Polyurethane/polyaniline and polyurethane‐poly(methyl methacrylate)/polyaniline conductive core‐shell particles: Preparation,morphology, and conductivity

Polyurethane/polyaniline (PU/PANI) and polyurethane‐poly(methyl methacrylate)/polyaniline (PU‐PMMA/PANI) conductive core‐shell particles were synthesized by a two‐stage polymerization process. The first stage was to produce a core of PU or PU‐PMMA via miniemulsion polymerization using sodium dodecyl sulfate (SDS) as the surfactant. The second stage was to synthesize the shell of polyaniline over the surface of core particles. Hydrogen chloride (HCl) and dodecyl benzenesulfonic acid (DBSA) were used as the dopant agents. Ammonium persulfate (APS) was used as the oxidant for the polymerization of ANI. Different concentrations of HCl, DBSA, and SDS would cause different conformations of PANI chains and thus different morphologies of PANI particles. UV–visible spectra revealed that the polaron band was blue‐shifted because of the more coiled conformation of PANI chains by increasing the concentration of DBSA. Besides, with a high concentration of DBSA, both spherical‐ and rod‐shape PANI particles were observed by transmission electron microscope, and the coverage of PANI particles onto the core surfaces was improved. The key point of formation of rod‐type PANI particles was that DBSA was served with a high concentration accompanied with the existence of HCl or SDS. The better coverage of PANI particles over the core surfaces by charging higher DBSA concentrations resulted in a higher conductivity of hybrid particles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3902–3911, 2007     

Conducting Elastomer Blends Based on Nitrile Rubber and Pani.DBSA

Electrically conductive elastomer blends based on polyaniline-dodecylbenzene sulfonic acid (Pani.DBSA) and nitrile rubber (NBR) were prepared by polymerization of aniline in the presence of NBR, using a direct, one-step in situ emulsion polymerization method. At the same PAni content, the conductivity of the in situ emulsion-polymerized blends is higher than that of blends produced by mechanical mixing of both components. In addition, a morphology with the presence of PAni in the form of microtubules was achieved by the in situ process. Stronger interaction between the components were also confirmed by Rheological processing analysis (RPA). The vulcanization process decreases the conductivity of the blends prepared by both methods. The in situ polymerized blends also display higher tensile strength and also higher crosslink density     

An investigation into the relationship between the electrical conductivity and particle size of polyaniline in nano scale

Polyaniline nanoparticle (nPANI) was successfully synthesized through ultrasonic-assisted reverse microemulsion polymerization method. The effect of four parameters including concentration of aniline (ANI) as monomer, molar ratio of dodecybenzene sulfonic acid (DBSA) as surfactant to ANI, molar ratio of ammonium peroxydisulfate (APS) as oxidant to ANI and polymerization temperaturewere systematically studied in terms of the structural characterizations of nPANI by applying the Taguchi method of experimental design. Data analysis indicated that there is a dependency between conductivity and particle size in the nanoscale; the maximum conductivity of nPANI was obtained when the diameter of the particles was 30?nm.     

Structure and properties of conducting bacterial cellulose-polyaniline nanocomposites

Conducting composite membranes of bacterial cellulose (BC) and polyaniline doped with dodecylbenzene sulfonic acid (PAni.DBSA) were successfully prepared by the in situ chemical polymerization of aniline in the presence of hydrated BC sheets. The polymerization was performed with ammonium peroxydisulfate as the oxidant agent and different amounts of DBSA. The composites were characterized by X-ray diffraction, attenuation reflectance Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), impedance spectroscopy and small angle X ray scattering (SAXS). The highest electrical conductivity value was achieved by using a DBSA/aniline molar ratio of 1.5 because this condition provided a better penetration of PAni.DBSA chains inside the hydrated BC sheet, as observed by SEM. The in situ polymerization gives rise to conducting membranes with the surface constituted by different degree roughness as indicated by Nyquist plots obtained from impedance spectroscopy and confirmed by SAXS measurements. This preliminary work provides a new way to prepare cellulose-polyaniline conducting membranes which find potential applications as electronic devices, sensors, intelligent clothes, etc.     

UV cured transparent films including non‐aqueous conductive microgels

UV cured transparent films containing non‐aqueous conductive microgels coated with poly(aniline)/dodecyl benzenesulfonic acid(DBSA) were obtained. The conductive microgels were prepared by interface polymerization of aniline/DBSA in the presence of non‐aqueous polymeric microgels. The electrical conductivity and the particle size of the prepared conductive microgel were 0.5 S/cm and 58 nm, respectively. The prepared conductive microgels were easily blended with a UV curable coating formulation, and then were cured to make highly optically transparent films. For the UV cured film containing about 35 wt% of the conductive microgels, a surface resistance in the range of 10⁷ to 10⁸ Ω/square was obtained. In a polar cosolvent, such as NMP and m‐cresol, the critical volume was shifted to the lower range, with a value of 10 wt%. The UV cured films containing the conductive microgels exhibited good electrical stability against the thermal aging and humidity. Copyright © 2002 John Wiley & Sons, Ltd.     

Polymerization of anilinium–DBSA in the presence of clay particles: kinetics and formation of core‐shell structures

This paper is an extension of previous work on polymerization of anilinium–DBSA (dodecylbenzenesulfonic acid) in an aqueous dispersion in the presence of mica or talc silicate particles. The presence of mica or talc particles greatly accelerates the polymerization process of anilinium‐DBSA and an encapsulated structure is formed as well. The catalytic effect of various metallic cations which exist in the chemical compositions of mica or talc on the polymerization kinetics of anilinium‐DBSA was investigated. The conductivity results along with microscopy observations prove a well formed encapsulated structure for the polyaniline/mica composites, but less for the polyaniline/talc composites. The anilinium‐DBSA complex and mica aqueous dispersions pretreated at different temperatures prior to polymerization have shown a significant effect on the polymerization rate of anilinium‐DBSA. The higher the dispersion temperature, the higher is the polymerization rate found. Copyright © 2001 John Wiley & Sons, Ltd.     

掺杂/脱掺杂诱导的聚苯胺织物浸润性开关

以三氟乙酸(TFA)作为掺杂剂,三氯化铁为氧化剂,采用原位化学氧化法制得了具有超疏水性能的聚苯胺/棉布复合导电织物(PANI/CCT),所得织物在外界酸度诱导下发生掺杂/脱掺杂反应而导致其由导电态向绝缘态的转变,从而实现超疏水到超亲水的可逆、快速变化.研究结果证实上述的超疏水/超亲水可逆的变化来自聚苯胺与纤维的微/纳米结构和TFA的低表面自由能的协同效应.     

Structure of Composite Films Containing Polyaniline Studied by DSC

A structural study of conductive composite films consisting of ethylene-co-vinylacetate (EVA) copolymer, polyaniline (PANI) and dodecylbenzenesulfonic acid (DBSA), a part of which being complexed with PANI, was performed by using differential scanning calorimetry (DSC) and presented for the first time. An additional crystalline phase is formed during the film formation by thickening EVA chain-folded lamellae with participation of‘free’ DBSA molecules at lower net PANI content (up to 5 mass%) and of both ‘free’ and complexed DBSA molecules (up to 7.5 mass%). At higher PANI content PANI-DBSA complex starts to form its own crystals and at 17.5 mass% of PANI mixed crystals of EVA with ‘free’ DBSA alkyl chains are preferably formed. It is also found that the Fox' equation correlating the glass transition temperature of a miscible blend system with its composition can be actually used in estimating the miscibility of EVA/PANI blends no matter the presence of DBSA. This revised version was published online in August 2006 with corrections to the Cover Date.     

Ageing of Conductive Polyaniline/Poly(Ethylene-co-Vinylacetate) Composites Studied by Thermal Methods

The long-term environmental ageing of conductive composite films containing ethylene-co-vinyl-acetate (EVA) copolymer and a complex of polyaniline (PANI) and dodecylbenzenesulfonic acid (DBSA) was studied by using differential scanning calorimetry (DSC). We assume that both phase separation and crosslinking of PANI main chains occur in the systems. On the other hand, the competition between PANI–DBSA complex self-organization and crystallization of EVA matrix result in structural changes and formation of continuous conductive network, responsible for significantly increased (ca five orders of magnitude) electrical conductivity of the aged films. This revised version was published online in August 2006 with corrections to the Cover Date.     

Effect of preparation method on nanoscopic structure of conductive SBS/PANI blends: Study using small‐angle X‐ray scattering

Small‐angle X‐ray scattering (SAXS) studies of electrically conductive blends based on polyaniline–dodecylbenzenesulfonic acid (PANI–DBSA)/styrene–butadiene–styrene (SBS) triblock copolymer were performed to investigate the influence of the blend preparation procedure on the nanoscopic structure of the blends. The blends were prepared by mechanical mixing (MM) procedure and by in situ polymerization (ISP) of aniline in the presence of SBS. The results indicate that pure PANI–DBSA presents an extended phase consisting of crystalline islands of nanometric size, with a good spatial correlation between them, embedded into an amorphous PANI phase. This feature was not observed in SBS/PANI–DBSA blends prepared by MM or ISP. In MM blends, the PANI phase is constituted by smaller domains, containing poorly spatially correlated crystalline islands, whereas in ISP blends with low or medium amount of PANI, there is no SAXS peak which could be related to a spatial correlation between PANI crystalline islands. The conductivity of the ISP blends is higher when compared to MM blends because of the higher homogeneity at nanometric scale. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3069–3077, 2007     

苯胺在十二烷基苯磺酸/水体系中的乳液聚合过程研究

利用光学显微镜和扫描电镜,对以水为介质、十二烷基苯磺酸(DBSA)为乳化剂的苯胺乳液聚合过程进行监测,发现苯胺在水体系中与DBSA反应形成DBSA-苯胺盐的棒状聚集结构,讨论了DBSA、苯胺、氧化剂的配比及浓度对聚合过程中棒状聚集结构的长度和数量及生成聚苯胺的电导率的影响,提出苯胺在DBSA/水体系中的乳液聚合反应是在胶束表面进行的,而棒状聚集结构中的DBSA-苯胺盐单体经水相扩散到乳胶粒子中,形成颗粒状的聚苯胺.     

Structural Investigations of Polyaniline Prepared in the Presence of Dodecylbenzenesulfonic Acid

Structural studies of powdered polyaniline (PANI) prepared in aqueous medium by the oxidative polymerization of aniline in the presence of dodecylbenzenesulfonic acid(DBSA) were performed by means of DSC and WAXS. The influence of the alkyl side-chains on the structure and crystallinity of the as-synthesized PANI—DBSA and on the structural transitions taking place in PANI upon washing and heating were investigated. It was found that DBSA induces crystallinity in the rigid matrix of PANI, and residual crystalline phases were also observed after the deprotonation of PANI—DBSA. For the first time, a melting peak and a relaxation transition of non-cross-linked PANI were registered.This revised version was published online in November 2005 with corrections to the Cover Date.     

Dielectric behavior of polyaniline synthesized by different techniques

Polyaniline doped with dodecylbenzenesulfonic acid (Pani.DBSA) was synthesized by different procedures: by a dedoping-redoping process, by one step inverted emulsion polymerization and by one step aqueous dispersion polymerization. The effect of these different techniques on the electric properties (dielectric constant, dielectric losses, and complex electric modulus) of the corresponding emeraldine base has been studied by thermal dielectric analyzer (DETA) in the temperature range −130 °C to 200 °C and in frequency range 0.03-10⁵ Hz. It was found that the preparation technique has significant influence on the dielectric properties of Pani. The different synthetic routes give rise to polyaniline with different distribution of electric relaxation process, indicating different chain structure. Emeraldine base from Pani.DBSA prepared by one step aqueous dispersion polymerization exhibits one single relaxation peak with narrow distribution whereas that prepared by inverted emulsion polymerization exhibits two relaxation peaks, indicating two-phase structure as indicated by a bimodal distribution of relaxation process. Emeraldine base from Pani.DBSA prepared by dedoping-redoping process presents an intermediary behavior. Percentage crystallinity of Pani.DBSA samples has also been investigated using wide-angle X-ray diffraction analysis. Pani.DBSA prepared by aqueous dispersion exhibited higher crystallinity degree, which agrees with the higher conductivity.     

磁场及反应条件对十二烷基苯磺酸掺杂聚苯胺聚合成膜速率的影响

在恒定磁场(0.6 T)条件下, 采用过硫酸铵(APS)为引发剂, 在乳液体系中合成了十二烷基苯磺酸(DBSA)掺杂的聚苯胺(PAn). 借助石英晶体微天平(QCM)实时监测苯胺(An)在金电极表面聚合成膜过程, 探讨了磁场、APS浓度、DBSA浓度及反应温度对DBSA掺杂聚苯胺聚合成膜速率的影响. 实验结果表明, PAn在金电极表面的成膜速率随磁场强度的增加而增大; 由反应物浓度与PAn成膜速率的关系, 得出相应的动力学反应级数; 由PAn膜的增长速率与温度的关系, 得到成膜过程的活化能为41.08 kJ/mol. 考察了PAn聚合过程的UV-Vis光谱, 并与QCM所得的结果进行了比较. 结果显示, 在相同时间内, 磁场环境下合成的PAn的吸收强度大于无磁环境下合成的PAn.     

原位聚合聚乙烯/蒙脱土纳米复合材料的结晶行为

用DSC研究了HDPE与MMT负载的催化剂熔融共混和原位聚合得到的两种纳米复合材料的熔融、 结晶行为和等温结晶动力学.  结果表明, HDPE与熔融共混样品的结晶度、 平衡熔点、 球晶生长速率和结晶能力大体相同; 原位聚合得到的HDPE/MMT纳米复合材料的结晶度和平衡熔点高于纯HDPE; 在相同过冷度条件下熔融结晶速率和结晶能力低于纯HDPE, 而在相同结晶温度Tc下, 熔融结晶速率和结晶能力则高于纯HDPE.  纯HDPE的晶体生长侧向单位面积表面自由能最小, 其次是熔融共混样品, 原位聚合样品最大, 且随ＭＭＴ含量的增加逐渐升高.     

Polyaniline/thermoplastic polyurethane blends: Preparation and evaluation of electrical conductivity

Conducting polymer blends whose undiluted components have different properties are promising materials for specific applications and have attracted interest in recent years. The aim of this study was to obtain and evaluate the electrical conductivity of polyaniline doped with dodecylbenzenesulfonic acid (PAni.DBSA)/polyurethane thermoplastic (TPU) blends. The PAni.DBSA was synthesized from DBSA-aniline (DBSAn) salt through an emulsion polymerization in tetrahydrofurane (THF) or in the presence of polyurethane thermoplastic solution, resulting in pure PAni.DBSA or PAni.DBSA/TPU blends. Blends of PAni.DBSA/TPU were also prepared through casting, at room temperature, after dissolving both components in THF as a common solvent. The insulator-conductor transition was very sharp and the percolation threshold was lower than 2.7 wt% of PAni.DBSA. The electrical conductivity of PAni.DBSA/TPU blends, prepared by both methods, reached maximum values at a PAni.DBSA concentration of 40 wt%, close to the value observed for the undiluted conducting polymer. However, for a PAni.DBSA content lower than 30 wt%, the electrical conductivity was dependent on the blend preparation method. Blends were characterized by infrared spectroscopy, thermogravimetric analysis (TG) and optical microscopy. The electrical conducting characteristics of the PAni.DBSA/TPU blends prepared using different procedures indicate a high potential for their successful application in electrical processes.     

Electrically conductive,melt‐processed ternary blends of polyaniline/dodecylbenzene sulfonic acid,ethylene/vinyl acetate,and low‐density polyethylene

Although polyaniline (PANI) has high conductivity and relatively good environmental and thermal stability and is easily synthesized, the intractability of this intrinsically conducting polymer with a melting procedure prevents extensive applications. This work was designed to process PANI with a melting blend method with current thermoplastic polymers. PANI in an emeraldine base form was plasticized and doped with dodecylbenzene sulfonic acid (DBSA) to prepare a conductive complex (PANI–DBSA). PANI–DBSA, low‐density polyethylene (LDPE), and an ethylene/vinyl acetate copolymer (EVA) were blended in a twin‐rotor mixer. The blending procedure was monitored, including the changes in the temperature, torque moment, and work. As expected, the conductivity of ternary PANI–DBSA/LDPE/EVA was higher by one order of magnitude than that of binary PANI–DBSA/LDPE, and this was attributed to the PANI–DBSA phase being preferentially located in the EVA phase. An investigation of the morphology of the polymer blends with high‐resolution optical microscopy indicated that PANI–DBSA formed a conducting network at a high concentration of PANI–DBSA. The thermal and crystalline properties of the polymer blends were measured with differential scanning calorimetry. The mechanical properties were also measured. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3750–3758, 2004     

Micelle-assisted synthesis of polyaniline/magnetite nanorods by in situ self-assembly process

Polyaniline/magnetite nanocomposites consisting of polyaniline (PANI) nanorods surrounded by magnetite nanoparticles were prepared via an in situ self-assembly process in the presence of PANI nanorods. The synthesis is based on the well-known chemical oxidative polymerization of aniline in an acidic environment, with ammonium persulfate (APS) as the oxidant. An organic acid (dodecylbenzenesulfonic acid, DBSA) was used to replace the conventional strong acidic (1 M HCl) environment. Here, dodecylbenzenesulfonic acid is used not only as dopant, but also as surfactant in our reaction system. So, DBSA can excellently control the morphology and size of PANI nanorods and magnetite particles. Magnetite particles were formed simultaneously during sedimentation, and the formed nanorods were also decorated by the particles. The resulting PANI/magnetite composites were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). It is found that PANI/magnetite nanorod composites have uniform size, superparamagnetism and a small mass fraction of magnetite, thermal stabilization even at a higher temperature.     

Resistivity-Temperature Behavior of CB-Filled HDPE Foaming Composites

High-density polyethylene/carbon black foaming conductive composites were prepared from acetylene black（ACEY） and super conductive carbon black（HG-1P） as conductive filler, low-density polyethylene（LDPE） as the second component, ethylene-vinyl acetate（EVA） and ethylene propylene rubber（EPR） as the third component, azobisformamide（AC） as foamer, and dicumyl peroxide（DCP） as cross-linker. The structure and resistivity-temperature behavior of high-density polyethylene（HDPE）/CB foaming conductive composites were investigated. Influences of carbon black, LDPE, EVA, EPR, AC, and DCP on the foaming performance and resistivity-temperature behavior of HDPE/CB foaming conductive composites were also studied. The results reveal that HDPE/CB foaming conductive composite exhibits better switching characteristic; ACET-filled HDPE foaming conductive composite displays better positive temperature coefficient（PYC） effect; whereas super conductive carbon black（HG-1P）-filled HDPE foaming conductive composite shows better negative temperature coefficient（NTC） effect.     

Effect of aniline formaldehyde resin on the conjugation length and structure of doped polyaniline: Spectral studies

A DBSA (n‐dodecylbenzene sulfate)‐complexed aniline formaldehyde [AF(DBSA)_1.0] was successfully synthesized with excess aniline (compared with formaldehyde) in the presence of n‐dodecylbenzene sulfonic acid (HDBSA), which was complexed with aniline monomer before polymerization. The resin was carefully characterized with ¹H and ¹³C NMR, electron spectroscopy for chemical analysis, and Fourier transform infrared and was demonstrated to be a polymer in which anilines were all complexed with HDBSA and became anilinium salts. A drastic decrease of the maximum absorption wavelength (ultraviolet–visible spectra) of DBSA‐doped polyaniline [PANI(DBSA)_0.5] was found when AF(DBSA)_1.0 was mixed, and this resulted from the reduced conjugation length. A similar effect on PANI(DBSA)_0.5 was found when free HDBSAs were mixed with PANI(DBSA)_0.5. Visual inspection with an optical microscope revealed that PANI(DBSA)_0.5/AF(DBSA)_1.0 gave uniform morphologies in various compositions, showing possible miscibility for this system. X‐ray diffraction patterns of PANI(DBSA)_0.5/AF(DBSA)_1.0 showed that the layered structure of PANI(DBSA)_0.5 was still present but became shorter in the polyblend because of the presence of AF(DBSA)_1.0. Solid‐state ¹³C NMR spectra revealed that the reduced conjugation length was derived from the interaction of alkyl groups between HDBSA, complexed DBSA, and dopant DBSAs. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3116–3125, 2005