3,4-乙撑二氧噻吩合成及其聚合物应用进展

3,4-乙撑二氧噻吩(EDOT)是导电聚合物——聚3,4-乙撑二氧噻吩(PEDOT)的单体。目前，国内EDOT的产量和品质等方面较国外有较大差距。因此，对EDOT的合成工艺进行深入研究有着重要的社会和经济效益。总结了EDOT的主要合成方法及其聚合物在防腐蚀涂层、超级电容器、钙钛矿太阳能电池、水凝胶等领域的应用与发展。     

聚(3,4-乙撑二氧噻吩)/木质素磺酸核壳粒子的制备工艺优化

以过硫酸钠为氧化剂,在木质素磺酸(LS)水溶液中通过化学氧化法聚合3,4-乙撑二氧噻吩(PEDOT),制备聚(3,4-乙撑二氧噻吩)/木质素磺酸(PEDOT/LS)水分散液。研究了木质素磺酸用量、氧化剂添加量、p H值、固含量和反应温度对产物PEDOT/LS的粒径及导电性的影响。实验得出较佳的反应条件是:木质素磺酸与EDOT单体质量比为2.0~2.5:1,氧化剂与EDOT摩尔比为1.3:1,反应体系p H值约1.5,固含量在1.8%~2.5%,反应温度10~20℃。用PEDOT/LS配制得到的涂层,表面电阻小于108??sq?1,光滑透明且附着力达到二级,满足抗静电剂的要求。     

导电高分子PEDOT／PSS保护银纳米颗粒的制备与表征

利用导电高分子聚（3，4-二氧乙基噻吩）／聚（对苯乙烯磺酸）（PEDOT／PSS）作保护剂，制备了银纳米颗粒，用UV-Vis和TEM对其进行了表征．结果表明，选择合适量的PEDOT／PSS保护剂可以得到大小分布较窄银纳米颗粒．     

用聚3,4-乙撑二氧噻吩对聚丙烯腈进行导电改性的研究

采用原位化学氧化聚合方法在聚丙烯腈纤维表面生成聚3,4-乙撑二氧噻吩,制备得到纤维表面均匀覆盖聚3,4-乙撑二氧噻吩的改性导电纤维,其电导率约为1×10-3S/cm。纤维表面与导电聚合物的相互作用改善了原纤维的耐热性能,并对其力学性能没有造成伤害。     

3,4-乙撑二氧噻吩的合成工艺研究进展

聚3,4-乙撑二氧噻吩具有导电率高、热稳定性好、成膜性好的特点。在光伏电池、抗静电与电磁屏蔽等领域具有良好的用途。由于传统的3,4-乙撑二氧噻吩单体合成过程繁杂,导致3,4-乙撑二氧噻吩单体收率低、价格昂贵,至今未得到良好应用。本文介绍了合成3,4-乙撑二氧噻吩单体的最新研究进展,着重讨论了以价廉易得的氯乙酸乙酯为原料,经亲核取代、酯缩合、烷基化、水解与脱羧合成3,4-乙撑二氧噻吩的新"五步法"合成路线。通过对3,4-乙撑二氧噻吩新"五步法"合成路线的分析,总结了各步最优合成方法与条件,为3,4-乙撑二氧噻吩研究开发提供了借鉴。     

4,7-二（2,3-二氢噻吩并[3,4-b][1,4]二噁英-5-基）苯并[1,2,5]噻二唑的合成及其电聚合

聚噻吩的重要衍生物聚（3,4-乙撑二氧噻吩）（PEDOT）是应用最成功的导电高分子聚合物之一。以苯并噻二唑为受体单元,设计合成了前驱体化合物4,7-二（2,3-二氢-噻吩并[3,4-b][1,4]二噁英-5-基）苯并[1,2,5]噻二唑（EDOT-BT-EDOT）,发现其具有优异的桔红色发光性能,对其进行电聚合能够获得相应聚合物材料P（EDOTBT-EDOT）。聚合物材料表现出良好的电化学活性和稳定性以及平整致密的表面形貌。     

聚（3，4-乙撑二氧噻吩）/樟脑磺酸复合材料的合成及其电化学性能

以樟脑磺酸(HCSA)为掺杂剂,FeCl3为氧化剂,通过化学氧化聚合合成了聚(3,4-乙撑二氧噻吩)/樟脑磺酸(PEDOT/HCSA)复合材料;采用FTIR和SEM对其结构和形貌进行了表征;探讨了掺杂剂与单体摩尔比、氧化剂用量和反应时间对产品导电性能的影响;分析了产品的电化学性能。结果表明,当n〔3,4-乙撑二氧噻吩(EDOT)〕:n(樟脑磺酸):n(氯化铁)=2:1:40,反应时间41 h时,复合材料具有良好的导电性能和电化学性能,电导率为10.4 S/cm,经150次充放电老化后比容量可保持在140 F/g左右,是一种潜在的超级电容器电极材料。     

热固化抗静电涂料的制备及性能研究

以聚苯乙烯磺酸钠(PSS)为掺杂剂,过硫酸钠(Na_2S_2O_8)、硫酸铁[Fe_2(SO_4)_3]为氧化剂,聚乙二醇(PEG)为非离子扩散剂,采用氧化EDOT(3,4-乙烯二氧噻吩)法制备水溶性抗静电剂PEDOT(聚3,4-乙烯二氧噻吩);然后加入水性聚氨酯(WPU)分散液(作为基体树脂),制备出热固化的绿色环保型抗静电涂料。研究结果表明:当m(PSS)∶m(EDOT)=2.5∶1、反应时间为18 h、n(—NCO)∶n(—OH)=2.2∶1、w(PEG)=12%(相对于WPU分散液总质量而言)和m(PEDOT)∶m(WPU)=7∶3时,制得的抗静电涂层具有透光率(94.8%)高、表面电阻率(0.022 MΩ)低和耐水性佳等特点。     

新方法合成3，4-乙撑二氧噻吩系列化合物

从2,3-二甲氧基-1,3-丁二烯衍生物出发,微波辐射下采用一锅法成功合成了一系列3,4-乙撑二氧噻吩类化合物.3,4-乙撑二氧噻吩类化合物的结构经13CNMR、1HNMR、IR和元素分析进行了表征.此外,本文讨论了原料的量、催化剂和溶剂对3,4-乙撑二氧噻吩(EDOT)收率的影响.     

聚3,4-乙烯二氧噻吩聚苯乙烯磺酸复合LB膜对有机电致发光器件性能的优化

采用Langmuir-Blodgett(LB)膜诱导沉积法制备聚3,4-乙烯二氧噻吩高度有序导电聚合物复合薄膜,研究了薄膜的导电性能并进一步研究薄膜在改善器件性能方面的作用。将其应用于有机电致发光二极的空穴缓冲层,将聚3,4-乙烯二氧噻吩聚苯乙烯磺酸复合LB膜沉积于铟锡氧化物(ITO)电极上,制备了以复合LB膜为空穴缓冲层的有机电致发光二极。发现复合LB膜改善了器件性能(启动电压降低、最大亮度增加),但进一步的研究表明,LB膜器件在一定时间后出现性能劣化,X射线反射率(XRR)分析表明薄膜的结构发生一定程度的改变,是导致器件性能变差的可能原因。     

Graphene/poly(3,4-ethylenedioxythiophene) hydrogel with excellent mechanical performance and high conductivity

We report a novel and easy route to synthesize a mechanically strong hydrogel composed of graphene and poly (3,4-ethylenedioxythiophene) (PEDOT). 3,4-Ethylenedioxythiophene played the role of reducing agent to convert a highly oxidative graphite oxide (h-GO) to graphene and in situ polymerized itself synchronously on the active sites of the graphene to construct the hydrogel. The content of the carbonyl groups in h-GO was found to have a major impact on the generation of the hydrogel. Also the morphology and the quantity of PEDOT formed in the hydrogel were considered to be the key factors for improving the mechanical performance of the hydrogel. As-prepared enhanced graphene/PEDOT hydrogel displayed a compressive fracture stress as high as 29.6 MPa, a storage modulus about 2.1 MPa at 10 rad/s, a good electrical conductivity of 0.73 S/cm and a high specific capacitance of 174.4 F/g, which make it a potential candidate for a number of technologies such as electrochemical sensor and supercapacitor.     

Preparation of surface initiated polystyrenesulfonate films and PEDOT doped by the films

Various substrates such as glass slides and silicon wafers were modified by styrylethyltrimethoxysilane to attach double bonds to those surfaces. The double bond layer was initiated and capped by benzoyl peroxide (BPO) and 2,2,6,6-tetramethylpiperidirooxy (TEMPO), respectively, to form ‘living’ free radical layer from which polystyrene brushes were grown. The density of double bonds on the surface controlled the orientation of polystyrene brush or film. The polystyrene films were then sulfonated by fuming sulfuric acid (H₂SO₄·xSO₃) to obtain polystyrenesulfonic acid (PSS) films with controlled polymer chain alignment. The lower double bond density led to a lower degree of polymer chain alignment. 3,4-Ethylenedioxythiophene monomer was diffused into PSS film and then polymerized. A conductive polyethylenedioxythiophene (PEDOT)/PSS film was obtained. The films were characterized by four-point probe, AFM and UV-VIS. The conductivity of PSS/PEDOT film measured along the direction which is normal to polymer chain alignment, is lower than that from commercial PSS/PEDOT.     

Copolymer from electropolymerization of thiophene and 3,4-ethylenedioxythiophene and its use as cathode for lithium ion battery

Electropolymerizations (EPs) of thiophene (Th), 3,4-ethylenedioxythiophene (EDOT) and the mixed monomers of Th and EDOT in 0.05 M Et₄NClO₄/propylene carbonate (PC) solution were performed to prepare polymer films as potential cathode materials in lithium ion battery. The incorporation of EDOT units into pure polythiophene (PTh) chain leads to large alternations on the experimental conditions of EPs and the properties of the resulting polymer films. Onset potential of the EPs was reduced with the participation of EDOT component. The resulting polymers, PTh, poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(thiophene-co-3,4-ethylenedioxythiophene) (PTh-EDOT) were then served as cathode materials to test their capabilities to transport lithium ion in 1.0 M LiPF₆/ethylene carbonate/dimethyl carbonate solution. With the inherent EDOT unit, PEDOT and PTh-EDOT have better charge capacity, stability and response rate than pure PTh. Among the copolymers, PTh-EDOT (1/1) even shows better stability than pure PEDOT homopolymer, advantage of using EDOT as copolymer component is thus evaluated.     

Synthesis and electro-optical properties of a new copolymer based on EDOT and carbazole

A new copolymer of 3,4-ethylenedioxythiophene (EDOT) and 5-(2-ethylhexyl)-1,3-bis(9-methyl-9H-carbazol-3-yl)-5H-thieno[3,4-c]pyrrole-4,6-dione (CzPDICz) was electrochemically synthesized using different monomer feed ratios. The resulting copolymer films were investigated in terms of their electrochemical and electro-optical behaviors. Properties of the obtained copolymer films through different monomer feed ratios were compared to each other and to individual poly(ethylenedioxythiophene; PEDOT) and homopolymer of CzPDICz in order to observe the differences in the properties with respect to PEDOT and P(CzPDICz). Copolymers exhibited well adherence on the electrode surface with having non-diffusional redox process. The monomer feed ratios were prepared as 9:1; 4:1, and 1:1 (EDOT:CzPDICz) and changes in the electrochemical and spectroelectrochemical behavior were noted with increasing CzPDICz ratio in the monomer mixture. Although no appreciable change in the optical band gap values of the copolymers was noted as compared to PEDOT, the neutral blue copolymers exhibited grayish color in their semi-oxidized states and transparent green in their fully oxidized states.     

Electrochemical immobilization of ascorbate oxidase in poly(3,4‐ethylenedioxythiophene)/multiwalled carbon nanotubes composite films

Immobilization of ascorbate oxidase (AO) in poly(3,4‐ethylenedioxythiophene) (PEDOT)/multiwalled carbon nanotubes (MWCNTs) composite films was achieved by one‐step electrochemical polymerization. The PEDOT/MWCNTs/AO modified electrode was fabricated by the entrapment of enzyme in conducting matrices during electrochemical polymerization. The PEDOT/MWCNTs modified electrodes were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The experimental results showed that the composite films exhibited better mechanical integrity, electrochemical activity, higher electronic and ionic conductivity, and larger redox capacitance compared with pure PEDOT films, which would be beneficial to the fabrication of PEDOT/MWCNTs/AO electrochemical biosensors. The scanning electron microscopy studies revealed that MWCNTs served as backbone for 3,4‐ethylenedioxythiophene (EDOT) electropolymerization. Furthermore, the resulting enzyme electrode could be used to determine L ‐ascorbic acid successfully, which demonstrated the good bioelectrochemical catalytic activity of the immobilized AO. The results indicated that the PEDOT/MWCNTs composite are a good candidate material for the immobilization of AO in the fabrication of enzyme‐based biosensor. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

导电聚合物PEDOT/PSS-MPEG的制备及性能

引言导电高分子既有导体材料的光电学特性,又有良好的力学性能和可加工性[1],这使得导电高分子材料具有广泛的应用前景。聚噻吩类有机导电材料[2]就是这类材料中的一种。聚噻吩的室温电导率     

Synthesis of poly(3,4‐ethylenedioxythiophene) nanoparticles via chemical oxidation polymerization

Poly(3,4‐ethylenedioxythiophene) (PEDOT) nanoparticles were synthesized via chemical oxidation polymerization using 3,4‐ethylenedioxythiophene as the starting monomer and ammonium peroxydisulfate (APS) as the oxidant. The effects of APS concentration, surfactant concentration and type of surfactant, namely dodecylbenzenesulfonic acid and sodium dodecylsulfate, were investigated. Distinct particle shapes were obtained: irregular, raspberry agglomerate, coralliform, orange‐peel, globular and plum shapes. The particle sizes and the electrical conductivity are in the ranges 60 to 900 nm and <1 to 153 S cm^?1, respectively, depending on the polymerization conditions. PEDOT synthesis in the absence of a surfactant yields a smaller particle size because a larger amount of initiator induces lower molecular weights and smaller PEDOT particles. The smaller PEDOT particles correspond to higher electrical conductivity because of the larger surface areas for electron transfer and a smaller amount of obstructing surfactant aliphatic segments. Moreover, particle size and shape can be varied, depending on surfactant type and concentration which dictate the micellar shapes in the polymerization reaction. This work is focused on the tailor‐made PEDOT shape and property relationship under synthesis conditions where several shapes have not been previously seen. © 2013 Society of Chemical Industry     

聚3,4-乙烯二氧噻吩/聚苯胺复合材料的制备与性能

以过硫酸铵(APS)和FeCl3为复合氧化剂,采用原位化学氧化聚合法合成了导电聚3,4-乙烯二氧噻吩/聚苯胺(PEDOT/PANI)复合材料,研究了苯胺浓度及加入时间、复合氧化剂配比和复合乳化剂配比对复合材料性能的影响,并对复合材料进行了分析. 结果表明,PEDOT/PANI复合材料合成的较佳工艺条件为：3,4-乙烯二氧噻(EDOT) 0.6 mol/L、复合氧化剂 0.6 mol/L(FeCl3:APS=1:2, mol)、复合乳化剂 0.4 mol/L(SDBS:CTAB=2:3, mol)、复合掺杂剂1.2 mol/L(H2SO4:SSA=4:1, mol)及苯胺0.8 mol/L, EDOT聚合2 h后加入苯胺溶液继续反应8 h. 复合材料的导电性、结晶性和热稳定性比纯导电聚合物好.     

Effects of alcoholic solvents on the conductivity of tosylate‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT‐OTs)

The effects of alcoholic solvents on the charge transport properties of tosylate‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT‐OTs) are investigated. The use of different alcoholic solvents in the oxidative chemical polymerization of 3,4‐ethylenedioxythiophene (EDOT) with iron(III)‐p‐tosylate led to a change in the electrical conductivity of PEDOT‐OTs. For example, PEDOT‐OTs prepared from methanol shows a conductivity of 20.1 S cm^?1 which is enhanced by a factor of 200 as compared to PEDOT‐OTs prepared from hexanol. The variation of charge transport properties on the use of different alcoholic solvents is consistent with the data recorded by UV‐visible and electrospin resonance (ESR) measurements. From XPS experiments, the PEDOT‐OTs samples prepared from different alcoholic solvents were found to have almost the same doping level, suggesting that the number of charge carriers is not responsible for the change in conductivity. Supported by XRD results, it was found that the use of alcoholic solvents with shorter chain length induces more efficient packing of PEDOT chains. It is proposed that the alcoholic solvents associated with the counter ion of PEDOT via hydrogen bonding give rise to a change in the molecular ordering of PEDOT chains during the polymerization step, hence enhancing or depressing the inter‐chain hopping rate of the resulting PEDOT‐OTs. Copyright © 2005 Society of Chemical Industry