Electrochemical synthesis and study of polydiphenylamine

The electrochemical oxidation of diphenylamine in acetonitrile produces an adherent conducting polymer film at the electrode. Conductivity measurements on pressed pellets of this polymer give a room temperature conductivity of 10 S cm⁻¹. The polymer can be cycled between 25 and 200°C without deterioration in the conductivity. Preliminary SEM/EDS studies suggest that there is one BF⁻₄ counter ion for every four monomer units in the oxidised polymer film.     

乙撑二氧噻吩在中性水溶液中的电化学聚合及行为研究

本文研究了乙撑二氧噻吩在中性水溶液中的电化学聚合过程以及聚乙撑二氧噻吩膜的电化学行为, 利用光电子能谱和红外光谱等方法对聚合物膜进行了表征, 研究表明在中性水溶液中制成的聚乙撑二氧噻吩膜修饰电极具有较好的电化学行为和稳定性。     

硫醇自组装膜对金电极上吡咯电化学聚合的影响

用电化学聚合法在多种烷基硫醇自组装膜修饰金电极上制备了聚吡咯.通过计时安培法、循环伏安法和交流阻抗技术研究了自组装膜的烷基链长和端基功能团对吡咯聚合过程和性质的影响.当自组装膜较完美时,聚吡咯沉积在自组装膜表面;而当自组装膜有一定缺陷时,吡咯在针孔处成核,然后继续生长并完全覆盖在自组装膜表面.研究结果表明,烷基硫醇的链越短,吡咯聚合越容易;疏水的烷基硫醇自组装膜有利于聚吡咯在电极表面的生长.     

电化学聚合漆酚铜配合物催化引发醋酸乙烯酯聚合的研究

将电化学聚合方法得到的聚合漆酚 (EPU)与氯化铜异丙醇溶液作用生成电化学聚合漆酚铜配合物(EPU Cu2 + ) .采用顺磁共振波谱 (ESR)、红外光谱 (FT IR)、XPS光电子能谱、原子发射光谱 (AES)、元素分析及AES等手段进行表征 ,确定该配合物的结构即每个铜离子与EPU分子中二个链节单元的羟基发生配位 .配合物中铜含量达 8 6 3% .实验表明 ,电化学聚合漆酚铜 (EPU Cu2 + )配合物膜在室温下的Na2 SO3水体系 (pH =7)中能催化引发醋酸乙烯酯 (VAc)按自由基加聚反应历程进行聚合 .讨论了温度、Na2 SO3浓度、VAc浓度和EPU Cu2 + 膜用量对聚合速率、诱导时间的影响 ,求得聚合速率的表达式Rp=0 0 7e- 2 82 5 RT[VAc]1 54[Na2 SO3]0 5,实验结果表明 ,EPU Cu2 + 配合物膜催化引发醋酸乙烯酯 (VAc)聚合的诱导期为 12 2s ,反应 2 4h后PVAc得率为79% , Mw =1 2 6× 10 6 , Mn=2 6 3× 10 5,多分散性系数为 4 79.     

Electrochemical formation of cation-exchanging polypyrrole films within various hydrophilic–hydrophobic domains

The electrochemical polymerization technique has been successfully applied to produce conducting polymer film of controlled ion exchange properties. Polypyrrole films were prepared by electro-oxidative polymerization with doping some alkylsulfonates or Nafion. The ion exchange characteristics across polypyrrole films were examined by means of a novel electrochemical technique, namely, the in situ electrochemical quartz crystal microbalance (EQCM) method. According to EQCM measurements, exchanging ion species was found to be successfully controlled by changing the hydrophilic–hydrophobic balance of the incorporated sulfonated-based dopants. The film's characteristics became anion- to cation-exchanging as the dopants became more hydrophobic in nature. The polypyrrole–Nafion(poly(perfluoroethylene sulfonate)) composite film became to be a complete cation exchanger.     

水溶液中噻吩的电化学聚合成膜

本文研究水溶液中噻吩的电化学聚合。高酸度水溶液中噻吩先经历化学低聚反应,低聚合物可在较负的电位阳极氧化成膜。     

多色显示电致变色聚合物叠层复合薄膜的可控制备

在氧化铟锡透明导电玻璃(ITO)电极上电化学聚合依次得到聚4,4',4″-三[4-(2-联噻吩基)苯基]胺(PTBTPA)和聚3,4-乙烯二氧噻吩(PEDOT)薄膜, 从而可控制备出叠层复合薄膜. 由红外光谱(FTIR)和场发射扫描电镜(SEM)表征了复合薄膜. 紫外-可见吸收光谱和电化学测试结果表明, 相对于PTBTPA薄膜(中性态橙色到氧化态深灰色)与PEDOT薄膜(中性态深蓝色到氧化态浅蓝色)的颜色变化, 叠层复合薄膜在不同的电压下能够展现出从橙色→蓝色→墨绿色的颜色变化, 并保持了较好的电化学活性和光学对比度. 这主要源于中性态吸收光谱和颜色显示互补的电致变色材料的选择. 本文提供了一种简单有效的制备多色乃至全色显示的电致变色材料的方法, 该方法同样适用于其它聚合物电致变色材料体系.     

电化学合成吡咯与己内酰胺导电共聚物

采用恒电位方法实现了吡咯与己内酰胺在导电玻璃电极上的直接电化学共聚,聚合反应在含有0.1mol/L吡咯和1.5 mol/L己内酰胺的硝基甲烷电解质溶液中进行,外加电位控制在1.2 V以上.聚合产物中聚吡咯与聚己内酰胺链段的组成可通过调节合成电位加以控制.共聚物的形貌、结构与性质采用扫描电子显微镜、热重分析、红外光谱等手...     

Oxidative polymerization of diphenylamine: A mechanistic study

The mechanism of oxidative polymerization of diphenylamine is considered. The kinetic study of diphenylamine polymerization and of the structure and molecular-mass characteristics of the reaction products has shown that the degree of oxidation of intermediates plays the key role in polyrecombination. The relationship between the polymerization procedure and the molecular mass of polydiphenylamine was revealed.     

The Electrochemical Polymerization of Thiophene in Aqueous Sotations of an Acid

People are more and more interested in polythiophene because of its night stability.At present,organic solvent system is still commonly used in electrochemical polymerization of thiophene and the related electrochemical studies.However,it is more practical to use aqueous solutions instead of organic solvents.The electrochemical polymerization of thiophene in aqueous solution of acid is discussed in this paper.In highly concentrated acidic solution,thiophene first undergoes low polymerization,and then the low polymer can be oxidized at the comparatively negative potential to form film.     

Electrochemical synthesis and characterization of polydiphenylamine

Electrochemical oxidation of diphenylamine(DPA)in acetonitrile solution producedan adhesive conducting polydiphenylamine(PDPA)film on the electrode,which exhibited multiplecolour variation in a wide range of potential.The polymer was characterized by cyclic voltam-merry,FTIR and ESR.The results indicate that the electropolymerization of diphenylamine per-forms via the 4,4＇C—C phenyl-phenyl coupling mechanism.FTIR,ESR and conductivity mea-surements for the different states of PDPA show that polydiphenylamine can be reversibly dopedand dedoped either chemically or electrochemically.It is evidenced also that there are paramagneticspecies—polarons in PDPA supposed to be the current carrier.     

红外光谱法研究苯胺和环氧丙烷的共聚机理及共聚物的表征

采用原位红外光谱技术对苯胺和环氧丙烷的电化学共聚机理进行了研究, 研究结果表明, 环氧丙烷能在苯胺及其低聚物阳离子自由基的催化作用下发生α位开环, 与苯胺发生电化学共聚, 生成了含有芳香-脂肪醚结构的共聚物. 采用显微红外成像技术研究苯胺和环氧丙烷共聚物在电极表面的生长特点发现, 该共聚物能在电极表面从中间向两侧有规律地生长.     

电化学聚合漆酚铜配合物的结构及其催化性能

 将电化学聚合法得到的聚合漆酚（EPU）与氯化铜的异丙醇溶液作用制成了电化学聚合漆酚铜配合物（EPU－Cu2＋）,并用顺磁共振波谱、红外光谱、X射线光电子能谱、动态机械热分析和原子发射光谱等手段进行了表征．结果表明,该配合物中每个铜离子与EPU分子中二个链节单元的羟基发生配位,铜含量达8．63％．实验结果还表明,该配合物在Na2SO3的水体系（pH＝7）中能催化引发MMA按自由基反应历程进行聚合．     

Electrochemical fabrication of novel fluorescent polymeric film: Poly(pyrrole–pyrene)

We describe herein the electrochemical characterization and polymerization of 4-pyren-1-yl-butyric acid 11-pyrrol-1-yl-decyl ester (pyrrole–pyrene) in CH₃CN. The electrochemical oxidation of the pyrrole group at 0.77 V vs Ag/Ag + 10 mM in CH₃CN led to the first example of a fluorescent polypyrrole film. The mechanism of deposition on platinum electrode was studied by voltammetry and chronoamperometry. The optical properties of the polymeric films electrogenerated on ITO electrodes were examined by UV–visible spectroscopy and fluorescence microscopy indicating an increase in fluorescence properties by increased polymer thickness. The electrochemical oxidation of pyrenyl group linked to the polypyrrole backbone was carried out at 1.2 V. This additional polymerization was demonstrated by UV–visible spectroscopy and induced the loss of the fluorescence properties of the resulting polymeric film.     

聚藏红T修饰电极的制备及对多巴胺的电催化性能

用循环伏安法在石墨电极和ITO导电玻璃上制备了藏红T聚合物薄膜修饰电极,研究了电聚合过程及循环伏安性质.聚藏红T膜修饰石墨电极在pH 6.81的PBS中循环扫描,有两对氧化还原峰,峰电位分别为Ep,a(P1)=-0.5 V,Ep,c(P1)=-0.575 V,Ep,a(P2)=-0.36 V,Ep,c(P2)=-0.425 V,而且聚合物较稳定.测定了聚藏红T膜的可见光谱性质.实验表明,聚藏红T膜修饰电极对多巴胺有明显的催化作用.     

An electrogenerated poly(pyrrole-benzophenone) film for the photografting of proteins

A photoreactive organic polymer was prepared by oxidative electrochemical polymerization of a pyrrole-benzophenone derivative on conductive surfaces; the resulting polypyrrolic film allowed, upon irradiation, the reagentless covalent grafting of proteins.     

The influence of polymer morphology on polymer film electrochemistry

The electrochemical behavior of functionalized polystyrene-coated electrodes shows a marked dependence on the nature of the electrolyte ions. Scanning electron microscope and surface profile measurements are presented which show that changes in polymer film volume and morphology accompany electrochemical oxidation. Changing polymer morphology by doping the films with soluble monomers during preparation is shown to produce large changes in electrochemical response. Diffusion coefficients were determined for a neutral organic dye dopant in each of the polymer films investigated, and these correlate very well with the oxidation overpotentials observed electrochemically. The nature of polymer film/solvent interactions and the mechanism by which counter ions penetrate the polymer phase is discussed and is related to other physical properties of amorphous polymers in terms of free volume concepts.     

Electropolymerization of 1-naphthylamine and the structure of the polymer film

The electrochemical polymerization of 1-naphthylamine in acetonitrile solution was studied by cyclic voltammetry. Infrared spectroscopy, elemental analysis and quantum chemical calculation were used to investigate the polymer film formed. The results showed that in an acetonitrile solution containing sodium perchlorate and hydrochloric acid, the polymerization of 1-naphthylamine occurred at thep-position. A possible structure of poly(1-naphthylamine) is suggested.     

New Approaches to Synthesizing Electroactive Polymers

The chemical oxidative polymerization of aniline in a heterophase system is studied. In the presence of a solid substrate, the aniline polymerization involves two kinetically and chemically independent processes, namely, the polymerization in the bulk solution and at the substrate surface. The growth of the polyaniline coating at the substrate surface includes three successive processes: interfacial polymerization, adsorptive polymerization, and destruction of the polymer chain. The interfacial oxidative polymerization of diphenylamine and phenothiazine is examined. The yield and chemical structure of polymers is shown to depend on the polymerization conditions.     

Investigation of conductivity and morphology of poly(diphenylamine-co-aniline) prepared via chemical and electrochemical copolymerization

Conductive poly(diphenylamine-co-aniline) was prepared by electrochemical and chemical oxidative polymerization. Using the electrochemical method, homo- and copolymer thin films with different feed ratio of aniline and diphenylamine were synthesized under cyclic voltammetric conditions in aqueous sulfuric acid on the surface of the working Glassy carbon electrode. The copolymer formation, their electrochemical behavior and the structure were examined. The analogous homo- and copolymers were prepared via a chemical oxidative polymerization by the interfacial method (chloroform and an aqueous solution) in 1M H₂SO₄ or 1M CH₃SO₃H in the presence of ammonium persulfate as an oxidant. SEM and conductivity measurements were applied for the characterization of the obtained copolymers.