掺杂聚苯胺制备及其在水性防腐防静电涂料中的应用

采用过硫酸铵(APS)为氧化剂,在十二烷基苯磺酸(DBSA)微胶束中用化学氧化法制备纳米棒状和球形聚苯胺;DBSA既起乳化剂也起掺杂剂的作用,并用红外光谱(FT-IR)、紫外光谱(UV-vis)、X-射线衍射(XRD)和扫描电镜(SEM)对合成的聚苯胺进行了表征.不同的聚苯胺后处理方式对制备的聚苯胺/水性环氧树脂复合涂层电导率和聚苯胺分散有明显的影响;研究了这些涂膜的耐盐水性能.该复合涂料的表面电导率最大值为10-5S/cm,其他性能满足使用要求.     

聚苯胺/nano-ATO导电复合材料的原位聚合与表征

用原位聚合法,以十二烷基苯磺酸(DBSA)/HC l混酸为掺杂剂,过硫酸胺(APS)为氧化剂,制备了聚苯胺/掺锑二氧化锡(ATO)导电复合材料。探讨了ATO用量对导电复合材料电导率的影响。在n(苯胺)∶n(APS)∶n(DBSA)=1∶1∶0.7,m(ATO)∶m(苯胺)=0.1∶1时,复合材料室温25℃的电导率最高可达8.35 S/cm,比通常方法合成的聚苯胺和nano-ATO的电导率分别提高约1至2个数量级。通过FTIR、XRD、SEM和TEM对目标物进行了表征,结果表明,苯胺优先在ATO纳米粒子表面聚合,形成聚苯胺包覆ATO的导电复合材料。     

CTAB存在下磺基水杨酸掺杂聚苯胺/碳纳米管复合材料的制备与表征

选择十六烷基三甲基溴化铵(CTAB)对碳纳米管进行表面处理,提高了碳纳米管在苯胺溶液中的分散性。在苯胺的盐酸溶液中,以过硫酸铵为氧化剂,磺基水杨酸为掺杂剂,采用化学氧化法制备了聚苯胺/碳纳米管复合材料。用四探针测试仪对产物的电导率进行了测试,结果表明,复合材料的电导率随碳纳米管加入量的增加而增大,当n(碳纳米管)/n(苯胺)=2时,复合材料的电导率为4.613S/cm,是纯苯胺电导率的2.44倍。用扫描电镜(SEM)、透射电镜(TEM)对产物的微观形貌进行了表征,结果表明,聚苯胺包覆在碳纳米管的表面,包覆层的厚度为60～90nm。用紫外光谱(UV-vis)和傅立叶变换红外光谱(FTIR)对产物的结构进行了表征,结果表明,聚苯胺与碳纳米管之间存在较强的相互作用。     

微乳液法制备导电聚苯胺及其在防腐涂层中的应用

采用微乳液聚合法,以十二烷基苯磺酸(DBSA)和盐酸(HCl)为掺杂剂、OP-10为助乳化剂、过硫酸铵为氧化剂,制备了聚苯胺悬浮液。探讨了主要原料用量和工艺参数对聚苯胺电导率的影响,确定最优反应条件为:n(DBSA):n(HCl)=3:2,n(酸):n(苯胺)=2:1,n(氧化剂):n(苯胺)=1:1,m(OP-10):m(苯胺)=2:3,反应时间9 h,反应温度30℃。将所制聚苯胺悬浮液直接与水性环氧乳液混合均匀后加入配套固化剂,通过电化学测量和浸泡试验研究了所得涂层的防腐性能。结果表明其防腐性能相比纯环氧涂层得到非常大的提高。     

原位乳液聚合聚苯胺/聚甲基丙烯酸甲酯复合物及其表征

以DBSA为乳化剂和掺杂剂,在水介质中采用原位乳液聚合法制备出了聚苯胺/聚甲基丙烯酸甲酯(PANI/PMMA)复合物。采用扫描电镜、红外光谱分析、紫外光谱分析、热失重分析、X射线光电子能谱分析对PANI/PMMA复合物进行了表征。结果表明:复合物产物粒径在80～120nm;电导率可达到10-2S/cm,接近于乳液聚合得到的DBSA掺杂态PANI;乳化剂DBSA以掺杂剂和稳定剂两种状态存在于复合物中。     

导电聚苯胺/OMMT纳米复合材料的研究

以十二烷基苯磺酸(DBSA)为掺杂剂和乳化剂,过硫酸铵(APS)为引发剂,采用乳液插层聚合方法制备了导电聚苯胺包覆有机蒙脱土(OMMT)纳米复合材料。探讨OMMT、APS和DBSA用量对复合材料电导率的影响。结果表明,在苯胺、APS、DBSA三者摩尔比为1：1：1．5时,苯胺与OMMT质量比为1：3.5时,复合材料的电寻率最高可达0．0571S／cm。用X射线衍射和傅立叶变换红外光谱对复合材料进行了表征。结果表明,聚苯胺已插层到OMMT层间,且聚苯胺在受限的纳米空间只能以有限层分子存在,很可能是伸展链构象。     

聚苯胺盐的合成及导电性能研究

用对甲苯磺酸作为掺杂剂对聚苯胺(PANI)进行掺杂，合成了导电聚苯胺盐(ES)。研究了掺杂剂用量、模压压力、模压温度、氧化剂用量对聚苯胺盐电导率的影响。结果表明：随着掺杂剂用量的增加，PANI的电导率也在不断的增大；当ES所受压力较高时，电导率提高；高温使PANI电导率上升；氧化剂与苯胺的最佳配比为1：1。     

光固化亲水酸性磷酸酯的合成及其对聚苯胺掺杂行为的研究(一)

以聚(乙二醇)甲基丙烯酸酯、三氯氧磷以及三乙胺等为原料合成光固化亲水酸性磷酸酯(UV-PP),对合成的产物进行表征。以UV-PP为掺杂剂、过硫酸铵(APS)为氧化剂，原位聚合苯胺制备了可光固化的导电聚苯胺分散体。利用红外光谱(FT-IR)、紫外-可见分光光度计(UV-Vis)、X射线衍射(XRD)、四探针电阻测试仪和激光粒度仪对产物进行表征测试，研究了氧化剂与掺杂剂用量对聚苯胺的合成以及掺杂行为的影响。结果表明：当UV-PP与苯胺单体以及APS的物质的量比为9∶3∶1,UV-PP为去离子水质量的10%时，合成聚苯胺分散体的粒径为114.46nm,水溶性最好，在室温下放置6周后粒径大小变化小于70nm,且纯聚苯胺的电导率可达10.36mS/mm。     

乳液聚合法制备聚苯胺及其导电性能

以十二烷基苯磺酸(DBSA)为乳化剂,十六醇(CA)为助乳化剂,盐酸和十二烷基苯磺酸（DBSA）为掺杂剂, 过硫酸铵为引发剂,采用乳液聚合法合成了导电聚苯胺（PAn）.研究了反应温度、反应时间及苯胺、十二烷基磺酸、十六醇、盐酸和过硫酸铵配比对聚苯胺电导率的影响.研究结果表明,较佳的工艺条件为：反应温度为7 ℃,反应时间为6 h,较佳的原料物质的量的比为苯胺∶十二烷基苯磺酸∶十六醇∶盐酸∶ 过硫酸铵=0.05∶0.028∶0.04∶0.01∶0.05;以十六醇为助乳化剂,采用十二烷基苯磺酸和盐酸为掺杂剂,提高了聚苯胺的导电性.同时对聚苯胺导电机理进行了分析.     

苯胺在聚醋酸乙烯酯中的聚合研究

以过硫酸铵为氧化剂,十二烷基苯磺酸为掺杂剂,将苯胺在聚醋酸乙烯酯(PVAc)基质中进行原位氧化聚合,制备导电聚苯胺PAn/PVAc复合材料,采用溶液浇铸法制成可溶性导电复合膜,电导率达10-2s/cm。考察了反应条件对复合膜电导率的影响,并进行了环境稳定性测试,用红外光谱进行了复合膜的结构表征,用扫描电镜对复合膜的表面形态进行了观察。     

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     

Effect of dopant mixture on the conductivity and thermal stability of polyaniline/nomex conductive fabric

Electrically conductive polyaniline (PANI)/[poly(m‐phenylene isophthalamide)] Nomex composite fabric was prepared by in situ polymerization of aniline doped by a mixture of hydrochloride (HCl) and various sulfonic acids such as benzenesulfonic acid (BSA), sulfosalicylic acid (SSA), and dodecylbenesulfonic acid (DBSA); their effect on conductivity and physical properties were then investigated. PANI/Nomex composite fabrics doped by a mixture of protonic acids exhibited higher conductivity than those doped by other single dopants such as camphorsulfonic acid (CSA), p‐toluenesulfonic acid (TSA), BSA, SSA, and HCl. The conductivity of PANI/Nomex fabrics especially doped by a mixture of HCl and DBSA was evenly maintained up to 100°C without depression of mechanical properties of Nomex. Their conductivity was also maintained under extension of the composite fabric. In addition, electrical conductivity of PANI/Nomex fabrics was highly increased by ultrasonic treatment, which facilitated better diffusion and adsorption of aniline by cavitation and vibration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2245–2254, 2002     

Effects of FeCl3/ammonium persulfate composite oxidant and magnetic field on film growth rate of polyaniline doped with dodecylbenzenesulfonic acid

Polyaniline (PANI) doped with dodecylbenzenesulfonic acid (DBSA) was synthesized by emulsion polymerization using FeCl₃/ammonium persulfate (APS) as composite oxidant. The effects of different magnetic field (MF) intensities, the molar ratios of FeCl₃/APS, and the concentrations of DBSA on the film growth rate of PANI were analyzed by using a quartz crystal microbalance (QCM) technique. The film growth rate of PANI increased with increasing MF intensity and the concentration of DBSA. However, the film growth rate of PANI decreased with increasing molar ratio of FeCl₃/APS. The polymerization conditions were optimized tentatively by cyclic voltammetry (CV) testing. The peak currents and conductivity were the largest for PANI prepared under the following conditions: MF intensity 0.4 T, molar ratio of FeCl₃/APS 2:1, and concentration of DBSA 0.05 mol/L. The UV–Vis spectra of the PANI polymerization showed that the absorption intensity of PANI polymerized in the presence of MF was greater than that of PANI polymerized in the absence of MF, at the same reaction time.     

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     

聚苯胺的制备及其导电性能

以苯胺为单体,过硫酸铵为氧化剂,盐酸为掺杂酸,采用化学氧化法制备出盐酸掺杂聚苯胺(PANI-HA),研究了过硫酸铵与苯胺单体摩尔比(n APS:n An)、HCl浓度、反应温度和反应时间对PANI-HA电导率的影响;采用正交分析法研究了各影响因素对PANI-HA电导率的主次关系。结果表明:影响PANI-HA电导率的主次关系为反应温度n APS:n An反应时间HCl浓度;制备PANI-HA的最佳工艺为nAPS:n An=1.0,HCl浓度1.0 mol/L,反应温度10℃,反应时间8 h。     

Aqueous dispersions of DBSA‐doped polyaniline: One‐pot preparation,characterization, and properties study

Aniline was polymerized in the presence of dodecylbenzene sulfonic acid (DBSA) as a functionalized protonic acid, in an aqueous medium to directly synthesize polyaniline (PANI)‐DBSA particles. DBSA acted as a dopant and a surfactant with stabilizing PANI‐DBSA dispersions by formation of strong hydrogen bonds. The NH⁺…SO interactions between the PANI chains and the DBSA appeared at 1026 cm^?1 in Fourier transform infrared (FTIR) spectrum. Elemental analysis was used to determine the degree of sulfonation (S/N ratio) of PANI chains and resulted that the sulfur‐to‐nitrogen ratio is 0.35. Thermogravimetric analysis (TGA) technique was used to analyze thermal properties of the particles and resulted that the synthesized PANI‐DBSA particles have high thermal stability. The moisture, DBSA and PANI contents of the PANI‐DBSA were estimated from TGA curve, and then the number of aniline repeating units doped with one DBSA molecule was approximately calculated. X‐ray diffraction (XRD) analysis confirmed that a chemical crosslinking reaction occurs between the PANI chains during thermal treatment of PANI‐DBSA. The morphology of PANI‐DBSA powder was investigated by scanning electron microscopy technique and showed that the PANI particles develops from round particles to a smooth surface. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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.     

不同酸掺杂聚苯胺的电化学聚合及性能

采用循环伏安（CV）法在镀金PET膜上分别聚合了硫酸（H2SO4）、十二烷基苯磺酸（DBSA）、硫酸-十二烷基苯磺酸掺杂的聚苯胺（PANI）膜,对比研究了掺杂酸种类对PANI结构和性能的影响。结果表明,SO42?、DBSA?可以随聚合过程进入PANI分子链;H2SO4掺杂的PANI具有较高的电导率,但是在空气中的稳定性较差;大分子的DBSA使PANI优先产生单螺旋的纤维,提高了PANI在平行分子链方向上的结晶度和在空气中的稳定性;相对于单一酸掺杂,复合酸掺杂的PANI在酸溶液中电扫描表现出优良的循环伏安特性,在保持较高电导率的同时,提高了PANI在空气中的稳定性。     

Effect of dopant and oxidant on the electrochemical properties of polyaniline/graphite nanoplate composites

Optimizing the synthesis parameters of polyaniline/graphite nanoplate (PANI/GNP) composite is essential to the final electrochemical performance. Herein, the electrochemical properties of PANI/GNP composites, prepared by in situ chemical polymerization using varying amounts of different oxidants, with or without the addition of 4‐dodecylbenzenesulfonic acid (DBSA) as dopant, were investigated. Cyclic voltammetric results suggested that a stoichiometric amount of the oxidant iron chloride (FeCl₃) was beneficial to the electrochemical properties of the composites. The use of ammonium persulfate (APS) instead of FeCl₃ as oxidant largely increased the actual PANI content, conductivity and specific capacitance of the PANI/GNP composites. The dopant DBSA increased the conductivity of the PANI/GNP composites but did not show a positive effect on the electrochemical behavior. The cyclic voltammograms of the PANI/GNP composites indicated that the pseudocapacitance of PANI contributes more than the electrical double‐layer capacitance of GNP to the capacitance of the composites, while the presence of GNP plays an essential role in the rate capability of the composites. In this study, PANI/GNP (1:1) composite synthesized with an APS to aniline molar ratio of 1 showed a balanced combination of high specific capacitance (180.5 F g^?1 at 20 mV s^?1) and good rate capability (78% retention at 100 mV s^?1). © 2018 Society of Chemical Industry