Effects of FeCl3/ammonium persulfate composite oxidant and magnetic field on film growth rate of polyaniline doped with dodecylbenzenesulfonic acid

Polyaniline (PANI) doped with dodecylbenzenesulfonic acid (DBSA) was synthesized by emulsion polymerization using FeCl₃/ammonium persulfate (APS) as composite oxidant. The effects of different magnetic field (MF) intensities, the molar ratios of FeCl₃/APS, and the concentrations of DBSA on the film growth rate of PANI were analyzed by using a quartz crystal microbalance (QCM) technique. The film growth rate of PANI increased with increasing MF intensity and the concentration of DBSA. However, the film growth rate of PANI decreased with increasing molar ratio of FeCl₃/APS. The polymerization conditions were optimized tentatively by cyclic voltammetry (CV) testing. The peak currents and conductivity were the largest for PANI prepared under the following conditions: MF intensity 0.4 T, molar ratio of FeCl₃/APS 2:1, and concentration of DBSA 0.05 mol/L. The UV–Vis spectra of the PANI polymerization showed that the absorption intensity of PANI polymerized in the presence of MF was greater than that of PANI polymerized in the absence of MF, at the same reaction time.     

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)。     

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。     

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     

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。     

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/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。     

DBSA掺杂聚苯胺的制备、表征及其导电性

采用过硫酸铵(APS)为氧化剂在十二烷基苯磺酸(DBSA)微胶束中化学氧化制备纳米棒状聚苯胺;DBSA既起乳化剂也起掺杂剂的作用。制备的掺杂聚苯胺用红外光谱(FTIR)、紫外光谱(UV-vis)、X-射线衍射(XRD)和扫描电镜(SEM)进行了表征;透射电镜(TEM)下首次观察到了聚苯胺的有序排列结构,晶面间距为5.99 Å。考察了掺杂剂/苯胺、氧化剂/苯胺的摩尔比和反应温度、时间等对聚苯胺电导率影响,最高电导率达到了0.72 S/cm。透射电镜怎能看到5.99     

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。     

Facile preparation of conductive paint made with polyaniline/dodecylbenzenesulfonic acid dispersion and poly(methyl methacrylate)

We investigated an easy way to prepare industrially a conductive paint made with polyaniline (PANI)/dodecylbenzenesulfonic acid (DBSA) dispersion and poly(methyl methacrylate) (PMMA) in organic media. First, water‐dispersible PANI doped with DBSA was chemically synthesized with aniline sulfate using ammonium persulfate in water, and the resulting PANI/DBSA was readily extracted from the reaction medium with a mixture of toluene and methyl ethyl ketone (MEK) (toluene:MEK = 1:1 (v/v)), which is useful for industrial applications. The obtained PANI/DBSA organic dispersion was mixed with PMMA organic solution to give the corresponding PANI/DBSA conductive paint containing PMMA. A film prepared with the resulting PANI/DBSA conductive paint was found to possess relatively good conductivity and low surface resistivity for a conductive paint utilized for an electrostatic discharge even at low PANI/DBSA content in the PANI/DBSA–PMMA composite film (the conductivity and the surface resistivity were 9.48 × 10^?4 S cm^?1 and 3.14 × 10⁶ Ω cm^?2, respectively, when the feed ratio of PANI/DBSA:PMMA was 1:39 (w/w)). Furthermore, it was found that the conductivity of the film composed of PANI/DBSA–PMMA composite can be readily and widely controlled by the PANI/DBSA content of the composite or by the amount of DBSA used during the PANI/DBSA synthesis. The highest conductivity of PANI/DBSA–PMMA composite film (7.84 × 10^?1 S cm^?1) was obtained when the feed ratio of PANI/DBSA:PMMA was 1:4 (w/w). Copyright © 2007 Society of Chemical Industry     

Processable dodecylbenzene sulfonic acid (DBSA) doped poly(N-vinyl carbazole)-poly(pyrrole) for optoelectronic applications

A soluble poly (n-vinyl carbazole)–polypyrrole (PNVC–Ppy) copolymer was prepared through oxidative chemical polymerization wherein dodecyl benzene sulfonic acid (DBSA) was used as a dopant to facilitate polymer-organic solvent interaction and ammonium persulfate (APS) was used as an oxidant. Compared with undoped PNVC–Ppy, the DBSA-doped PNVC–Ppy copolymer showed higher solubility in some selected organic solvents. The composition and structural characteristics of the DBSA-doped PNVC–Ppy were determined by Fourier transform infrared, ultraviolet–visible, and X-ray diffraction spectroscopic methods. Field emission scanning electron microscopic method was employed to observe the morphology of the DBSA-doped PNVC–Ppy copolymer. The electrical conductivity of the DBSA-doped PNVC–Ppy copolymer was measured at room temperature. The conductivity increased with increasing concentration of APS oxidant, and the highest conductivity was recorded at 0.004 mol/dm³ APS at a polymerization temperature of ?5 °C. The increased conductivity can be explained by the extended half-life of pyrrole free radical at a lower temperature and a gradual increase in chain length over a prolonged time due to the slow addition of APS. Furthermore, the obtained soluble copolymer exhibits unique optical and thermal properties different from those of PNVC and Ppy.     

Polymerization of anilinium/DBSA in the presence of clay particles: Catalysis and encapsulation

This paper describes polymerization of anilinium‐DBSA complex to PANI‐DBSA (DBSA doped polyaniline) in an aqueous dispersion in the presence of mica or talc clays. It is found that the clay presence significantly accelerates the polymerization kinetics by metal ions, such as Fe⁺² ions, present in the clays. Polymerization occurs preferentially on the clay particles' surface, causing their encapsulation with PANI‐DBSA shells. Further coating with PANI‐DBSA takes place on the already coated particles with thin PANI‐DBSA shells by an autoacceleration effect of anilinium‐DBSA polymerization by PANI. It is suggested that the catalytic/autoacceleration effect dominating in the coating process of clay particles with PANI‐DBSA can be extended to other particle/coating systems, which are already under investigation.     

Microwave absorption properties of a conductive thermoplastic blend based on polyaniline

Summary Conductive thermoplastic blends of polystyrene and polyaniline doped with dodecylbenzene sulfonic acid, DBSA and polystyrene sulfonic acid were prepared in an internal mixer. We used a block copolymer of styrene and butadiene as compatibilizer. Different formulations were tested according to a statistical response surface method. The electrical conductivity and the microwave radiation absorbing properties of the blends were evaluated. The concentration of the compatibilizer and polyaniline and the blend film thickness affect the attenuation properties of the materials.     

Synthesis of ammonium persulfate microcapsule with a polyaniline shell and its controlled burst release

Polymer hydraulic fracturing is important for increasing production during petroleum exploitation. After fracturing, the high-viscosity polymer should be completely decomposed by gel breakers (ammonium persulfate [APS]) to realize high conductivity in the proppant pack. A new series of polyaniline microcapsules loaded with APS for the preparation of delayed-release gel breakers were synthesized via in situ polymerization. The silica nanoparticles were doped in polyaniline to control the release of the encapsulated APS. The morphology, shell wall thickness, and elemental composition of the microcapsules were characterized by scanning electron microscopy, transmission electron microscopy, and two-dimensional scanned energy-dispersive X-ray spectroscopy. The results revealed that the microcapsules were irregularly spherical with average diameters of about 5–6 μm and had shell thicknesses of 150–300 nm, and the silica nanoparticles had been successfully doped in the polyaniline shell. The microcapsules had a burst release pattern, and their initial release time was precisely controlled by adjusting the concentration and temperature of the sodium hydroxide solution. With increased demands for high performance delayed-release microcapsules, the prepared polyaniline microcapsules loaded with APS show great potential for practical applications in petroleum exploitation, self-healing coating, fiber printing, and grease.     

Electrically conducting polyaniline‐PBMA composite films obtained by extrusion

Poly(n‐butyl methacrylate) (PBMA)–polyaniline (PANI) composite films were obtained by extrusion by use of two methods: the first method consisted of polymerizing a thin layer of PANI, with Cl^? as dopant, on the extruded film of PBMA; the second method was based on blends of PBMA and PANI produced by the extrusion of the two polymers by using dodecylbenzene sulfonic acid (DBSA) as dopant. The thermal properties, electrical conductivity, and morphology of the composite films obtained were measured. The sensitivity of the composites films as detectors of hydrogen peroxide and ammonia was evaluated. The change in the electrical resistance on exposure to different aqueous solutions of these components shows a linear behavior. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 179–183, 2003     

Formation mechanism of a nanotubular polyanilines prepared by an emulsion polymerization without organic solvent

A nanotubular polyaniline (PANINT) was prepared from a simple emulsified polymerization method without oil solvent present. A mechanism of the formation of the nano-fibers/tubes was proposed to show that it started with the connecting arrangement of the neighboring anilinium micelles before and during polymerization, which resulted in the formation of the intermediate morphology of centipedes converting into rod-like nanofibers later. The obtained PANINTs displayed not only nanofibrous structure but owned an unusual dispersing behavior in toluene. SEM and TEM showed the dendrite-like networks of nanofibers connected and glued together by the free (not complexed to polyaniline backbone) n-dodecylbenzene sulfonic acid (DBSA) molecules. After removing the free DBSA by acetone, the clear/well-defined empty nanotubes can be seen from TEM in the magnified micrograph. The Atomic force microscopic (AFM) microgaphs demonstrated the cottage like surface morphology of the un-perturbed PANINTs and the morphology was converted to an anisotropic/oriented rods after rubbing on the wet/cast PANINTs' dispersion of toluene before entire evaporation.     

Elastic polyaniline with EPDM and dodecylbenzenesulfonic acid as plasticizers

Elastomeric polyaniline was prepared by being mixed with ethylene–propylene–diene (EPDM) rubber in low concentrations (10, 20, or 30 wt %). The mixture was made in an internal mixer coupled to a torque rheometer. The polyaniline was doped with dodecylbenzenesulfonic acid (DBSA) via reactive processing during the mixing. When the EPDM rubber was added to the polyaniline and DBSA, the doping reaction was not interrupted, as demonstrated by an increase in the torque values. We chose the relative DBSA and EPDM concentrations to obtain the highest conductivities (10⁻¹ to 10⁻³ S cm⁻¹) and the best mechanical properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1768–1775, 2001     

Effect of dopant and oxidant on the electrochemical properties of polyaniline/graphite nanoplate composites

Optimizing the synthesis parameters of polyaniline/graphite nanoplate (PANI/GNP) composite is essential to the final electrochemical performance. Herein, the electrochemical properties of PANI/GNP composites, prepared by in situ chemical polymerization using varying amounts of different oxidants, with or without the addition of 4‐dodecylbenzenesulfonic acid (DBSA) as dopant, were investigated. Cyclic voltammetric results suggested that a stoichiometric amount of the oxidant iron chloride (FeCl₃) was beneficial to the electrochemical properties of the composites. The use of ammonium persulfate (APS) instead of FeCl₃ as oxidant largely increased the actual PANI content, conductivity and specific capacitance of the PANI/GNP composites. The dopant DBSA increased the conductivity of the PANI/GNP composites but did not show a positive effect on the electrochemical behavior. The cyclic voltammograms of the PANI/GNP composites indicated that the pseudocapacitance of PANI contributes more than the electrical double‐layer capacitance of GNP to the capacitance of the composites, while the presence of GNP plays an essential role in the rate capability of the composites. In this study, PANI/GNP (1:1) composite synthesized with an APS to aniline molar ratio of 1 showed a balanced combination of high specific capacitance (180.5 F g^?1 at 20 mV s^?1) and good rate capability (78% retention at 100 mV s^?1). © 2018 Society of Chemical Industry     

The effect of dopant on structural, thermal and morphological properties of DBSA-doped polypyrrole

Polypyrrole is prepared with different molar ratios of dodecylbenzene sulfonic acid (DBSA) (0.1, 0.2, 0.3 and 0.4) by in situ chemical polymerization method. The reaction temperature was 0–5 °C for 24 h. The FTIR spectrum confirmed the attachment of sulfonyl group in the pyrrole structure. The intensity of polypyrrole increased with increase in sulfur content. SEM graphs revealed the granular morphology of the doped polymer surface. DBSA has had strong effect on morphology with formation of aggregated particles at higher concentrations. Higher concentration of DBSA-doped PPy shows higher thermal stability. The promotion of electron from ground state to excited state of polypyrrole is confirmed by UV spectroscopic studies. Various sizes in particle distribution of DBSA-doped PPy were analyzed by a particle size analyzer. Solubility of polypyrrole was determined at room temperature. The solubility and quantity of polypyrrole increased with higher dopant concentration. Current–voltage (I–V) characteristics were carried out over the temperature range 313–343 K, which was found to be linear. The conductivity of doped-PPy showed high conductivity at low concentration of dopant while, conductivity decreased with increasing concentration of DBSA. The higher doping level of DBSA was confirmed by elemental analysis.     

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