导电聚苯胺在电流变液中的应用

简述了电流变液的研究现状,着重介绍了含聚苯胺粒子电流变液的应用现状及发展前景。     

Electrorheological suspensions

The electrorheological properties of polyaniline suspensions are typical of most electrorheological systems and are a function of many parameters such as suspension concentration, applied field strength and the relative permittivity of the particles. When only one parameter is varied, the suspensions' electrorheological effects increase with increasing concentration of dispersed phase, field strength and particle relative permittivity. The rheograms of the suspensions at different field strengths and concentrations have been studied. The dependence of the dynamic yield stress on particle concentration has also been determined.     

Elastic polyaniline with EPDM and dodecylbenzenesulfonic acid as plasticizers

Elastomeric polyaniline was prepared by being mixed with ethylene–propylene–diene (EPDM) rubber in low concentrations (10, 20, or 30 wt %). The mixture was made in an internal mixer coupled to a torque rheometer. The polyaniline was doped with dodecylbenzenesulfonic acid (DBSA) via reactive processing during the mixing. When the EPDM rubber was added to the polyaniline and DBSA, the doping reaction was not interrupted, as demonstrated by an increase in the torque values. We chose the relative DBSA and EPDM concentrations to obtain the highest conductivities (10⁻¹ to 10⁻³ S cm⁻¹) and the best mechanical properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1768–1775, 2001     

Electrorheological effects of polyaniline‐type electrorheological fluids

Three kinds of particles—polyaniline (PANI), poly(o‐toludine) (POT), and brominated polyaniline (Br‐PANI)—were synthesized. With chlorinated paraffin as a disperse oil, their electrorheological (ER) effects were determined so that the influence of the phenyl substitute group on the ER effects could be considered. POT exhibited the strongest ER effect, whereas the Br‐PANI ER effect was relatively poor. With the concept of polarization, this phenomenon was interpreted. The influence of the antidoping condition on the ER effects was also examined. An optimal antidoping condition was found for each kind of particle. Composite PANI/polyacrylamide (PAAm) and PANI/lithium polyacrylate (PAA‐Li) particles were further prepared by emulsion polymerization. The testing results showed that the composite particles with certain amounts of PAAm or PAA‐Li exhibited good ER effects. The dielectric and conductive behaviors were also determined so that the results could be explained. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 733–740, 2003     

X‐ray photoelectron spectroscopy and electrical conductivity of polyaniline doped with dodecylbenzenesulfonic acid as a function of the synthetic method

X‐ray photoelectron spectroscopy (XPS) has been employed to investigate the protonation degree of polyaniline doped with dodecylbenzenesulfonic acid (Pani. DBSA) obtained by different synthetic methods. The protonation degree has been compared to electrical conductivity. Pani.DBSA prepared through the redoping process in an agate mortar displays conductivity values within the range of 1 S/cm. A protonation level of 48% with almost all imine groups being protonated. Pani.DBSA was also synthesized by oxidative polymerization of aniline in the presence of DBSA, which acts simultaneously as a surfactant and as protonating agent. This in situ doping polymerization was carried out in aqueous or toluene media. In both cases, protonation degrees higher than 50% have been achieved, indicating that a substantial portion of amine units have also been protonated. Higher doping degree has been achieved by aqueous dispersion polymerization of aniline. The C/N and S/N molar ratios obtained by XPS analysis indicate that the polyaniline chains obtained by in situ polymerization are protonated by both sulfonate and hydrogen sulfate anions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 556–565, 2001     

功能酸二次掺杂聚苯胺的防腐蚀性能

聚苯胺具有独特的掺杂脱掺杂特性,能在特定的反应条件下合成出形貌较好的纳米纤维,使得通过脱掺杂和二次掺杂能制备出拥有特殊防腐官能团的新型纳米材料。将硫酸体系中合成的聚苯胺纳米纤维经氨水脱掺杂,再用磷酸、对甲苯磺酸和酒石酸等功能酸在脱掺杂态聚苯胺基础上制备出二次掺杂态聚苯胺,测试了聚苯胺/环氧树脂复合涂层的防腐蚀性能,并与功能酸一次掺杂态聚苯胺进行了对比。结果表明,功能酸掺杂的聚苯胺都有一定的防腐蚀效果;功能酸二次掺杂态聚苯胺比一次掺杂态聚苯胺有更好的防腐蚀性能,二次掺杂态聚苯胺涂层拥有更高的阻抗,其中酒石酸二次掺杂态聚苯胺涂层的阻抗最高,浸泡120 d后为3.48×10⁷ Ω·cm²,较其一次掺杂态聚苯胺涂层高出一个数量级。     

有机酸掺杂聚苯胺的制备及其结构分析

研究了用十二烷基苯磺酸（DBSA）、磺基水杨酸（SSA）、对氨基苯磺酸（ABSA）和柠檬酸（CA）4种有机酸作掺杂剂制备掺杂态聚苯胺DBSA-PANI、SSA-PANI、ABSA-PANI、CA-PANI的工艺,并制备了样品。经FT-IR和SEM分析表明：4种酸均具有掺杂态聚苯胺的特征吸收峰,其中DBSA-PANI和SSA-PANI的掺杂峰更明显;而ABSA和CA掺杂后的聚苯胺为微纳米粒子结构。大尺寸的有机酸离子掺杂在聚苯胺的链间,可更有效地减弱分子间的相互作用使聚苯胺溶解性提高,导电性增加。样品导电性能最好的是磺基水杨酸掺杂的聚苯胺,电导率接近1 S/cm。     

Conductive epoxy/amine system containing polyaniline doped with dodecylbenzenesulfonic acid

We developed a conductive epoxy/amine system containing polyaniline doped with dodecylbenzenesulfonic acid (PAni.DBSA). The curing behaviors of diglycidyl ether of bisphenol A with triethylenetetramine (TETA), PAni.DBSA, and both amine compounds at different concentrations were investigated by differential scanning calorimetry (DSC). Epoxy/TETA systems containing PAni.DBSA presented two distinct exothermic peaks at 90°C due to the cure by TETA as a hardener and at 236°C related to PAni.DBSA as the curing agent. The presence of PAni.DBSA in the systems constituted by epoxy/hardener in stoichiometric proportions resulted in a decrease in the glass‐transition temperature of the epoxy matrix, as indicated by DSC and dielectric analyses. Electrical conductivity was determined in the epoxy/amine networks, with the TETA concentration kept constant and also in stoichiometric proportions of mixed hardener (TETA + PAni.DBSA) to epoxy resin. The last condition resulted in a higher electrical conductivity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:4059–4065, 2006     

十二烷基苯磺酸掺杂聚苯胺的制备及性能

用十二烷基苯磺酸（DBSA）的水溶液对化学合成的聚苯胺（PAn)进行掺杂,获得了导电的DBSA掺杂PAn(PAn-DBSA),通过对本征态聚苯胺（PAnEB)掺杂率的计算和电导率的测定,研究了DBSA用量及其溶液浓度对掺杂效果的影响,结果表明,当DBSA／PAnEB(摩尔比）小于0．1时,溶液浓度的影响很小,当DBSA／PAnEB大于0．2时,溶液浓度的影响非常大,而且,高浓度比低浓度对提高掺杂率和电导率更有利。热重分析表明,PAnEB,PAn-DBSA在空气中的热分解温度分别为350和250℃,表现出良好的热稳定性。     

Facile preparation of conductive paint made with polyaniline/dodecylbenzenesulfonic acid dispersion and poly(methyl methacrylate)

We investigated an easy way to prepare industrially a conductive paint made with polyaniline (PANI)/dodecylbenzenesulfonic acid (DBSA) dispersion and poly(methyl methacrylate) (PMMA) in organic media. First, water‐dispersible PANI doped with DBSA was chemically synthesized with aniline sulfate using ammonium persulfate in water, and the resulting PANI/DBSA was readily extracted from the reaction medium with a mixture of toluene and methyl ethyl ketone (MEK) (toluene:MEK = 1:1 (v/v)), which is useful for industrial applications. The obtained PANI/DBSA organic dispersion was mixed with PMMA organic solution to give the corresponding PANI/DBSA conductive paint containing PMMA. A film prepared with the resulting PANI/DBSA conductive paint was found to possess relatively good conductivity and low surface resistivity for a conductive paint utilized for an electrostatic discharge even at low PANI/DBSA content in the PANI/DBSA–PMMA composite film (the conductivity and the surface resistivity were 9.48 × 10^?4 S cm^?1 and 3.14 × 10⁶ Ω cm^?2, respectively, when the feed ratio of PANI/DBSA:PMMA was 1:39 (w/w)). Furthermore, it was found that the conductivity of the film composed of PANI/DBSA–PMMA composite can be readily and widely controlled by the PANI/DBSA content of the composite or by the amount of DBSA used during the PANI/DBSA synthesis. The highest conductivity of PANI/DBSA–PMMA composite film (7.84 × 10^?1 S cm^?1) was obtained when the feed ratio of PANI/DBSA:PMMA was 1:4 (w/w). Copyright © 2007 Society of Chemical Industry     

One-step preparation of electrorheological suspension containing poly(lithium acrylate) via inverse emulsion polymerization and study of its electrorheological effect

Electrorheological (ER) fluid or suspension containing lithium salt of poly(acrylic acid) were synthesized directly by inverse emulsion polymerization. Effects of the amounts of crosslinking agent and the stabilizer and neutralization degree used in the polymerization, as well as water content of the polymer particles on the ER activity were investigated. The ER suspension exhibited maximum yield stress at optimum amounts of stabilizer and crosslinking agent used in the inverse emulsion polymerization, as well as at optimum water content of the polymer particles. Glycerol was tried to be used as an activator instead of water and was shown to have a favorable effect on the thermal stability of the ER suspension. Core–shell-type polymer particles were synthesized through inverse emulsion polymerization with supplemental addition of a second monomer. The ER suspension containing particles with poly(lithium acrylate) as core and polyacrylamide as shell showed better ER behavior than those without the polyacrylamide shell. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 2169–2174, 1998     

有机酸掺杂聚苯胺的研究进展

聚苯胺是一种非常有前途的导电聚合物。掺杂能提高聚苯胺的导电性、稳定性及其他性能,聚苯胺的掺杂受到了人们的广泛关注,尤其是有机酸的掺杂。有机酸种类众多且性能各异,能够使聚苯胺很多性质发生变化。本文重点综述了分别以单一有机酸、有机酸和金属氧化物、有机酸和无机酸、有机酸和其他无机物为掺杂剂合成聚苯胺的研究现状,详细介绍了各种掺杂态聚苯胺的性能及应用,简要介绍了影响聚苯胺性能的因素,并比较了不同掺杂态聚苯胺的优缺点。分析结果表明：与单一有机酸掺杂的聚苯胺相比,采用两种类型的掺杂剂共掺杂合成的聚苯胺具有更突出的性能及更大的应用前景。提出了采用两种或两种以上不同类型的掺杂剂共掺杂将是聚苯胺今后的主要研究方向。     

Nano titanium oxide organosol: Synthesis,characterization, and application for electrorheological fluid

A liquid–liquid phase transfer method was employed to prepare novel nano titanium oxide/silicone oil organosol. First, titanium oxide nanoparticles were synthesized in aqueous phase and then modified with several surfactants. It is found that only sodium dodecyl benzene sulfonate (SDBS) and sodium dodecyl sulphate (SDS) can cap nanoparticles and then nanoparticles could be transferred into organic phase by the phase transfer method. The transfer process was certified by the rapid change of color for the aqueous and organic phase. Other surfactants including hexadecyltrimethyl ammonium bromide (CTAB) and oleic acid were unable to ensure the phase transfer in the organic phase. The procedure was also verified by high‐resolution transmission electron microscopy (HRTEM), particle size analyzer, UV–vis, etc. The results also showed the narrow size distribution of the nanoparticles. The mechanism of phase transfer is also discussed for different surfactant. Because of its good antisedimentation and high electrorheological effect, organosol is a novel path for the design and application of electrorheological fluid. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of composition on the conductivity and morphology of ligno sulfonic acid sodium salt doped polyaniline

A systematic approach is developed to study the ligno sulfonic acid sodium salt (LSA) protonation or doping process with polyaniline emeraldine base (Pani‐EB) in organic solvents like dimethyl sulfoxide, and the influence of LSA‐doping on the properties of polyaniline was investigated in detail. The composition of Pani‐EB and LSA was varied in the weight ratio of 1:1 to 1:50 to investigate the effect of the dopant concentration on the conductivity and morphology. The doping process was confirmed by UV–vis and FTIR spectroscopes. The composition analysis indicates that only 50% of the LSA is used for the doping process irrespective of the weight ratio of LSA/Pani‐EB in the feed. The four probe conductivity measurement suggests that the conductivity of the doped samples are increasing with the increase in the ratio of Pani‐EB/dopant composition, and the high conductivity of the doped material was obtained in the range of 1.0 × 10^?2 S/cm. Scanning electron microscopy reveals that LSA induces a selective aggregation in the polyaniline chains to produce needlelike or rod‐shape morphology of sizes having ～0.2 μm diameter and 1 μm length. At very higher amount of LSA, the microrods are completely collapsed and form uniform continuous morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2650–2655, 2006     

硅钨酸掺杂聚苯胺催化合成2-异丙基-1,3-二氧环戊烷

采用回流法自制了硅钨酸(H4SiW12O40)掺杂聚苯胺(PAn)催化剂H4SiW12O40/PAn。通过异丁醛和乙二醇为原料合成标题化合物,探讨了硅钨酸掺杂聚苯胺催化剂对缩醛反应的催化活性,较系统地研究了原料物质的量比、催化剂用量、反应时间诸因素对产率的影响。实验表明,硅钨酸掺杂聚苯胺催化剂是合成标题化合物的良好催化剂,在n(乙二醇)∶n(异丁醛)=1.5∶1,催化剂用量为反应物料总质量的1.2%,环己烷为带水剂,反应时间1.0h的优化条件下,标题化合物的收率可达88.8%。     

酸掺杂聚苯胺催化马来酸丁酯化及动力学

用对甲苯磺酸作为搀杂剂对水相氧化法合成的盐酸搀杂的聚苯胺(HC l/PANI)进行搀杂,制备了由聚苯胺(PANI)负载对甲苯磺酸的固体酸催化剂(PTSA/PANI)。以PTSA/PANI为催化剂、马来酸酐和正丁醇为原料合成马来酸二丁酯。考察了原料配比、催化剂用量和反应时间等因素对反应的影响以及催化剂的重复使用性能,测定了反应动力学。最佳反应工艺条件为:n(正丁醇)∶n(马来酸酐)=3.33∶1、w(PTSA/PANI)=3.81%、反应温度≤130℃、反应时间3 h。结果表明,在该条件下马来酸酐的转化率为96.23%;催化剂经重复使用5次后,马来酸酐的转化率为90.82%;确定反应级数为二级,表观活化能为41.0 kJ/mol。对甲苯磺酸搀杂聚苯胺催化剂具有催化活性高、稳定性好、容易制备、无环境污染等优点。     

Organic/inorganic hybrid of polyaniline/BaTiO3 composites and their electrorheological and dielectric characteristics

Barium titanate (BaTiO₃) inorganic particles which possess large electronic resistance and excellent dielectric properties were employed to synthesize conducting polyaniline (PANI)/BaTiO₃ composites via an in situ oxidative polymerization, since conducting PANI/inorganic composites have been considered as a superior candidate of electrorheological (ER) fluids because of their physical properties, unique structure, and the combined merits of the two phases. The influence of the fraction of BaTiO₃ particles in the as‐synthesized composites on the physical properties (morphology and crystal structure) and the ER behaviors were examined. Yield stress data obtained were analyzed based on the universal yield stress equation as a function of applied electric field and it was found that the universal yield stress equation collapses these data onto a single curve independent of BaTiO₃ particle concentration. Their shear stresses under an applied electric field were also found to be fitted well with the Cho–Choi–Jhon model. In addition, the investigated dielectric spectra were found to be useful to interpret the differences in the ER performances for the PANI/BaTiO₃ composite based ER fluids. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

过氧化钨酸-过氧化氢化学聚合法合成掺杂态聚苯胺

在过氧化钨酸-过氧化氢均相催化氧化体系中,在盐酸或对甲基苯磺酸的存在下合成出掺杂态聚苯胺(PANI/HCl和PANI/TSA)。反应终了后,加入碘化钾除去体系中剩余的过氧化氢。产物分离过程中,使用了抽滤法与甲苯-水共沸蒸馏法两种方法。与抽滤法相比,用共沸蒸馏法处理反应后的产物能得到高产率的掺杂态聚苯胺。使用傅立叶红外吸收光谱(FTIR)和紫外-可见光吸收光谱(UV-vis)研究了两种掺杂态聚苯胺的化学构造变化。使用四端子法测定了掺杂态聚苯胺的导电性能,其导电率能达到10-3S/cm数量级。     

不同酸掺杂聚苯胺对THF气体敏感性的研究

分别研究了盐酸(HC l)掺杂的聚苯胺和十二烷基苯磺酸钠-盐酸(SDBS-HC l)掺杂聚苯胺导电薄膜在四氢呋喃(THF)气体中的敏感行为,实验表明,相比盐酸掺杂的聚苯胺薄膜敏感行为,SDBS-HC l掺杂聚苯胺薄膜在四氢呋喃(THF)气体中敏感行为显示出较高的响应度,更好的可逆性和线性,以及快速的响应性。因此,SDBS-HC l掺杂聚苯胺薄膜有望成为一个很好的传感材料。     

Fabrication of DBSA‐doped polyaniline nanorods by interfacial polymerization

An interfacial polymerization was used to fabricate dodecybenzenesulfonic acid (DBSA)‐doped polyaniline (DBSA‐PANI) nanorods with diameter range from 40 nm to 1 μm. The molar ratio of aniline to ammonium peroxydisulfate (APS), the concentrations of DBSA and reaction temperature had an effect on the morphology and size of products. It was found that lower concentration of DBSA and lower temperature will be helpful to the formation of rod‐like PANI nanostructures with a relative small diameter. UV–vis and FTIR measurements were used to characterize the chemical structure of the obtained samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008