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。     

磺酸掺杂煤基聚苯胺/HDPE导电复合材料的制备

采用热掺杂法制得十二烷基苯磺酸 (DBSA)掺杂态煤基聚苯胺 (CBP) ,并采用熔融共混工艺 ,制备出HDPE/CBP DBSA导电复合材料 ,研究了掺杂时间和掺杂温度对CBP电导率以及CBP DBSA用量对HDPE/CBP DBSA复合材料电阻率的影响。结果表明 :当m (DBSA)∶m (CBP) =1 6,70℃下退火 2h时 ,CBP DBSA的电导率可达0 179S/cm ;红外光谱说明DBSA对CBP起到了较好的掺杂作用。当CBP DBSA的质量分数为 13 %时 ,复合材料的体积电阻率达到 2 9× 10 7Ω·cm ,同时具有较好的力学性能     

聚苯胺和聚对苯二甲酰对苯二胺导电复合物的研究

聚对苯二甲酰对苯二胺(PPTA)与导电性聚苯胺(PAn)共混,得到一种既有PPTA的液晶性,又有PAn导电性的全新材料。PPTA和PAn以不同质量比共溶于浓硫酸后,可制成线材及薄膜,在1mol/1HCl水溶液中成型及拉伸。实验结果表明:PPTA的液晶性随PAn加入量的增加稍有减弱;线状PPTA/PAn的抗张强度随PAn混入量的增加而增大(从41.20N/mm~2增至44.80N/mm~2);断裂伸长与PAn混入量的多少无关(仍保持在4%),PPTA/PAn复合物的电导率随PAn含量的增加而升高,当PPTA:PAn=2:1(质量比)时,其电导率为2.3×10~(-1)S/cm,较纯PAn(3-5S/cm)小一个数量级,复合物的衍射图在2θ=22.7°及25°处有两个峰,分别与纯PPTA及统PAn的峰的位置相同,因此说明二者是以分子复合形式存在。SEM图表明复合物线材表面呈取向排列,且PPTA与PAn混合均匀。     

DBSA掺杂聚苯胺在导电塑料中的应用

以十二烷基苯磺酸(DBSA)作为掺杂酸合成掺杂态聚苯胺,并以掺杂态聚苯胺和特导炭黑做为导电填料,线性低密度聚乙烯(LLDPE)为基体,乙烯-乙酸乙烯酯(EVA)作为增塑剂,掺杂态聚苯胺和特导炭黑作为导电填料,制备导电塑料。使用四探针法测定了掺杂态聚苯胺和导电塑料的电导率,使用扫描电子显微镜、X射线衍射、红外光谱法、热重法对掺杂态聚苯胺进行分析和表征,并且测试了导电塑料的力学性能和流动性能。研究表明:掺杂态聚苯胺具有良好的导电性能,可以作为导电塑料的导电填料使用;并且使用掺杂态聚苯胺和特导炭黑作为导电填料制备的导电塑料比单独使用掺杂态聚苯胺具有更好的导电性能,力学性能。     

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。     

不同态煤基聚苯胺的结构与性能

采用溶液再掺杂法制备了DBSA二次掺杂态煤基聚苯胺(CBP-R-DBSA),得出较佳的二次掺杂条件:时间24 h,温度30℃,酸浓度1.2 mol/L,所得产物电导率为6.08×10-2 S/cm.分析探讨了煤基聚苯胺的掺杂-脱掺杂过程及不同态煤基聚苯胺的结构与性能,结果表明:原位聚合引入的外加酸与煤大分子酸对聚苯胺具有协同掺杂效应,煤基聚苯胺的掺杂-脱掺杂不完全可逆,煤表面酸性基团的掺杂作用相应减少了聚苯胺链上的掺杂活性点,这限定了DBSA对U-CBP的有效二次掺杂,其掺杂效果逊于乳液聚合原位掺杂.     

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。     

聚苯胺的合成及其光谱特性

:采用化学氧化聚合法 ,以苯胺为单体 ,过硫酸铵 (APS)为氧化剂 ,在酸性介质中合成聚苯胺(PAn) ,聚合物的比浓粘度 (ηSP) C=0 .1=1 d L/ g,酸掺杂后电导率 (σ)为 1 0 0 S/ cm。讨论了单体与氧化剂的比例、反应体系的温度以及聚合反应的时间对聚合产物的影响。采用傅里叶红外光谱 (FTIR)和紫外可见光光谱 (UV- Vis)对聚苯胺掺杂前后结构的变化 ,表明聚苯胺主链结构经质子酸掺杂后由于电子的离域形成了共轭结构 ,从而使聚苯胺有良好的导电性能。     

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。     

掺杂态聚苯胺的乳液聚合及其与环氧树脂所制涂层的耐蚀性

以十二烷基苯磺酸钠(SDBS)为乳化剂,采用乳液聚合法制备了盐酸或磷酸与十二烷基苯磺酸(DBSA)共掺杂的聚苯胺[(HCl+DBSA)-PANI或(H_3PO_4+DBSA)-PANI]。用扫描电镜、傅里叶变换红外光谱仪、X射线衍射仪和四探针电导率测试仪表征了掺杂聚苯胺的形貌、结构和电导率。将添加了掺杂态聚苯胺的E44环氧树脂刷涂在Q235低碳钢表面得到复合涂层(PANI/EP),并通过电化学阻抗谱和浸泡试验考察了它们在3.5%NaCl溶液中的耐蚀性。两种共掺杂态聚苯胺都呈束状结构,(HCl+DBSA)-PANI的结构更均一。添加PANI可以明显提高环氧涂层对碳钢的防腐作用,其中(HCl+DBSA)-PANI的效果更好。     

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)。     

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     

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。     

柠檬酸复合掺杂剂制备聚苯胺及其性能

该文以十二烷基苯磺酸与柠檬酸复合掺杂剂制备聚苯胺,对聚苯胺的电导率、溶解性、电致变色性能进行了研究,采用循环伏安法、红外光谱、热重对聚苯胺进行了表征,结果表明,柠檬酸与十二烷基苯磺酸摩尔比为1∶1时,聚苯胺的电导率最大,可达6.67 S/cm;二者摩尔比为0.25∶1时,聚苯胺在二甲苯中的溶解度为1.475 8 g,在1.5 V电压下变色均匀,响应时间短,可实现黄—黄绿—绿—蓝—深蓝范围内的可逆变色。     

新型共混十二烷基苯磺酸掺杂的聚苯胺导电胶的合成

以摩尔比为１： １的苯胺与过硫酸铵为反应物,在 ｃ（ＨＣｌ）＝ １ｍｏｌ／Ｌ盐酸中于室温下合成的聚苯胺,经２５％（ω）氨水处理后得本征态聚苯胺,收率７２％。用５０％（ω）十二烷基苯磺酸的乙醇溶液６０ｍｌ与３ｇ本征态聚苯胺在室温下反应２４ｈ,可制得导电态的掺杂十二烷基苯磺酸的聚苯胺,电导率３．９８Ｓ／ｃｍ。然后在６０℃下将环氧树脂Ｅ－４４和上述掺杂态聚苯胺（ｍ：＝１：０,４）经良好搅拌１ｈ,得均匀的黑色导电胶。该电胶可溶解在二甲苯中,并能与体积比为１：１的邻苯二甲酸在８０℃下经４ｈ可完全固化,电导率为０．１１８Ｓ／ｃｍ。     

Thermal dynamic processing of polyaniline with dodecylbenzene sulfonic acid

To attain an intrinsically conductive and processible polymer, polyaniline (PANI)/dodecylbenzene sulfonic acid (DBSA) blends of several compositions were processed at various elevated temperatures in a Brabender plastograph. The blends' temperatures during processing, as affected by the blends' composition and initial process temperature, were monitored. Accordingly, the process includes the following main stages: heating the blend, exothermic PANI-DBSA doping reaction accompanied by a paste to a solidlike transition, and plasticization of the resulting PANI/DBSA complex by the excess DBSA. Composition analysis of the process products sampled at the various stages showed that the initial blends, prior to their thermal processing, already consisted of partially doped PANI particles, having a core/shell structure; the core consists of PANI_base and the shell of PANI(DBSA)_0.32 complex. In addition, at the paste-to-solidlike transition, the doping reaction is completed; further mixing does not affect the complex composition, but results in conductivity reduction. The morphology of the blends sampled at the various processing stages was studied by electron microscopy. From the conductivity and processibility point of view, optimal PANI/DBSA blend composition and processing temperature were identified. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2199–2208, 1997     

Melt‐processed polyaniline nanofibers/LDPE/EAA conducting composites

The melt‐processable polyaniline nanofibers doped with superfluous dodecylbenzenesulfonic acid (PANI‐DBSA) were synthesized using the interfacial polymerization and thermal doping technique. Conducting composites composed of PANI‐DBSA nanofibers, low‐density polyethylene (LDPE), and ethylene‐acrylic acid copolymer (EAA) as compatibilizer were prepared by melt processing. The effects of PANI‐DBSA nanofibers on the electrical conductivity, and mechanical properties, and morphological structure of the composites were investigated. As a result, the conducting composites had lower percolation threshold (4 wt%) due to the easy formation of conducting paths for fibrillar‐like PANI‐DBSA in the LDPE matrix, which was also confirmed by the frequency dependence of the real part of the AC conductivity. The Scanning electron microscopy (SEM) images indicated that the PANI‐DBSA nanofibers were dispersed uniformly in the matrix. The mechanical properties of the composites were improved at the low PANI‐DBSA load (about 1 wt%), but they were deteriorated at high PANI‐DBSA content. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Doping effect of organic sulphonic acids on the solid‐state synthesized polyaniline

Polyaniline (PANI) salts doped with organic sulfonic acids (methanesulfonicacid, p‐toluenesulphonic acid, and dodecylbenzenesulphonic acid) were first synthesized by using solid‐state polymerization method. The polymers were characterized by Fourier transform infrared (FTIR) spectra, ultraviolet‐visible spectrometry, X‐ray diffraction, cyclic voltammetry, scanning electron microscopy, transmission electron microscopy, and conductivity measurements. It was found that PANI doped with p‐toluenesulphonic acid is formed in conductive emeraldine oxidation state, and displayed higher doping level and cyrstallinity. On the contrary, PANI doped with dodecylbenzenesulphonic acid was lower at doping level and highly amorphous. In accordance with these results, the conductivity and electrochemical acitivity was also found to be higher in p‐toluenesulphonic acid‐doped PANI, and these properties were opposite in the case of dodecylbenzenesulphonic acid. The results also revealed that the morphology of dodecylbenzenesulphonic acid‐doped PANI was remarkably different from other PANI salts. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007