掺杂态聚苯胺的制备与表征

以本征态聚苯胺为原料,以盐酸、硫酸、5-磺基水杨酸、对甲苯磺酸和十二烷基苯磺酸为掺杂酸,制备出盐酸掺杂聚苯胺、硫酸掺杂聚苯胺、5-磺基水杨酸掺杂聚苯胺、对甲苯磺酸掺杂聚苯胺和十二烷基苯磺酸掺杂聚苯胺。对掺杂态聚苯胺的结构、电导率、溶解性和热稳定性进行测试,分析了掺杂酸对本征态聚苯胺的结构与性能的影响。     

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。     

SSA-PANI/ATP导电纳米复合材料的制备和表征

用原位聚合法在凹凸棒土（ATP）的表面包覆上5-磺基水杨酸（SSA）掺杂的聚苯胺（PANI）,合成了SSA-PANI/ATP纳米复合材料,研究了SSA掺杂量、聚合温度、苯胺包覆率、聚合时间和过硫酸铵（APS）用量对复合材料体积电阻率的影响。结果表明：在m（An）∶m（APS）∶m（ATP）∶m（SSA）=1∶2.45∶3.33∶2.08,聚合温度为20℃,聚合时间为4 h时,复合材料体积电阻率可达到3.5Ω.cm。并通过TG-DTA、XRD、FTIR和TEM对该条件下制备的纳米复合材料进行了表征。     

3D打印用聚苯胺/双酚A型环氧丙烯酸树脂的制备与性能研究

通过共混制备了十二烷基苯磺酸掺杂的聚苯胺/双酚A型环氧丙烯酸光敏树脂(DBSA-PANI/BAEA),再通过数字光处理(DLP)技术实现了3D打印。研究了掺杂态聚苯胺对光敏树脂的黏度、固化凝胶率、力学强度和体积电阻率的影响,并通过扫描电镜(SEM)对树脂的冲击断面形貌进行了观察。结果表明,随着掺杂态聚苯胺的增加,树脂的冲击强度明显增加,树脂的电性能也有一定程度的提高,但是树脂的拉伸强度出现了下降。当掺杂态聚苯胺的添加量超过0. 2%时,电镜照片中的片层结构数目逐渐增多,树脂的韧性获得相应的提高。当添加量达到0. 4%时,树脂的固化凝胶率仅为75. 5%;若继续添加掺杂态聚苯胺,树脂将难以打印。     

酸掺杂聚苯胺的研究进展

聚苯胺是最有应用价值的导电高分子之一,介绍了聚苯胺的结构,重点综述了单一无机酸掺杂、单一有机酸掺杂、复合酸掺杂、掺杂-脱掺杂-再掺杂、制备掺杂态聚苯胺的研究进展.最后,提出了聚苯胺的研究方向.     

聚苯胺/顺丁橡胶导电复合膜的制备及性能研究

采用两种方法实现顺丁橡胶和掺杂态聚苯胺的复合,即溶液法和机械共混法,并对这两种方法制备的复合样品的性能进行了分析研究。结果表明,溶液法比机械共混法制备的样品性能好。聚苯胺/顺丁橡胶导电复合膜的电导率,随着掺杂态聚苯胺含量的增加而增大。     

不同酸掺杂聚苯胺/环氧涂层的防腐蚀性能研究

制备了分别由盐酸、硫酸、磷酸、植酸、甲基磺酸和十二烷基苯磺酸掺杂的聚苯胺(依次记为HCl-PANI、H2SO4-PANI、H3PO4-PANI、PA-PANI、MSA-PANI和DBSA-PANI)与本征态聚苯胺(EB-PANI),通过傅里叶变换红外光谱仪、紫外可见分光度计、X射线衍射仪、拉曼光谱仪及扫描电镜对它们的结构与形貌进行了表征。将不同的聚苯胺材料分别添加到环氧树脂中并涂覆在Q235碳钢表面,得到不同的聚苯胺/环氧(PANI/EP)涂层,对其铅笔硬度、附着力及湿润性进行测试,并通过电化学阻抗谱考察了它们在3.5%NaCl溶液中的耐蚀性,讨论了不同添加量、不同掺杂酸对聚苯胺/环氧涂层耐蚀性的影响。结果表明上述7种聚苯胺均呈珊瑚状结构。添加了聚苯胺的环氧涂层的防腐性能得到了不同程度的提高,其中聚苯胺的最佳添加量为0.6%,HCl-PANI与PA-PANI的效果最好。     

聚苯胺的合成、表征及气敏性能研究

用化学氧化聚合法,以苯胺(An)为单体,过硫酸铵(APS)为氧化剂,控制反应温度,在酸性介质(无机酸和有机酸)中合成聚苯胺(PAn)。用傅里叶红外光谱(FTIR)和紫外可见光光谱(UV-Vis)对聚苯胺掺杂前后结构的变化进行了测试,讨论了酸掺杂对聚合产物结构的影响。结果表明电子的离域使聚苯胺主链结构经质子酸掺杂后形成了共轭结构。常温下,通过聚苯胺的气敏性能测试,得知有机酸掺杂的聚苯胺的气敏性能更好,其中用磺基水杨酸掺杂的聚苯胺对1000ppm氨气的灵敏度最高,达到了14.8580,具有实际应用价值。     

聚苯胺的合成、表征及气敏性能研究

用化学氧化聚合法,以苯胺(An)为单体,过硫酸铵(APS)为氧化剂,控制反应温度,在酸性介质(无机酸和有机酸)中合成聚苯胺(PAn).用傅里叶红外光谱(FTIR)和紫外可见光光谱(UV-Vis)对聚苯胺掺杂前后结构的变化进行了测试,讨论了酸掺杂对聚合产物结构的影响,结果表明电子的离域使聚苯胺主链结构经质子酸掺杂后形成了共轭结构.常温下,通过聚苯胺的气敏性能测试,得知有机酸掺杂的聚苯胺的气敏性能更好,其中用磺基水杨酸掺杂的聚苯胺对1000 ppm氨气的灵敏度最高,达到了14.8580,具有实际应用价值.最后初步探讨了聚苯胺的气敏机理.     

微波辅助合成掺杂态聚苯胺及其性能研究

以苯胺为单体,过硫酸铵为引发剂,采用微波法制备了H2SO4掺杂的聚苯胺(PANI-H2SO4)和本征态聚苯胺(PANI-EB)。分析了微波作用时间和温度在聚合过程中对聚苯胺性能的影响,并最终确定最佳的合成工艺条件:微波作用时间为25min,微波作用温度为40℃。此时,得到的掺杂聚苯胺的电导率最高,达到50 S/cm。利用四探针测试仪、红外光谱仪、扫描电镜、X-射线衍射仪等对产物进行了分析与表征。研究结果表明:与本征态聚苯胺相比,掺杂态聚苯胺的吸收峰变宽而且向低频方向移动,且具有较强的结晶性能。     

有机/无机酸复合掺杂导电聚苯胺的合成及性能研究

采用化学氧化聚合法以苯胺为单体,过硫酸胺为氧化剂,在有机/无机混合酸的水溶液中合成导电聚苯胺.考察了有机/无机混合酸对聚苯胺性能的影响,并通过四探针、差热分析、红外光谱及拉曼光谱研究聚苯胺掺杂前后结构的变化.结果表明,当聚合温度为20℃、磺基水杨酸和硫酸的摩尔浓度比为0.25:1时,掺杂态聚苯胺电导率和溶解度达到最大值;其中电导率可达13.5 S·cm~(-1),在氮甲基吡咯烷酮(NMP)中溶解度可达85%.差热分析表明,有机/无机酸复合掺杂聚苯胺热稳定性较单一酸掺杂聚苯胺热稳定性有很大的提高;红外光谱和拉曼光谱表明;掺杂后聚苯胺具有导电性是因为其分子链上电荷离域形成了共轭结构.     

Thermal stability studies of transparent conducting polyaniline composite films on their conductivity and optical spectra

The thermal stability of highly transparent and conducting polyaniline–Nylon 6 (PAn-N) composites films doped with various protonic acids such as hydrochloric acid (HCI), benzenesulfonic acid (BSA), sulfosalicylic acid (SSA), and p-toluenesulfonic acid (TSA) was investigated at different elevated temperatures under air atmosphere. Two different degradation kinetic processes of electrical conductivity were found depending on the species of protonic acids. The conductivity degradation of PAn-N composite films doped with SSA and TSA were found to obey first-order reaction kinetics, while that of the other dopants was found to follow multiorder kinetics. Spectroscopic studies revealed that the thermal de-doping process of doped composite films, which reversed the doping process, took place without major structural modifications of the polyaniline in the composite system but was not completely reversible. From the differential scanning calorimetry (DSC) study, the crystal structure of the composite films was found to be affected by the formation of polyaniline in matrix polymer and depended on the types of dopant species. © 1995 John Wiley & Sons, Inc.     

Investigation of charge transport properties in conducting copolymers of aniline with 3‐aminobenzenesulfonic acid for their applications as antistatic encapsulation materials blended with low‐density polyethylene

The electrostatic charge dissipative (ESD) properties of conducting self‐doped and PTSA-doped copolymers of aniline (AA), o‐methoxyaniline (methoxy AA) and o‐ethoxyaniline (ethoxy AA) with 3‐aminobenzenesulfonic acid (3‐ABSA) blended with low‐density polyethylene (LDPE) were investigated in the presence of external dopant p‐toluenesulfonic acid (PTSA). Blending of copolymers with LDPE was carried out in a twin‐screw extruder by melt blending by loading 1.0 and 2.0 wt% of conducting copolymer in the LDPE matrix. The conductivity of the blown polymers blended with LDPE was in the range 10^?12–10^?6 S cm^?1, showing their potential use as antistatic materials for the encapsulation of electronic equipment. The DC conductivity of all self‐doped homopolymers and PTSA‐doped copolymers was measured in the range 100–373 K. The room temperature conductivity (S cm^?1) of self‐doped copolymers was: poly(3‐ABSA‐co‐AA), 7.73 × 10^?4; poly(3‐ABSA‐co‐methoxy AA), 3.06 × 10^?6; poly(3‐ABSA‐co‐ethoxy AA), 2.99 × 10^?7; and of PTSA‐doped copolymers was: poly(3‐ABSA‐co‐AA), 4.34 × 10^?2; poly(3‐ABSA‐co‐methoxy AA), 9.90 × 10^?5; poly(3‐ABSA‐co‐ethoxy AA), 1.10 × 10^?5. The observed conduction mechanism for all the samples could be explained in terms of Mott's variable range hopping model; however, ESD properties are dependent upon the electrical conductivity. The antistatic decay time is least for the PTSA‐doped poly(3‐ABSA‐co‐AA), which has maximum conductivity among all the samples. © 2013 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     

磁场环境下氧化剂和掺杂剂浓度对聚苯胺性能的影响

在不同磁场强度下,用过硫酸铵(APS)为氧化剂,磺基水杨酸(SSA)为掺杂剂合成导电聚苯胺(PAn),通过对PAn掺杂率的计算和电导率的测定,研究了氧化剂和掺杂剂浓度对PAn性能的影响。采用红外光谱、X射线衍射、粒径分析等研究了制备的PAn性能与结构。实验结果表明磁场对苯胺聚合的影响是正向的,氧化与掺杂条件的变化是影响电导率的重要因素。     

Electrical conductivity enhancement of predoped polyaniline by stretch orientation

A method for the reproducible production of isotropic free standing camphorsulfonic acid doped polyaniline with a conductivity of (300 ± 30) Scm⁻¹ is described. The paper then goes on to describe a method of stretch orienting such films to enhance the conductivity parallel to the draw direction to (890 ± 30) Scm⁻¹ . This improvement is attributed to orientation of both the crystal and amorphous phases. The samples produced by this method are the first stress oriented predoped polyaniline specimens reported in the literature.     

二次掺杂聚苯胺的PAN复合纤维抗静电性能研究

将苯胺与聚丙烯腈(PAN)纤维接枝聚合,第一次采用5-磺基水杨酸(SSA)掺杂制得PAN/聚苯胺(PANI)复合纤维,再以盐酸(HCl)第二次掺杂制得PAN/PANI复合纤维;研究了第二次掺杂的反应条件及PAN/PANI复合纤维的抗静电性能。结果表明:红外光谱分析证明了PAN/PANI复合纤维中有PANI存在;HCl第二次掺杂最佳条件为HCl浓度2 mol/L,反应温度0℃,反应时间6 h,PAN/PANI复合纤维的比电阻约2 kΩ.cm;第二次用HCl掺杂的复合纤维的抗静电性能比第一次用SSA掺杂的抗静电性能更好。