不同质子酸掺杂对聚苯胺合成与性能的影响

由化学氧化法制得的聚苯胺(PANI)被不同质子酸掺杂。研究盐酸(HCl)、硫酸(H2SO4)、樟脑磺酸(CSA)和十二烷基苯磺酸(DBSA)掺杂对PANI产率、溶解性以及电导率的影响。研究发现,HCl掺杂的PANI电导率为0.263 4 S/cm、产率可达到78.83%。还讨论不同HCl浓度和不同过硫酸铵/苯胺(APS/An)的物质的量比对HCl掺杂PANI产率和电导率的影响,当HCl的浓度达到1.2 mol/L、APS/An物质的量比为0.6时,PANI的电导率和产率均为最大值。     

对负离子对氧化石墨烯/聚苯胺电磁性能的影响

以过硫酸铵为引发剂,控制掺杂质子浓度为1 mol/L,分别以Cl–、CSA–(樟脑磺酸根)和SO42–为对负离子,通过原位化学氧化聚合法制备得到掺杂态氧化石墨烯/聚苯胺复合材料.采用SEM、FTIR和XRD对复合材料进行形貌和结构表征,采用四探针法、矢量网络分析仪分别测试复合材料的电磁参数,并计算材料的阻抗和反射损耗(RL).结果表明,3种复合材料均呈现聚苯胺纳米椎体包覆氧化石墨烯片层的三明治形貌.对负离子为SO42–时,复合物的电导率最高为5.500 S/cm,同时介电损耗能力最强.而樟脑磺酸掺杂复合物的驻波比在14.2 GHz处可达到1.1,更接近行波状态,具有最佳阻抗匹配性能.其最佳反射损耗为–30 dB(9.93 GHz,2.75 mm),有效吸波频宽(RL<–10 dB的频率范围)最高可至4.85 GHz(12.30～17.15 GHz,2 mm).     

不同酸掺杂聚苯胺形貌控制及对多巴胺检测研究

通过研究HCl、H3PO4和樟脑磺酸(CSA)掺杂对聚苯胺(PANI)纳米纤维形貌的影响得到其结构可控制备的规律。以掺杂PANI为电极材料对多巴胺(DA)进行差示脉冲伏安法测试,结果表明HCl和H3PO4掺杂的PANI对DA的电化学氧化活性较好,而H3PO4和CSA掺杂的PANI在DA检测中表现出较好的稳定性。     

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。     

聚苯胺的合成工艺优化及其性能表征

采用化学氧化聚合法在苯胺/过硫酸铵/HCl的水溶液体系中合成聚苯胺,并对其聚合条件([S2O2-8]/[An]比、HCl浓度变化等)进行了优化,以提高PAn的电导率和产率。通过四探针、傅立叶红外吸收光谱(FTIR)、XRD、CV等测试方法对聚苯胺电导率及掺杂前后结构的变化进行了分析。结果表明,当[S2O2-8]/[An]=1∶1、[HCl]=0.8 mol/L时电导率达到最大值2.13 S/cm,产率为94.37%。聚合物具有一定的结晶性,通过CV曲线可以分析出PAn具有掺杂/脱掺杂的电化学活性。     

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.     

磷酸二次掺杂聚苯胺纳米纤维的合成及其性能的研究

采用无模板直接混合法制备了硫酸一次掺杂聚苯胺,经氨水解掺杂得到本征态聚苯胺,然后在磷酸体系中对本征态聚苯胺进行二次掺杂。研究了不同的磷酸浓度,反应时间,搅拌时间等对二次掺杂聚苯胺电导率和产率的影响,得到磷酸二次掺杂聚苯胺合成的优化条件,并通过四探针测试仪、扫描电镜、红外光谱、紫外光谱以及电化学测试技术,对掺杂态聚苯胺进行了研究与表征。结果表明,室温下磷酸浓度为1 mol·L-1,搅拌反应24 h时,磷酸二次掺杂聚苯胺的电导率以及产率达到最大值,电导率为0.25 S·cm·1,产率达到138.7%。扫描电镜表征显示,磷酸二次掺杂可获得形貌良好的聚苯胺纳米纤维,其长度可达400~600 nm,且纤维直径均匀;紫外谱图和红外谱图表明磷酸能有效的掺杂到本征态聚苯胺中,改善其电导率及产率;电化学测试结果表明磷酸二次掺杂聚苯胺较一次掺杂聚苯胺有着更好的防腐蚀性能。     

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.     

壬基酚聚氧乙烯醚硫酸掺杂聚苯胺的电导率研究

以壬基酚聚氧乙烯醚(10)硫酸(NPES)为聚苯胺掺杂剂,研究了掺杂剂及其掺杂反应时间、温度等条件对聚苯胺导电性的影响.结果表明:长链NPES的掺杂能够提高聚苯胺导电性,且随着掺杂反应时间的增加,电导率在20h后即达到最大值0.6S/cm;随着掺杂温度的降低,在冰浴条件下,NPES掺杂聚苯胺的电导率较常温时提高两个数量...     

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。     

Polyaniline/polyimide blends as gas sensors and electrical conductivity response to CO–N2 mixtures

The effects of dopant type, doping level, polyimide (PI) content and temperature on electrical conductivity response of polyaniline (PANI) and polyaniline/polyimide (PANI/PI) blends to CO–N₂ gas mixtures were systematically investigated. At the same doping level, HNO₃‐doped PANI has a greater electrical conductivity response and sensitivity towards CO than that of camphor sulfonic acid (CSA)‐doped PANI because the former has a more ordered structure. The interaction mechanism between CO and PANI is proposed to occur at the attack site, ? N?H? or the amine nitrogen where CO withdraws an electron. Addition of PI causes a small change in electrical conductivity under atmospheric conditions when PI content is below the percolation threshold value of 55 wt%. Addition of PI reduces brittleness and improves electrical conductivity sensitivity towards CO; the effect is more pronounced at higher temperatures. Copyright © 2005 Society of Chemical Industry     

Electrical and structural analysis of conductive polyaniline/polyimide blends

Conducting films of dodecylbenzenesulfonic (DBSA)‐doped polyaniline/polyimide (PANI/PI) blends with various compositions were prepared by solvent casting followed by a thermal imidization process. Electrical and physical properties of the blends were characterized by infrared spectroscopy, an X‐ray diffraction technique, thermal analysis, a UV‐vis spectrophotometer, a dielectrometer, and conductivity measurements. The blends exhibited a relatively low percolation threshold of electrical conductivity at 5 wt % PANI content and showed higher conductivity than that of pure DBSA‐doped PANI when the PANI content exceeded 20 wt %. A lower percolation threshold and a lower compatibility was shown between the two components in the blends than those of PANI–camphorsulfonic acid/polyamic acid (PANI–CSA/PAA). A well‐defined layered structure due to the alignment of the long alkyl chain dopant perpendicular to the PANI main chain was evidenced by WAXD spectra. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2169–2178, 1999     

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 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     

Electrically conductive carbon nanopipe-graphite nanosheet/polyaniline composites

Carbon nanopipe (CNP)–graphite nanosheet (GNS)/polyaniline (PANI) composites are synthesized by in situ chemical oxidative polymerization. The structural analysis (electron microscopy, Raman and X-ray diffraction) reveal that PANI is uniformly coated on both CNP and GNS structures resulting in the formation of a network of uniform composite structures. Thermogravimetric analysis shows that CNP–GNS/PANI composites are thermally stable up to 300 °C; the polymeric backbone degrades above 300 °C. CNP–GNS/PANI composites doped with m-cresol, a mixture of camphor sulfonic acid (CSA) and chloroform, and a mixture of CSA and m-cresol are electrically conductive. The electrical conductivity strongly depends on the dopants and about six orders of variation in conductivity can be achieved through the choice of the dopant.     

Processable conductive blends of polyaniline/polyimide

By using camphorsulfonic acid (CSA) to protonate polyaniline (PANI), the counterion enabled the PANI–CSA complex processable as a solution phase. So camphorsulfonic acid (CSA)-doped polyaniline/polyimide (PANI/PI) blend films were prepared by the solvent casting method using N-methylpyrrolidinone (NMP) as a cosolvent followed by thermal imidization. The conductivity of the PANI–CSA/PAA (50 wt % PANI content) is greater than that of the pure PANI sample at room temperature. As the thermal imidization proceeded, molecular order of polymer chain structure was improved in the resulting PANI–CSA/PI film due to the annealing effect of PANI chain, and this PANI–CSA/PI film showed higher conductivity than PANI–CSA and PANI–CSA/PAA film. PANI–CSA/PI blend films had a good thermal stability of conductivity at high temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1863–1870, 1998     

Compatibilization of Conductive Polyethylene/Polyaniline Blends

Summary: The compatibilization of polyethylene/polyaniline (PE/PANI) blends and the preparation of plasticized PANI/camphorsulfonic acid (CSA) complexes suitable for melt blending were studied. Rheological properties of the components essentially affected the morphology of the blend and thereby the electrical conductivity. The hydrogen bonds between the PANI complex and the functionalized metallocene PE used as compatibilizer compensated the unfavorable viscosities of the components. Mechanical properties of PE/PANI blends were improved, and electrical conductivity of the blends remained the same or increased through addition of functionalized metallocene polyethylene. Plasticized PANI/CSA complex with good electrical conductivity was successfully prepared.

Compatibilization of PANI/CSA complex and OH‐functionalized polyethylene.     

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。     

PANI-DBSA/MMA-BA共聚物导电涂料的结构与性能表征

以十二烷基苯磺酸(DBSA)掺杂的聚苯胺(PANI)为导电组分,三氯甲烷为溶剂,采用溶液共混法制备聚苯胺/丙烯酸酯共聚物(AA)导电薄膜。对导电薄膜进行了导电性能测试,扫描电镜(SEM)、红外光谱(FT-IR)及差示扫描量热(DSC)分析。结果表明:导电薄膜的电导率随PANI-DBSA含量的增加而增加,体系的逾渗阈值低于4%(质量分数)。共混体系表现出良好的相容性。     

聚苯胺/氧化钇复合材料的合成及热稳定性研究

合成了对甲基苯磺酸(p-TSA)掺杂的导电聚苯胺(PANI)及聚苯胺/氧化钇(PANI/Y2O3)复合材料.比较了不同实验条件对两种材料电导率的影响,研究了两种材料的热稳定性及粒径分布.结果表明,在所研究实验条件下,PANI/Y2O3的电导率低于PANI,而热稳定性则优于PANI;Y2O3的掺入使PANI的粒径减小.