymeric acids used for doping purpose, poly(vinyl sulphonic acid) doped polyaniline is found to be more conducting than those doped with other acids. From the temperature dependent conductivity measurements, an increase in conductivity with increase in temperature was observed.     

聚苯胺/聚砜复合材料的制备及其超级电容性能

通过化学聚合法,制备出盐酸掺杂聚苯胺（PANI）,将其与聚砜（PSF）溶液混合,定量滴加到玻碳电极上制得PANI/PSF复合膜电极。 采用扫描电子显微镜、红外光谱以及X射线衍射对其结构和形貌进行表征。 根据循环伏安曲线、恒电流充放电曲线和电化学阻抗,研究了其作为电极的超级电容性能。 结果表明,多孔结构的PANI/PSF复合材料具有良好的电容性能,其比电容可达到497 F/g,并且该超级电容器具有较小的内阻和较好的循环稳定性。     

掺杂态聚苯胺LB膜的制备与性质

掺杂樟脑磺酸的聚苯胺在纯水表面可以形成稳定的单分子层,采用Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔｔ技术可以将其较好地转移到氟化 基片上制成薄膜,对其ＬＢ膜的红外和紫外－可见－近红外光谱研究表明,在膜的压缩或转移过程中有少量的樟脑磺酸分子发生脱掺杂的现象,并且该ＬＢ膜在室温下对乙醇有较好的气敏性。