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.     

乳聚法制备聚苯胺复合膜及其电致变色性能研究

以十二烷基苯磺酸(DBSA)为掺杂剂,在非有机溶剂的两相体系中以聚乙烯醇(PVA)为成膜助剂,采用乳液聚合法合成了可直接用于制备电致变色膜的聚苯胺PAn/PVA乳液,用提拉成膜法制备了复合膜。研究了PVA含量、苯胺(An)与DBSA的量比、氧化剂过硫酸铵(APS)与An的量比及反应温度对膜的电致变色性、导电性的影响。结果表明:在w(PVA)为4.3%、n(An)∶n(DBSA)∶n(APS)=0.80∶1.00∶0.80、反应温度为5℃时,PAn/PVA复合膜具有较好的电致变色性及粘结性能。其本征态电化学活性的氧化峰电位范围出现在0.43V。     

导电聚苯胺的合成与表征

采用微乳液聚合法,以苯胺为单体、十二烷基苯磺酸(DBSA)/盐酸(HCl)复合酸掺杂制备了导电聚苯胺,通过红外光谱对其结构进行了表征,考察了合成工艺条件对聚苯胺导电性能的影响,探讨了有机无机复合酸体系对聚苯胺热稳定性的影响。在复合酸十二烷基苯磺酸与盐酸物质的量比为3∶2、复合酸与单体物质的量比为2.0∶1、聚合温度为20℃、聚合时间为10h的优化条件下,所得到的掺杂态聚苯胺导电性能最佳。适当配比的有机无机复合酸掺杂后,导电聚苯胺的热稳定性显著提高。     

乳液聚合法制备聚苯胺/聚乙烯醇电致变色材料

以十二烷基苯磺酸(DBSA)为掺杂剂,在非有机溶剂的两相体系中以聚乙烯醇(PVA)为成膜助剂,采用现场乳液聚合法合成了可直接用于制备电致变色膜的聚苯胺(PAn)/PVA乳液。研究了PVA含量、苯胺(An)与DBSA的量比、氧化剂过硫酸铵(APS)与An的量比及反应温度对膜的电致变色性、导电性的影响。实验结果表明:在w(PVA)=4 3%、n(An)∶n(DBSA)∶n(APS)=0 86∶1∶0 86、反应温度为8℃时,所制得的PAn/PVA乳液可直接制成具有良好电致变色性的自支撑膜(电致变色响应时间小于0 5s,电导率可达2 69×10-4S/m)。     

磺酸原位掺杂煤基聚苯胺的制备及性能研究

采用化学原位乳液聚合法合成十二烷基苯磺酸(DBSA)掺杂煤基聚苯胺导电复合材料(CBP-DBSA)。研究了反应体系中煤粉用量，聚合温度，聚合时间、苯胺单体浓度及过硫酸铵、DBSA用量对复合材料电导率的影响，确定了较佳的反应条件．同时考察了热处理温度对CBP-DBSA电导率的影响，并且通过FTIR、TGA测试手段对复合材料的结构、热稳定性进行了表征和分析。     

十二烷基苯磺酸掺杂聚苯胺的性能研究

用十二烷基苯磺酸 (DBSA)对本征态聚苯胺 (PAn)进行掺杂 ,得到溶解性、成膜性和光电性能俱佳的掺杂态聚苯胺。红外光谱研究表明 :DBSA掺杂PAn的吸收峰都向低频方向移动。探讨DBSA浓度、掺杂温度和时间以及洗涤滤液pH值对聚苯胺电导率的影响。结果表明 :当c(DBSA) =1 0mol/L ,T =32 3K ,t=8h ,洗涤滤液 pH =3时 ,聚苯胺的电导率为 0 90 9S/cm。紫外 -可见吸收光谱表明 ,掺杂态聚苯胺的吸收峰变宽而且发生红移。X射线衍射在 2θ =8 86°,1 7 7° ,2 1 4°和 2 6 7°处出现 4个较强的低角度衍射峰 ,表明DBSA掺杂的聚苯胺具有较强的结晶性能。     

复合氧化剂法制备聚苯胺乳液及其应用性能的研究

采用正相微乳液法,以苯胺为单体、十二烷基苯磺酸为掺杂剂、抗坏血酸和过硫酸铵为复合氧化剂制备聚苯胺乳液及性能良好的聚苯胺粉体,考察了复合氧化剂组成和用量对聚苯胺性能的影响,并探讨了聚苯胺乳液直接应用于带锈涂料中防腐性能的变化规律,结果表明:以抗坏血酸与过硫酸铵复合作为氧化剂,过硫酸铵与抗坏血酸质量比为13∶1,十二烷基苯磺酸与苯胺物质的量比为1.25∶1.00,合成的聚苯胺性能优良;添加0.5%的聚苯胺乳液于带锈涂料中,可以有效地提高带锈涂料的防腐性能。     

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。     

石墨烯/聚苯胺复合材料的制备及其光催化性能

以苯胺和氧化石墨烯溶液为原料,采用乳液聚合法,根据m(氧化石墨烯)∶m(苯胺)为0∶10、1∶20和1∶10合成不同石墨烯/聚苯胺复合材料。采用紫外可见分光光度计、SEM、XRD及FT-IR对复合材料进行表征。XDR和FT-IR表明,乳液聚合合成了石墨烯/聚苯胺复合材料。SEM表明,聚苯胺以氧化石墨烯为载体,分散在其表面。光催化结果表明,石墨烯/聚苯胺复合材料的光催化性能较纯聚苯胺明显提高,m(氧化石墨烯)∶m(苯胺)=1∶20的石墨烯/聚苯胺复合材料的光催化性能高于m(氧化石墨烯)∶m(苯胺)=1∶10,原因可能在于微观结构的不同。     

聚丙烯/聚苯胺共混材料的界面结构及抗静电性能研究

采用乳液聚合方法,利用聚丙烯(PP)二甲苯溶液为种子对苯胺单体进行了核-壳聚合。利用DSC、高倍显微镜及偏光显微镜等对聚苯胺热稳定性及与PP共混的界面进行了测试分析。聚苯胺(PANI)与聚丙烯(PP)进行共混可以制成抗静电性较高,溶解性和熔融性较好的导电复合材料。     

Synthesis and characterization of organo‐attapulgite/polyaniline‐dodecylbenzenesulfonic acid based on emulsion polymerization method

Organo‐attapulgite (OAT) was obtained by pretreating attapulgite (AT) with hexadecyltrimethyl ammonium bromide (HDTMABr) and dodecylbenzenesulfonic acid doped polyaniline (PAn‐DBSA) (OAT/PAn‐DBSA) was synthesized by emulsion polymerization at different OAT weight ratios. The perhaps polymerization procedure was supposed. The chemical structure and electronic absorption of the composites was confirmed by FTIR and UV–Vis spectroscopy, respectively. According to the X‐ray diffraction (XRD) results, it can be concluded that HDTMABr and PAn‐DBSA was just adsorbed on the surface of AT during the cation‐exchange process and OAT respectively without destroying the crystalline structure of AT or OAT. The composites showed a higher thermal stability than pure PAn‐DBSA by introduction of OAT into this polymerization system by using TGA analysis. Morphologies of the samples were confirmed by TEM and it showed that OAT was dispersed well in organic solvent after AT was pretreated with HDTMABr. The morphologies of OAT/PAn‐DBSA also supported the perhaps formation procedure we hypothesized. The electrical conductivity of the composite decreased with increasing the feed weight ratios of OAT in this polymerization system. POLYM. COMPOS., 2008 © 2007 Society of Plastics Engineers     

Didecyl ester of 4‐sulfophthalic acid as a plast dopant and emulsifier in the chemical polymerization of aniline into polyaniline salt

Polyaniline salt was synthesized through the chemical oxidation of aniline with sodium persulfate as the oxidant and didecyl ester of 4‐sulfophthalic acid via three different polymerization pathways (aqueous, emulsion, and interfacial). In these polymerization processes, the ester acted as a novel plast dopant and as an emulsifier. The yield, conductivity, and number of ester units present in the polyaniline salts were determined. A polyaniline salt prepared by emulsion polymerization was soluble in chloroform and showed excellent solution‐processing properties. Polyaniline samples prepared by aqueous or interfacial polymerization were not soluble in chloroform. A soluble polyaniline salt was successfully synthesized through the washing of an organic layer containing the polyaniline salt with water in emulsion polymerization. X‐ray diffraction spectra of polyaniline salts prepared by the three different methods showed an ordered, layer‐type supramolecular structure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

可溶导电聚苯胺材料的合成研究

采用乳液聚合方法，合成有机大分子酸DBSA掺杂的可溶导电聚苯胺。探讨DBSA和引发剂用量对掺杂聚苯胺电导率及其溶解性的影响。合成了电导率较高和很好溶解性的导电聚苯胺材料，可以用作抗静电材料。     

聚苯胺微乳液合成及其电致变色性

用 (NH4) 2 S2 O8为氧化剂 ,在功能质子酸 水 正丁醇三元体系中 ,用微乳液法合成了聚苯胺。以聚苯胺的电导率和电致变色性能为标准 ,讨论了引发剂、DBSA、反应温度和反应时间对聚苯胺性能的影响 ,并对影响聚苯胺 /聚乙烯醇复合膜的性能因素作了初步探讨。结果表明 :与用常规乳液法合成的聚苯胺相比 ,用微乳液法合成的聚苯胺与聚乙烯醇所成的膜 ,其电导率提高了 2个数量级 ,电致变色性能也更好。     

Studies on the synthesis of low molecular weight,one‐dimensional polyanilines prepared by fast emulsion polymerization using (n‐dodecylbenzenesulfonic acid)/HCl emulsifiers

Low molecular weight polyaniline nanotubes were prepared by fast emulsion polymerization in the presence of both n‐dodecylbenzenesulfonic acid (DBSA) and HCl(aq). The anilinium monomers associated with DBSA emulsifiers were found to self‐arrange into strands of associated cylindrical micelles before polymerization, as monitored by their optical activity and optical image. In the presence of some HCl(aq), the monomer‐associated cylindrical micelles expanded and the polymerization rate could be speeded up. It was found that the low molecular weight (viscosity‐averaged molecular weight) polyaniline obtained can easily lead to the formation of highly conductive, one‐dimensional nanotubes or nanofibers monitored by the variation of optical activities and λ_max of the UV–visible–near IR spectra during polymerization. The DBSA/HCl ratio played an important role in the eventual properties and morphologies of the one‐dimensional polyanilines, which can be illustrated by conductivity, SEM and transmission electron microscopy measurements. The resultant one‐dimensional polyaniline nanotubes can be arranged into a layered structure by orientation, illustrated by AFM and wide‐angle X‐ray diffraction. © 2012 Society of Chemical Industry     

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     

Viscoelastic characterization of semiconducting dodecylbenzenesulfonic acid doped polyaniline electrorheological suspensions

Dodecylbenzenesulfonic acid (DBSA)‐doped polyaniline particles were synthesized via emulsion polymerization, and electrorheological (ER) fluids were prepared by dispersing the synthesized polyaniline particles in silicone oil. The viscoelastic properties of DBSA‐doped polyaniline/silicone oil ER systems were examined using a vertical oscillation rheometer (VOR), which is designed for the rheological measurement of ER fluids, with a high voltage generator. Viscoelastic data obtained from the VOR were compared with those obtained from a commercial Physica rotational rheometer. The data from VOR were quite reliable in a broad range of both strain and frequency. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 108–114, 2001     

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