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。     

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.     

聚苯胺的掺杂及其应用

介绍聚苯胺(PANI)的结构、特性、掺杂机制和掺杂方法,综述了PANI在金属防腐、电磁屏蔽、电化学电容器、传感器等领域的应用及近期的研究成果。     

可溶于水的导电性聚苯乙烯磺酸掺杂聚苯胺的合成

以苯胺（An)为单体,过硫酸铵（APS）为氧化剂,在聚苯乙烯磺酸（PSSA）的水溶液中合成了可完全溶于水的导电性聚苯乙烯磺酸掺杂聚苯胺。结果表明,当APS与An的摩尔比为1：2,PSSA的浓度为0．19mol/L,APS溶液的滴加时间为3h,反应温度为14℃,产物电导率的最高值为0．13S/cm,而且可完全溶于水,形成稳定的墨绿色溶液。     

导电高分子材料聚苯胺的研究进展

聚苯胺(PAn)是目前研究最为广泛的导电高分子材料之一。基于国内外最新研究文献,综述了PAn的结构、导电和掺杂机理及常见的合成方法,重点介绍了几种制备微米或纳米级PAn的方法,并对其在各领域应用前景作了简要介绍。     

质子酸掺杂聚苯胺导电材料的合成

导电聚苯胺结构和导电性能较稳定，所用掺杂剂的毒性也较小，是目前最有发展前景的导电功能材料。本实验用化学氧化合成方法，较系统地研究了质子酸种类、氧化剂种类、用量以及聚合反应温度等因素对苯胺聚合反应及产物性能的影响，并通过傅立叶红外吸收光谱（FTIR）研究了聚苯胺掺杂前后结构的变化。     

磺酸掺杂导电聚苯胺共混物的研究进展

就化学原位聚合、溶液共混、机械熔融共混制备磺酸掺杂导电聚苯胺／聚合物复合材料的研究进展作一综述，简述了各种方法的优缺点和目前的应用情况。     

大分子酸的掺杂条件对聚苯胺导电性的影响

研究了掺杂酸种类、氧化剂浓度、反应温度、有机酸浓度对聚苯胺导电性的影响,选用过硫酸铵(APS)作为氧化剂,磺基水杨酸(SSA)和对甲苯磺酸(TSA)两种有机酸作为掺杂酸,经过试验探索得到最佳的工艺:苯胺与APS、掺杂酸的摩尔比为1∶1∶1,聚合温度0℃,APS浓度为1.0 mol/L,SSA和TSA的浓度分别为0.3 mol/L和0.4 mol/L。     

导电聚苯胺的研究进展

概述了聚苯胺的几种合成方法及其溶解性问胚,并介绍了聚苯胺复合材料及聚苯胺的应用。     

镨掺杂的聚苯胺及其性能的研究

以苯胺、硝酸镨合成了本征态聚苯胺和掺杂态聚苯胺.采用扫描电镜、导电测试仪、红外光谱、TGA和XRD等对产物进行表征.结果表明硝酸镨很好地掺杂于聚苯胺基体内,当硝酸错与苯胺的摩尔比为1:1.5时,产物的电导率较好,为0.015 5 S/cm.     

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。     

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。     

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。     

有机酸控制合成多级结构聚苯胺

在丙烯酸(AA)的溶液中,用三氯化铁为氧化剂氧化聚合苯胺,得到了多级纳/微米结构的聚苯胺(PANI)。讨论了丙烯酸和苯胺单体以及搅拌等条件对产物形貌及其结构的影响。研究发现,通过调整AA浓度,能可控的制备PANI球形和塔型多级结构。利用FTIR和XRD对产物分子结构进行了表征。     

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。     

Thermal doping of polyaniline by sulfonic acids

The thermal doping of the emeraldine base (EB) form of polyaniline using two different sulfonic acids, dodecylbenzene sulfonic acid (DBSA) and p‐toluenesulfonic acid (pTSA) has been studied. Differential scanning calorimetry was used to record thermal events associated with the doping process. EB undergoes thermally induced doping with both acids at temperatures depending on the initial quantity of the dopant present. The doping temperatures show an increasing trend with increasing proportion of acid. The enthalpy of doping is also composition dependent. Conductivity values determined by the four‐probe method are given for each sample. The highest conductivities were attained at a mole ratio of 1 (dopant:EB) for both EB(DBSA) and EB(pTSA). © 2003 Society of Chemical Industry     

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     

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。     

Acrylic acid‐doped polyaniline sensitive to ammonia vapors

Acrylic acid and HCl‐doped polyanilines were synthesized by chemical oxidative polymerization. The synthesized materials were used as sensors for ammonia. Comparison of the responses of the two polymers reveal that the acrylic acid‐doped polymer exhibits higher sensitivity and reversibility. Further, the resistance is observed to decrease on exposing the acrylic acid‐doped polyaniline to saturated ammonia vapors. A reversed trend is observed in the case of HCl‐doped polyaniline. The results are explained in terms of the differences in the chemical interactions of the two polymers with respect to ammonia vapors. The proposed mechanism is further supported by the X‐ray diffraction and FTIR analysis. The X‐ray diffractogram of acrylic acid‐doped polymer shows an enhancement in the crystallinity on exposure to ammonia vapors, while the HCl‐doped polymer exhibits a loss in crystallinity. The FTIR spectra shows a higher doping level in acrylic acid doped polymer as observed from the intense peak of the dopant ion at 1158 cm⁻¹, which is seen to be shifted to a lower wavenumber i.e. ∼1128 cm⁻¹ on exposing the polymer to ammonia vapors. On the other hand, in HCl‐doped polyaniline, the peak of the dopant ion ∼1120 cm⁻¹ is initially less intense, which is further suppressed on exposure to ammonia. Conductivity measurements show a large vapor‐induced increase in conductivity, in the case of ammonia‐exposed acrylic acid‐doped polyaniline, which results in the formation of a more crystalline‐conducting phase. Exactly the opposite results were obtained in the case of HCl‐doped polyaniline exposed to ammonia. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1994–1998, 2001