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.     

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。     

有机磺酸共掺杂聚苯胺结晶性和热稳定的研究

使用十二烷基苯磺酸和甲烷磺酸作为共掺杂剂制备出高导电可溶聚苯胺,甲磺酸作为聚苯胺的主要掺杂剂保证了产品的高电导率,同时十二烷基苯磺酸改善聚苯胺溶解性能和加工性能,使其具有良好的分散性和稳定性。利用X-射线衍射仪和热重分析仪进一步分析了,聚苯胺有序化程度和导电性能的关系,结果表明,十二烷基苯磺酸掺杂后的聚苯胺分子链的有序化发生改变,链间距表达导致其电导率降低,而热稳定性能和溶解性能的到了明显改善。     

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.     

钒酸基/聚苯胺修饰薄膜的制备及湿敏性能研究

采用交替沉积法制备了钒酸基/聚苯胺薄膜,讨论酸种类和不同层数对薄膜湿敏性能的影响,实验结果表明:钒钛酸/聚苯胺复合膜的湿敏性能优于钒酸/聚苯胺薄膜,双层钒钛酸/聚苯胺薄膜的湿敏性能均优单层,该湿敏薄膜的湿滞为5%RH,灵敏度变化了三个数量级,响应时间为8s,恢复时间为13s,线性度和稳定性均较理想。     

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.     

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。     

富马酸掺杂聚苯胺的制备和表征

本文以过硫酸铵作为氧化剂,富马酸作为掺杂酸,采用化学氧化聚合方法合成了富马酸掺杂聚苯胺(PANI)。分别对富马酸掺杂聚苯胺的化学结构、热稳定性、粒径大小及分布、微观形貌和结晶性进行了表征分析。结果表明:所制备的富马酸掺杂聚苯胺为粒径均匀的纳米棒状结构,且具有良好的热稳定性和较好的结晶性。     

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。     

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。     

Fixed‐bed column removal of chemical oxygen demand,anions, and heavy metals from paper mill wastewater by using polyaniline and polypyrrole nanocomposites on carbon nanotubes

This research endeavored to develop a new application of polypyrrole (PPy) and polyaniline (PAn) synthesized in the presence of ferric chloride and potassium iodate as oxidants and coated on carbon nanotubes (CNT). The removal of heavy metals, anions, and chemical oxygen demand from paper mill wastewater was compared when polyaniline, polypyrrole, and their nanocomposites with carbon nanotubes were used for this purpose. It was found that PPy/CNT and PAn/CNT could be used as effective adsorbents in the wastewater treatment. Also, the synthesized products were investigated in terms of morphology, molecular structure, and thermal stability by using scanning electron microscopy, Fourier‐transform infrared spectroscopy, and thermal gravimetric analysis. J. VINYL ADDIT. TECHNOL., 19:213‐218, 2013. © 2013 Society of Plastics Engineers     

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     

Poly(butylene terephthalate)/poly(ethylene glycol) blends with compatibilizers

Polymer blend systems offer a versatile approach for tailoring the properties of polymer materials for specific applications. In this study, we investigated the compatibility of polybutylene terephthalate (PBT) and poly(ethylene glycol) (PEG) blends processed using a twin-screw extruder, with the aim of enhancing their compatibility. Phthalic anhydride (PAn) and phthalic acid (PAc) were used as potential compatibilizers at different concentrations to improve interfacial interactions between PBT and PEG. Blend morphologies were characterized using scanning electron microscopy, which revealed improved interfacial compatibility and reduced phase separation with the incorporation of small amounts of PAn and PAc. Differential scanning calorimetry analysis indicated changes in the melting temperature (T_m) and glass transition temperature (T_g) of the blends owing to the compatibilizing effects of PAn and PAc. Dynamic mechanical analysis further corroborated the influence of the compatibilizers on the T_g and viscoelastic behavior. Thermogravimetric analysis demonstrated enhanced thermal stability with the addition of either PAn or PAc. Rheological measurements indicated an increase in complex viscosity with increasing compatibilizer content, indicating improved compatibility. The degradation point (T_d) of PBT/PEG blend increased from 158 to 200 and 319°C with the incorporation of 5 phr PAn and 2 phr PAc, respectively. Mechanical properties, including tensile strength, Young's modulus, and Izod impact strength, were evaluated. For instance, the tensile strength of PBT/PEG blend was enhanced from 43.5 to 48.7 and 49.7 MPa by incorporating 5 phr PAn and 2 phr PAc, respectively. However, the impact strength of PBT/PEG blend increased from 3.0 to 4.3 and 4.2 kJ/m² with the addition of 1 phr PAn and 1 phr PAc, respectively. The findings demonstrated that adding 5 phr PAn or 2 phr PAc to the PBT/PEG blends was advantageous, achieving a harmony of performance benefits and compromises. Rheological observations contributed significantly to the mechanical and thermal properties. Overall, the study highlights the significance of utilizing PAn and PAc as effective compatibilizers for enhancing the properties of PBT/PEG blends, making them potential candidates for various applications.     

Polyaniline/polyacrylate core–shell composites: Preparation,morphology and anticorrosive properties

Polyaniline/partially phosphorylated poly(vinyl alcohol)/polyacrylate nanoparticles ((PAn/P-PVA)_x/PAc_y) were synthesized by encapsulation of varying amounts of PAn/P-PVA nanoparticles (x = 0.3, 0.5 or 0.7 g) with PAc (y = 4, 6 or 8 g acrylate monomers) via emulsifier-free emulsion polymerization. A monomer conversion level of 93.9% was achieved for the synthesis of the (PAn/P-PVA)_0.5/PAc₄ nanoparticles. X-ray diffraction analysis revealed that PAc was intercalated between the PAn/P-PVA layers, whilst transmission electron microscopy analysis of the different nanoparticles revealed they were spherical PAn/P-PVA agglomerates coated with PAc. Thermogravimetric analysis revealed that the thermal stability of the (PAn/P-PVA)/PAc nanoparticles decreased with increasing amounts of PAc. Cyclic voltammetry based analysis of the different (PAn/P-PVA)/PAc nanoparticles coated onto carbon fiber electrodes revealed that the PAn/P-PVA nanoparticles were encapsulated sufficiently by the non-conductive PAc and that the peak current decreased with increasing amounts of acrylate. With respect to the corrosion resistance in 1.0 M sulfuric acid, steel coated with the (PAn/P-PVA)_0.7/PAc₈ nanocomposite showed the best corrosion resistance (11.4%), but for the nanocomposites at each PAn/P-PVA loading level, the anticorrosive properties increased with increasing PAc levels, presumably due to the increasing tortuosity of the diffusion pathway through the coating for any corrosion agents.     

A hydrogen peroxide sensor based on a horseradish peroxidase/polyaniline/carboxy-functionalized multiwalled carbon nanotube modified gold electrode

We have developed a polyaniline/carboxy-functionalized multiwalled carbon nanotube (PAn/MWCNTCOOH) nanocomposite by blending the emeraldine base form of polyaniline (PAn) and carboxy-functionalized multiwalled carbon nanotubes (MWCNT) in dried dimethyl sulfoxide (DMSO) at room temperature. The conductivity of the resulting PAn/MWCNTCOOH was 3.6 × 10⁻³ S cm⁻¹, mainly as a result of the protonation of the PAn with the carboxyl group and the radical cations of the MWCNT fragments. Horseradish peroxidase (HRP) was immobilized within the PAn/MWCNTCOOH nanocomposite modified Au (PAn/MWCNTCOOH/Au) electrode to form HRP/PAn/MWCNTCOOH/Au for use as a hydrogen peroxide (H₂O₂) sensor. The adsorption between the negatively charged PAn/MWCNTCOOH nanocomposite and the positively charged HRP resulted in a very good sensitivity to H₂O₂ and an increased electrochemically catalytical current during cyclic voltammetry. The HRP/PAn/MWCNTCOOH/Au electrode exhibited a broad linear response range for H₂O₂ concentrations (86 μM–10 mM). This sensor exhibited good sensitivity (194.9 μA mM⁻¹ cm⁻²), a fast response time (2.9 s), and good reproducibility and stability at an applied potential of −0.35 V. The construction of the enzymatic sensor demonstrated the potential application of PAn/MWCNTCOOH nanocomposites for the detection of H₂O₂ with high performance and excellent stability.     

导电聚苯胺／丁苯吡胶乳复合聚合物

以丁苯吡胶乳（ＰＳＢＲＬ）为稳定剂，苯胺（Ａｎ）进行氧化聚合，制得的导电ＰＡｎ／ＰＳＢＲＬ复合聚合物可直接浇铸成膜，亦可经破乳后用其沉淀物经热压成膜。氧化聚合条件：［ＨＣｌ］＝１．４ｍｏｌ／Ｌ，［Ａｎ］＝０．５ｍｏｌ／Ｌ，［氧化剂］＝０．２５ｍｏｌ／Ｌ。胶膜性质：当该复合聚合物中ＰＡｎ含量约为５０％时，电导率可达５×１０２Ｓ／ｍ左右，拉伸强度约１３ＭＰａ，扯断伸长率为５３％，在空气气氛中贮存２８ｄ电导率基本不变。     

Polyaniline Hydrochloride for a Novel Application: Accelerator and Filler for Phenol-Formaldehyde Resin

Abstract

In this work, a study has been made of a novel application of polyaniline hydrochloride (PAn.HCl) in the field of adhesives. Different concentrations of PAn.HCl (0%, 3%, 8%, 13%, 15%, 25%, 35%, 45% and 55% w/w) were blended with phenol formaldehyde resin (resole) by mechanical mixing and the effect of the blending on the adhesive strength and gel time of resin solution was studied. It was discovered that PAn.HCl had an accelerating effect upon the curing of the resin and the curing time was found to be significantly reduced. It was also discovered that PAn.HCl can play a role as a filler in phenolic resin polymer matrices, resulting in an improvement in the mechanical properties (adhesive strength) of the prepared resins. Resole and its blends with PAn.HCl were characterized in terms of their structure, by Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The room temperature d.c. electrical conductivities of resole and resole/PAn.HCl blends were studied by the conventional four-point probe method.     

Effects of interactions among polyaniline,camphorsulfonic acid and silica on the structure and properties of their conductive hybrids

In this work, the effects of interactions among polyaniline (PAn), camphorsulfonic acid (CSA), and silica on the structure and properties of their sol‐gel hybrids are investigated. These interactions were revealed by FTIR, UV–vis spectra, and XRD patterns. The interaction between PAn and CSA raises conductivities of the CSA‐doped PAn/SiO₂ (c‐PAn/SiO₂) hybrids. Moreover, the hydrogen bonding interaction between c‐PAn and silicic acid (precursor of SiO₂) leads to a less degree of three‐dimensional network structure of the SiO₂ component in a hybrid with higher PAn content. In addition, because of the interactions among CSA, Pan, and SiO₂, the conductive c‐PAn‐rich phase distributes uniformly in the hybrid and thermal resistance of the hybrid is enhanced consequently. Besides, the c‐PAn/SiO₂ hybrid with higher SiO₂ content exhibits more significant blue‐shift of its polaron band, lower conductivity, and higher thermal resistance. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Effects of interactions among polyaniline, dodecylbenzylsulfonic acid and silica on the morphology and properties of their sol–gel hybrids

In this work, the effects of interactions among polyaniline (PAn), dodecylbenzylsulfonic acid (DBSA) and silica on the morphology and properties of their sol–gel hybrids are investigated. DBSA acts as dopant for PAn and an efficient catalyst for the formation of SiO₂ network. Also, DBSA promotes the dissolution of PAn in organic solvent for preparing uniform hybrids. The interaction between DBSA and PAn components raises conductivities of the DBSA-doped PAn/SiO₂ (d-PAn/SiO₂) hybrids. Moreover, the hydrogen bonding interaction between d-PAn and SiO₂ precursor (silicic acid) leads to a less degree of three-dimensional network structure of the SiO₂ component in a hybrid with higher d-PAn content. In addition, because of the interactions among DBSA, PAn, and SiO₂, the conductive d-PAn-rich phase distributes uniformly in the hybrids. Besides, the d-PAn/SiO₂ hybrid with higher SiO₂ content exhibits lower conductivity, higher thermal resistance and more significant blue-shift of its polaron band.     

聚苯胺/聚乙烯醇微乳液导电涂料的研制及其性能的测试

采用氧化聚合方法合成可溶性的聚苯胺/聚乙烯醇(PAn/PVA)复合导电涂料.研究了反应体系中聚苯胺的含量、反应时间、温度及酸浓度对导电涂料电导率的影响,确定了较佳的聚合反应条件,同时对其稳定性、导电性、力学性及其表面结构等进行了测试.结果表明,PAn/PVA导电涂料稳定性好,在空气中放置80h电导率无明显变化,涂料涂层的电导率最高可达4.57s/cm,加入环氧树脂可明显改善涂层的附着力.