导电聚合物电致变色材料*

由于在电致变色、显示、军事等领域的广泛应用,电致变色材料受到了人们越来越多的关注。本文综述了聚苯胺(PANI)类、聚噻吩(PTh)类、聚吡咯(PPy)类及复合导电聚合物电致变色材料的性能及其研究进展,同时简单地叙述了这些材料作为电致变色材料的应用前景,指出具有丰富颜色变化、良好的稳定性及成膜性的共聚物及有机/无机复合导电聚合物材料是未来电致变色材料发展的方向。     

导电聚合物基电致变色器件的研究进展

导电聚合物作为电致变色活性材料是目前最有应用前景的智能材料之一。本文概述了电致变色器件的基本结构和导电聚合物的电致变色机理,着重介绍了多种导电聚合物基电致变色器件的特点、组成及制备,并展望了未来电致变色器件的发展及应用趋势。     

3-辛基噻吩的质谱分析

共轭聚合物通常具有一些独特的物理性质,如高的电导率、电致发光、电致变色、非线性光学性质等。这类共轭聚合物包括聚苯胺、聚噻吩、聚吡咯、聚对苯乙炔、聚对苯等。自英国剑桥大学的Burrougs等人[1]采用聚对苯乙炔成功地制备了第一个聚合物电致发光器件以来,对聚合物电致发光     

导电聚合物LB膜

本文回顾了ＬＢ膜技术在导电聚合物体系中的利用，内容涉及共轭型导电聚合物（包括聚吡咯、聚噻吩、聚对亚苯基亚乙烯基、聚苯胺及其衍生物）ＬＢ膜的制备、结构表征、电导率与分子结构和分子堆砌之间的关系以及其他导电聚合物ＬＢ膜的研究现状。     

低掺杂吡咯低聚物-聚苯乙烯复合膜／电解质溶液体系的介电谱解析——选择渗透性和膜内离子扩散行为

制备了十二烷基苯磺酸掺杂的吡咯低聚物（DBSA-oligopyrrole,DOPY）／聚苯乙烯复合膜,首次在40Hz-4 MHz频率范围测量了该膜在5种电解质中和不同酸度条件下的介电谱,并在等效电路模型和界面极化理论基础上分析了弛豫的特征并确定了弛豫机制,并利用介电参数对各测量结果进行了膜参数的解析,获得了关于该DOPY／PS复合膜对不同电解质的渗透能力和离子导电特征的原位信息,以及介质环境的酸度对电参数的影响：介电参数给出了聚吡咯在聚苯乙烯中的最佳含量：理论解析给出了DOPY／PS复合膜对不同电解质溶液的透过性及选择性规律．结果表明：由于聚吡咯的存在明显提高了纯聚苯乙烯膜的渗透能力,在本研究条件下,确定质量百分数为1％的DOPY／PS复合膜的渗透性能最优;定量计算了膜内大约含有0．80mol／m^3的负电量,预测了复合膜对含有不同阴离子的电解质具有选择透过性;此外,分析了由于膜本身的性质受溶液pH的影响从而造成的透过性随溶液pH变化的原因．此研究首次将介电解析从以往的分离膜体系拓展到了复合型导电聚合物膜体系．     

聚苯胺的图形化沉积

自1976年发现第一个有机聚合物聚乙炔掺杂后具有类似金属的导电性以来，先后发现了聚吡咯、聚噻吩和聚苯胺(PAn)等导电聚合物，其中聚苯胺以其合成方法简单、稳定性好、较高的电导率及良好的电化学性能等被预言为是最有应用前景的导电高分子材料之一。近年来，随着导电聚合物研究的广泛开展和不断深入，     

纳微米聚(3,4-二氧乙基噻吩)导电高分子的合成及其性能研究

在导电高分子家族中,聚(3,4-二氧乙基噻吩)(PEDOT)由于具有高的电导率、环境稳定性、透明性以及良好的成膜性等优异性能而广泛地应用于有机电致发光器件、太阳能电池、防静电、电致变色器件、传感器等领域.本论文研究了绝缘高分子聚乙二醇(PEG)和乙二醇、一缩二乙二醇等有机极性溶剂提高PEDOT/PSS(聚苯乙烯磺酸钠)电导率的机理,并通过改变稳定剂、掺杂剂等因素制备了具有不同结构和性能的PEDOT胶体颗粒以及PEDOT/PMMA(聚甲基丙烯酸酯)复合微球,取得了以下主要的创新性结果:1.通常,在导电高分子中加入绝缘高分子会降低其电导率.然而在PEDOT/PSS中加入绝缘高分子PEG,不但没有降低其电导率,反而大大提高了其电导率.PEG浓度对复合膜电导率的影响很大.其电导率最大值比PEDOT/PSS提高了两个数量级.而且,复合膜电导率最大值随PEG分子量的增加而降低,呈现良好的线性关系.     

聚吡咯电化学制备实验的改进——一个开放式综合实验设计

聚吡咯作为一种具有特异光电性能的π-共轭类导电高分子,其制备实验也逐步走进大学课堂,成为融合化学、物理、材料等多个学科知识的代表性实验。项目组以本校“聚吡咯的电化学制备实验”为基础,将其从一个简单的任务式制备实验,改进成一个集制备条件自主选择以及导电性能表征为一体的综合性开放式实验：首先在三电极体系下进行电化学聚合,并以此为切入点,展开对聚合条件的开放式探索,然后使用循环伏安法对所得聚吡咯薄膜进行电致变色实验,最后测试其电导率并展开讨论和分析。本改进实验内容丰富,有助于学生综合技能的提升和科学思维的培养,更加贴合现代化学学科发展。     

过渡金属一取代Keggin结构钼磷酸盐掺杂的聚吡咯的制备、表征与导电性研究

０引言有机高分子－多酸导电聚合物是８０年代末兴起的一类新型有机－无机杂化材料。由于它兼有无机组分和有机聚合物基块的性能，并能衍生出新的导电性、光学性、耐摩擦、力学性能、功能梯度等，它现已成为材料科学和化学科学研究的前沿课题之一犤１犦。多酸是一类含有氧桥的多核配合物，具有强酸性、强氧化性、优良的催化活性、光致变色、电致变色性及高质子导电性等，可作为构建有机－无机杂化材料的基块犤２，３犦。聚吡咯是一类有机高分子，其合成简便、空气稳定性好、易于掺杂，通过掺杂可形成高电导率的高分子材料。若将多酸掺杂聚吡…     

聚噻吩类电致变色材料的研究进展

电致变色材料广泛应用于显示屏、智能窗、国防军事伪装等各方面,得到了人们的广泛关注。本文介绍了聚噻吩及其衍生物的变色机理,综述了聚噻吩、PEDOT、D-A型材料、D-A-D型材料、噻吩共聚物及其有机/无机纳米复合材料的性能及其研究进展,并简要介绍了噻吩类电致变色材料的应用前景,指出合成颜色变化丰富、稳定性和成膜性好、易加工、并有很好导电性能的D-A-D材料、共聚物及其有机/无机纳米复合材料是聚噻吩类电致变色材料发展的主要趋势。     

Properties of nanometric and micrometric multilayered films made of three conducting polymers

The electrochemical, electrical and morphological properties of multilayered films formed by alternated layers of poly(3,4-ethylenedioxythiophene), polypyrrole, and poly[N-(2-cyanoethyl)pyrrole], which were prepared by electrochemical layer-by-layer deposition, have been investigated and compared with those of multilayered films formed by two conducting polymers. Results indicate that the electrochemical behavior of the films formed by three conducting polymers depends on the micrometric or nanometric thickness of the layers. Thus, the electroactivity increases until the thickness of these films reaches a threshold value (∼2 μm), while the electrostability of the films is very remarkable when their thickness is close to ∼4 μm or higher. On the other hand, comparison between multilayered systems made of two and three conducting polymers indicates that the third component introduces heterogeneity in the interfaces between consecutive layers, reducing the ability to store charge. Among the latter, multilayered films formed by poly(3,4-ethylenedioxythiophene) and polypyrrole have been found to be particularly electroactive and electrostable. The surface morphology and topography of the layers have been used to rationalize the electrochemical properties of the different materials.     

All-solid-state reference electrodes based on conducting polymers

A novel construction of solution free (pseudo)reference electrodes, compatible with all-solid-state potentiometric indicator electrodes, has been proposed. These electrodes use conducting polymers (CP): polypyrrole (PPy) or poly(3,4-ethylenedioxythiophene) (PEDOT). Two different arrangements have been tested: solely based on CP and those where the CP phase is covered with a poly(vinyl chloride) based outer membrane of tailored composition. The former arrangement was designed to suppress or compensate cation- and anion-exchange, using mobile perchlorate ions and poly(4-styrenesulfonate) or dodecylbenzenesulfonate anions as immobilized dopants. The following systems were used: (i) polypyrrole layers doped simultaneously by two kinds of anions, both mobile and immobilized in the polymer layer; (ii) bilayers of polypyrrole with anion exchanging inner layer and cation-exchanging outer layer; (iii) polypyrrole doped by surfactant dodecylbenzenesulfonate ions, which inhibit ion exchange on the polymer/solution interface. For the above systems, recorded potentials have been found to be practically independent of electrolyte concentration. The best results, profound stability of potentials, have been obtained for poly(3,4-ethylenedioxythiophene) or polypyrrole doped by poly(4-styrenesulfonate) anions covered by a poly(vinyl chloride) based membrane, containing both anion- and cation-exchangers as well as solid potassium chloride and silver chloride with metallic silver. Differently to the cases (i)-(iii) these electrodes are much less sensitive to the influence of redox and pH interferences. This arrangement has been also characterized using electrochemical impedance spectroscopy and chronopotentiometry.     

纳米结构导电聚合物材料研究进展

具有纳米结构的导电聚合物因其诱人的应用前景越来越引起人们的重视。本文综述了聚苯胺、聚吡咯以及聚噻吩等导电聚合物的零维、一维、二维以及三维纳米结构的合成方法,并介绍了聚合物纳米结构的表征以及研究现状和应用前景。参考文献60篇。     

Considerations about the electrochemical estimation of the ionization potential of conducting polymers

The energy gap and ionization potential of some conducting polymers such as polypyrrole and the polythiophene derivatives, poly(3-methylthiophene) and poly(3-hexylthiophene), are estimated using optical and electrochemical techniques. With these parameters we have constructed the energy level diagrams of the polymers. Electronic Publication     

Cellulose as matrix component of conducting films

Conjugated polymers gain growing importance as conductive materials in industrial applications in various fields of electronic devices. Cellulose with its extraordinary supramolecular structure and material properties can help to awake the possibilities for conducting polymers in interplay of the two materials. The ability of additional derivatization, the stiff and oriented molecular structure and the inherent strength, stability and film-forming properties give cellulose a complementary role to the brittle conjugated polymers, cellulose imparting the features of a stable and robust carrier component. To go forward this way, making a composite out of cellulose and conducting polymers is a prerequisite. Different strategies to form composite materials of non-derivatized cellulose and conductive organic polymers were tested. Significant differences between various mixing strategies as well as between the conducting polymers polyaniline (PAni), polypyrrole (PPy), and polythiophen (PTh) were observed. In situ synthesis of the conducting polymers in cellulose solutions and microcellulose dispersions as well as blending of pre-synthesized conducting polymers in these cellulose systems were tested. Unexpectedly, not homogenous mixtures showed best results in respect to film formation and conductivity, but composites formed by heterogeneous mixtures of the conducting polymers within a cellulose gel. Best results were obtained with finely dispersed PAni. The results support development studies towards circuitry and photo-current systems based on cellulose carriers.     

Design of New Reaction Fields for Spherical Polypyrrole Particle Synthesis

Summary: Polypyrrole conducting polymers have been investigated widely for various applications because of their thermal and environmental stability and good electrical conductivity. Using chemical oxidative polymerization for the synthesis of polypyrrole particles, the reaction rate is very fast. In this study, we designed two new reaction fields for the synthesis of spherical polypyrrole nanoparticles. In the first system, oxidative polymerization of monomer droplets infused in a water/oil (W/O) emulsion reaction field was investigated. The second system employed dispersed monomer in an aqueous solution with a low concentration of oxidant in which polymerization was augmented by ultrasonic irradiation. Effective control of the reaction rate was important for enabling the synthesis of fine spherical polypyrrole particles.     

Specific interactions in complexes formed by polythiophene derivatives bearing polar side groups and plasmid DNA

The interaction between plasmid DNA and polythiophene derivatives bearing substituents with polar groups has been examined using electrophoresis assays, and both UV-Vis and CD spectroscopies. Results clearly indicate that such conducting polymers form stable adducts with DNA, even although the interactions strongly depend on the chemical constitution of the polymers. Furthermore, digestion assays with EcoRI and BamHI evidence that the polymers form specific interactions with the DNA, protecting the target nucleotide sequences of these restriction enzymes. On the other hand, UV-Vis and CD spectra show that the interactions induce a fast and very significant exposition of the nitrogen bases, which is consequence of the structural alterations induced in the circular DNA. These results have been compared with those previously reported for polypyrrole, poly(3,4-ethylenedioxythiophene) and poly(3-methylthiophene). Finally, a model based on the intercalation of the conducting polymer between the two DNA strands has been proposed.     

导电高分子的最近进展

因为导电高分子结合了金属与塑料的优点,他们一直受到很大的关注。但是他们的应用受到一些因素的影响,包括他们的电学性质,稳定性和可加工性。近来,导电高分子的性能得到很大的提高。他们在许多领域的重要应用被论证,比如透明电极,可拉伸电极,神经界面,热电转换和能量储存。这篇文章简单综述了导电高分子的电导提高和它们在热电转换,超级电容器和电池的应用。     

Polypyrrole coating of inorganic and organic materials by chemical oxidative polymerisation

Polypyrrole is one of the most frequently studied conducting polymers, having high electrical conductivity and stability, suitable for multi-functionalised applications. Coatings of chemically synthesised polypyrrole applied onto various organic and inorganic materials, such as polymer particles and films, nanoparticles of metal oxides, clay minerals, and carbon nanotubes are reviewed in this paper. Its primary subject is the formation of new materials and their application in which chemical oxidative polymerisation of pyrrole was used. These combined materials are used in antistatic applications, such as anti-corrosion coating, radiation-shielding, but also as new categories of sensors, batteries, and components for organic electronics are created by coating substrates with conducting polymer layers or imprinting technologies.     

Conducting polymer hydrogels

Conducting polymer hydrogels are gels, which are swollen with water, and contain a conducting polymer along with a supporting polymer as constituents. Polyaniline, polypyrrole or poly(3,4-ethylenedioxythiophene) represent the conducting moiety, while water-soluble polymers the other part. Various ways of hydrogel preparation are reviewed. The properties, such as mixed electronic and ionic conductivity, redox activity, and responsivity, are conveniently combined with materials properties afforded by supporting polymers, such as elasticity, mechanical integrity, and biocompatibility. The derived materials, aerogels obtained after freeze-drying of hydrogels, or carbogels produced after carbonization of aerogels, are also considered. The applications are expected especially in biomedicine and energy-storage devices but many other uses proposed in the literature are listed and discussed.