聚(3,4-乙撑二氧噻吩)复合材料的制备及性能研究

以带亲水基的四种不同的磺酸为掺杂剂,通过化学氧化聚合制备了相应的聚(3,4-乙撑二氧噻吩)(PEDOT)复合材料,通过红外色谱和SEM进行表征,对比测试了掺杂剂种类用量、氧化剂的配比以及反应时间等影响因素对产品电导性的影响。结果表明,以樟脑磺酸作掺杂剂的PEDOT的复合材料空间结构特殊,导电性最好。     

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。     

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.     

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。     

双电离子导电聚合物复合材料

正本发明提供一种复合材料,包括导电聚合物,例如聚(3,4-乙二氧基噻吩)(PEDOT)和离子导电聚合物,例如聚(环氧乙烷)(PEO)。该复合材料形成用于包括锂离子电池在内的电化学应用中的三维电极的双导体。     

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.     

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。     

微波辐射下一锅法合成3,4-乙撑二氧噻吩类化合物

首次从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.实验表明,该法具有反应条件温和、收率高和操作简单的优点.3,4-乙撑二氧噻吩类化合物的结构经 ~1HNMR 、~13CNMR、IR和元素分析进行了表征.也讨论了原料的量、催化剂和溶剂对3,4-乙撑二氧噻吩(EDOT)收率的影响.     

聚乙撑二氧噻吩/二氧化硅复合材料制备及导电性研究

以表面含磺酸基团的改性二氧化硅纳米微球为填料,以三氯化铁(FeCl3)为氧化剂,对甲苯磺酸钠(TSANa)为掺杂剂,氧化聚合乙撑二氧噻吩(EDOT),制备了具有良好导电性的PEDOT/SiO2复合材料。并利用X射线光电子能谱(XPS)、扫描电子显微镜(SEM)和四探针等手段进行了表征。结果表明:当FeCl3与EDOT的摩尔比为0.8,TSANa的质量分数为10%,反应时间为4 h,得到的复合材料具有较高的电导率。     

The structure and properties of PEDOT synthesized by template-free solution method

In this study, a simple one-step template-free solution method was developed for the preparation of poly(3,4-ethylenedioxythiophene) (PEDOTs) with different morphologies by adjusting various ratios of oxidant (FeCl₃·6H₂O) to monomer (3,4-ethylenedioxythiophene (EDOT)). The results from structural analysis showed that the structure of PEDOT was strongly affected by the oxidant/monomer ratio, and the polymerization degree, conjugation length, doping level, and crystallinity of PEDOT decreased with increasing of the oxidant/monomer ratio. The morphological analysis showed that PEDOT prepared from an oxidant/monomer ratio of 3:1 displayed a special coral-like morphology, and the branches of ‘coral’ would adjoin or grow together with increasing content of oxidant in the reaction medium; consequently, the morphology of PEDOT changed from coral to sheets (at an oxidant/monomer ratio of 9:1). The electrochemical analysis proved that the PEDOT prepared from an oxidant/monomer ratio of 3:1 had the lowest resistance and the highest specific capacitances (174 F/g) at a current density of 1 A/g with a capacity retention rate of 74% over 1,500 cycles, which indicated that the PEDOT with a coral-like morphology could be applied as a promising electrode material for supercapacitors.     

Facile synthesis and light scattering characteristics of polystyrene/poly(3,4-ethylenedioxythiophene) nanocomposite particles

Polystyrene/poly(3,4-ethylenedioxythiophene) (PS/PEDOT) nanocomposite particles with uniform size and well-defined morphology have been synthesized using the proposed strategy, which involves swelling of 3,4-ethylenedioxythiophene (EDOT) into PS seed particles, followed by its diffusion and polymerization on the PS surface. This process affords much more effective control over the structure and morphology of the resultant nanocomposites by changing the EDOT/PS weight ratio, reaction temperature, and the rate of addition of the doping acid. The PS/PEDOT nanocomposite particles have been extensively characterized using transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), elemental microanalyses and X-ray photoelectron spectroscopy (XPS). Furthermore, the correlation between nanostructure of the resultant nanocomposite particle and its electromagnetic response performance (e.g., mass extinction effect in infrared region) was investigated.     

Electrical conductivity of poly(3,4-ethylenedioxythiophene):p-toluene sulfonate films hybridized with reduced graphene oxide

Reduced graphene oxide-poly(3,4-ethylenedioxythiophene):p-toluene sulfonate (rGO-PEDOT:PTS) hybrid electrode films were synthesized directly on a substrate by interfacial polymerization between an oxidizing solid layer and liquid droplets of 3,4-ethylenedioxythiophene (EDOT) produced by electrospraying. The EDOT reduced the graphene oxide by donating electrons during its transformation into PEDOT:PTS, and hybrid films consisting of rGO distributed in a matrix of PEDOT:PTS were obtained. These rGO-PEDOT:PTS hybrid films showed excellent electrical conductivities as high as 1,500 S/cm and a sheet resistance of 70 Ω sq^-1. The conductivity values are up to 50% greater than those of films containing conductive PEDOT:PTS alone. These results confirm that highly conductive rGO-PEDOT:PTS hybrid films can potentially be used as organic transparent electrodes.     

Influence of different organic solvents and oxidants on insulating and film-forming properties of PEDOT polymer

Processing of conjugate polymers has always been a challenge because of their poor solubility and infusibility in organic and inorganic solvents. The processibility and applications of intrinsically conductive polymers can be enhanced by producing their solutions or dispersions in different suitable solvents. It can also be achieved by preparing undoped or electrically neutral polymers, which can further be transformed in a semiconductor after an oxidation/reduction reaction. The present study focuses on the preparation of active dispersions of poly(3,4-ethylenedioxythiophene) (PEDOT) conductive polymer in various organic solvents. For this purpose, the polymerization of 3,4-ethylenedioxythiophene (EDOT) monomer was carried out in three different organic solvents, ethanol, 1-butanol, and acetonitrile, with two commonly used oxidants, ferric(III) chloride and ferric(III) p-toluenesulfonate. In this regard, the oxidant and monomer solutions with variable molar concentrations (0.25, 0.5, and 1.0 M) were prepared in particular solvents and then the solutions were mixed with different monomer/oxidant volume ratios. The obtained dispersions of PEDOT can readily be polymerized on the surface of different materials after solvent evaporation and a uniform film can be achieved. The effect of molar as well as volume concentrations of EDOT monomer and oxidant on insulating (undoped/neutral) and film-forming properties of PEDOT was investigated. These dispersions were applied on a transparent PET film and cellulosic fibers (viscose), dried at room temperature and analyzed using scanning electron microscope, optical microscope, and ATR-FTIR spectroscopic analysis. The electrical characterization of undoped PEDOT-coated fibers was performed on Keithley Picoammeter. This study contributes to obtaining a simpler and instantaneous polymerization method of PEDOT preparation and enhancing its application area.     

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.     

The influence of poly(3,4-ethylenedioxythiophene) modification on the transport properties and fuel cell performance of Nafion-117 membranes

Nafion-117/PEDOT composite membranes were synthesized by in situ chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) using ammonium persulfate as an oxidant. The polymerization of EDOT in Nafion membranes for various EDOT/oxidant treatment sequences was studied for the first time. PEDOT introduction leads to a slight decrease in both the ion-exchange capacity and water uptake of the composite membranes, as well as to an increase in cationic transport. Membranes initially treated with an oxidant exhibit better conductivity and lower hydrogen permeability. The effect of both modification of Nafion-117 membranes by PEDOT and hot-pressing of hydrogen-oxygen membrane-electrode assemblies (MEAs) on the performance of proton-exchange membrane fuel cells was studied. The maximum power density of the fabricated MEAs increases 1.5-fold: from 510 (for a pristine Nafion-117 membrane) to 810 mW cm⁻² (for a membrane modified by PEDOT). The current density at a voltage of 0.4 V reaches 1248 and 2246 mA cm⁻², respectively.     

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.     

Truly solid state electrochromic devices constructed from polymeric ionic liquids as solid electrolytes and electrodes formulated by vapor phase polymerization of 3,4-ethylenedioxythiophene

Using polymeric ionic liquids, namely poly[1-(2-(2-(2-(methacryloyloxy)ethoxy)ethoxy)ethyl)-3-methylimidazolium]bis(trifluoromethylsulfonyl)imide or tetracyanoborate, and poly(3,4-ethylenedioxythiophene) (PEDOT) as an ion conductor and electrodes, respectively, the all-polymer-based thin-film symmetrical electrochromic devices (ECDs) have been constructed and tested. The proposed architecture serves as a prove of concept that polymeric ionic liquids (PILs) can be themselves used as solid electrolytes thus avoiding any electrolyte leakage since the ionic liquid species are grafted on the polymer backbone. Three different methods for the synthesis of PEDOT electrode films, including two new approaches consisted in vapor phase polymerization of 3,4-ethylenedioxythiophene (EDOT) in the presence of ionic monomer and poly(ethylene glycol)(di)methacrylates, have been investigated. Two oxidants, Fe[(CF₃SO₂)₂N]₃ and Fe[(CN)₄B]₃, bearing the same anions as PILs were prepared for the first time and utilized in the vapor phase polymerization of EDOT. It was found that the more compact structure and the highest conductivity are achieved for PEDOT electrodes prepared by vapor phase polymerization of EDOT in the presence of ionic monomer and poly(ethylene glycol)(di)methacrylates, followed by radical polymerization of the latters. The simplicity of ECDs assembly, their fast switching times (3–5 s), high coloration efficiency (up to 430 cm²/C), satisfactory optical contrast (up to 28.5%), absence of any liquids and good performance in air and in vacuum were found among the advantages of the proposed technology.     

Characterization and conversion determination of stable PEDOT latex nanoparticles synthesized by emulsion polymerization

In this research, poly(3,4-ethylenedioxythiophene) (PEDOT) latex nanoparticles with good colloidal stability were prepared by emulsion polymerization and the conversions of EDOT were determined. Two kinds of oxidants, Iron(III) p-toluenesulfonate Fe(OTs)₃ and hydrogen peroxide H₂O₂, were introduced to decrease the use of iron salt and therefore reduce the particle coagulation. The ferrous ions (Fe²⁺) produced during the polymerization would be re-oxidized back to the reactive ferric ions (Fe³⁺) with the help of H₂O₂. This cyclic oxidation-reduction process resulted in the sustained regeneration of Fe³⁺ ions and led to a higher conversion. A dark blue PEDOT latex with long-term dispersion stability was obtained when Fe(OTs)₃ and H₂O₂ were added in sequence. The results obtained from dynamic light scattering and TEM measurements showed that the sizes of nanoparticles were around 100 nm. To determine the conversion of EDOT, two methods (gravimetric analysis and UV-visible method) were used and compared. For the first time, the UV-visible method was established to quantitatively determine the conversion of EDOT monomer. From the measurement, the conversion of EDOT in this system was determined as 74-75%. The PEDOT film prepared by drying the latex solution had conductivity up to 6.3 S/cm.