Ring‐opening polymerization of caprolactone using novel polyaniline salt catalyst

Hybrid composite of polyaniline metal oxide composite, polyaniline‐dodecyl hydrogen sulfate salt with ferric oxide, was prepared for the first time via simple one‐step process of oxidizing aniline with ferric tris(dodecyl sulfate). Ferric tris(dodecyl sulfate) acts as an oxidant, emulsifier, dopant for polyaniline and also source of ferric oxide. Polyaniline salt composites were prepared via aqueous, emulsion, and interfacial polymerization pathways. Polyaniline salt composite was successfully demonstrated as polymer based solid acid catalysts in the ring‐opening polymerization of ε‐caprolactone for the first time. This methodology gave low molecular weight poly(ε‐caprolactone) (MW‐4035) with highly crystalline polymer of flower petals like morphology in 52 wt% yield (with respect to the amount of ε‐caprolactone used). Advantages of this methodology are the use of easily synthesizable, easily handlable, recyclable, cheaper, and eco‐friendly nature of the catalyst. POLYM. ENG. SCI., 55:2245–2249, 2015. © 2015 Society of Plastics Engineers     

Simultaneous Oxidation and Doping of Aniline to Polyaniline by Oxidative Template: Electrochemical Performance in Supercapacitor

Polyaniline salts containing sulfuric acid and cetyltrimethylammonium sulfate dopants were prepared by aqueous (PANI-Aq), emulsion (PANI-Em), and interfacial (PANI-In) polymerization pathways using cetyltrimethylammonium peroxodisulfate as an oxidative template. Formation of polyaniline was confirmed from infrared and X-ray diffraction spectral results. Value of conductivity (15 S cm^?1) of the polyaniline salt prepared by emulsion polymerization pathway was higher with that of the conventional polyaniline salt. PANI-Aq, PANI-Em, and PANI-In showed layered, flower petals, and nanorod and flower petals morphologies, respectively. These polyaniline salts were used as electrode in supercapacitor. Specific capacitance of PANI-Em, PANI-Aq, and PANI-In were 520, 484, and 474 F g^?1, which were higher than the conventional PANI-H₂SO₄ salt (390). Energy density was 26, 24.2, and 23.6 Wh kg^?1, respectively at a power density of 120 W kg^?1. After 3000 charge-discharge cycles, retention in the specific capacitance values of polyaniline salts was 86% (PANI-Em), 85.4% (PANI-Aq) and 76.1% (PANI-In).     

Preparation and characterization of soluble polyaniline

Polyaniline, which is soluble in common organic solvents, has been synthesized through the oxidative chemical polymerization of aniline in the presence of benzene diazonium chloride salt in an aqueous HCl acid medium. The blue‐black polyaniline thus prepared exists in a lower oxidation state than emeraldine. An X‐ray photoelectron spectroscopy study has shown that the intrinsic oxidation state of the polymer is 0.38. An elemental analysis has shown that the fractional doping level or degree of oxidation of the blue‐black polyaniline is 0.26. The product is believed to consist of a lower number of imine nitrogens in comparison with the polyemeraldine base. This fact is also corroborated by the lower electrical conductivity of the polymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Inverted emulsion polymerization route to polyaniline‐3D nanofiber network using sulfonated‐p‐cresol as novel dopant

Sulfonated‐p‐cresol (SPC) was used as novel dopant for the first time in the synthesis of polyaniline in 3D nanofiber networks (PANI‐3D). Polyaniline in 3D nanofiber network was prepared using organic solvent soluble benzoyl peroxide as oxidizing agent in presence of SPC and sodium lauryl sulfate (SLS) surfactant via inverted emulsion polymerization pathway. The influence of synthesis conditions such as the concentration of the reactants, stirring/static condition, and temperature etc., on the properties and formation of polyaniline nanofiber network were investigated. Polyaniline in 3D nanofiber network with 40–160 nm (diameter), high yield (134 wt % with respect to aniline used), and reasonably good conductivity (0.1 S/cm) was obtained in 24 h time. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polyaniline‐supported acid catalyst: Esterification of cinnamic acid with alcohols

Polyaniline‐supported acid salts such as polyaniline‐hydrochloride, polyaniline‐sulfate, and polyaniline‐nitrate were prepared by oxidation of aniline using benzoyl peroxide and ammonium persulfate as oxidizing agents. Polyaniline salts were used as catalysts in the esterification of cinnamic acid with alcohols. Polyaniline‐sulfate salt was found to be the best catalyst for the esterification of cinnamic acid. The reusability, handling, and recovery of the catalyst were found to be good. The yield of the ester depended on the type of the polyaniline salt, amount of the catalyst, amount of alcohol, and both the time and the temperature of the reaction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1584–1590, 2005     

Polyaniline–maleicacid–dodecylhydrogensulfate salt as sensor material for toxic gases

This article reports the results of novel polyaniline material as gas sensor, capable of operating at room temperature for toxic gases. Polyaniline–maleicacid–dodecylhydrogensulfate salt (PANI‐MA‐DHS) was prepared by emulsion polymerization pathway, which is soluble in N, N‐dimethyl formamide. PANI‐MA‐DHS was coated on a ceramic bead by simple brush coating method and used as sensor material. The resistance change of PANI‐MA‐DHS material for NH₃, CO₂, SO₂, and H₂S gases at different concentrations (10, 100, 1000, and 10,000 ppm level) was monitored for sensor characteristics. The stability of the polyaniline material under continuous exposure of gas level from 10 to 10,000 ppm was also studied. This novel gas sensor material has advantages such as excellent sensing ability, low cost, fast regeneration time (～ 1–2 min), simple experimental setup, and operable at room temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

聚苯胺溶解性研究

以苯胺氧化聚合和乳液聚合两种方法合成聚苯胺(PAn),研究了溶剂、聚合方法、反应温度、导电态、十二烷基苯磺酸用量等因素对聚苯胺溶解性的影响。结果表明,N-甲基吡咯烷酮是本征态聚苯胺的良溶剂,用乳液聚合法合成的聚苯胺其溶解性明显高于化学氧化法合成的聚苯胺,当乳液中十二烷基苯磺酸∶苯胺(摩尔比)=2.0∶1,聚合温度25℃时合成溶解率大的PAn。     

Polyaniline salts and complexes: Efficient and reusable catalyst for the one‐pot synthesis of 5‐(methoxycarbonyl)‐6‐methyl‐4‐phenyl‐3,4‐dihydropyrimidin‐2(1h)‐one

Polyaniline salts were prepared by doping polyaniline base with different Bronsted acids (sulfuric, nitric, phosphoric, perchloric, hydrochloric acid) and organic acids (p‐toluene sulfonic acid, 5‐sulfosalicylic acid). Polyaniline complexes were also prepared using Lewis acids (aluminum chloride, ferric chloride). Polyaniline salts and polyaniline complexes were used as catalysts in Biginelli reaction for 5‐(methoxycarbonyl)‐6‐methyl‐4‐phenyl‐3,4‐dihydropyrimidin‐2(1H)‐one synthesis. Benzaldehyde and urea were reacted with methyl acetoacetate using polyaniline‐p‐toluene sulfonate salt as catalyst with different reaction time, temperature, and amount of catalyst. The use of polyaniline catalysts is feasible because of the easy preparation, easy handling, stability, easy recovery, simple work‐up procedure, reusability, excellent activity with less amount of catalyst, and eco‐friendly nature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1741–1745, 2006     

乳酸掺杂聚苯胺／PP 树脂复合材料

乳液聚合法聚合乳酸掺杂聚苯胺。再使用开炼机混炼PP/聚苯胺,最后平板硫化仪得到永久抗静电聚苯胺/PP。研究发现,聚苯胺/PP复合材料的相容性好。通过掺杂,乳酸中解离出的H＋与聚苯胺分子链上的N原子结合,使聚苯胺获得永久、稳定的导电性。结果证明,随着聚苯胺的添加量,体积电阻减小三个数量级,冲击强度、拉伸强度和硬度足以满足很多应用的要求。     

Synthesis of higher soluble nanostructured polyaniline by vapor‐phase polymerization and determination of its crystal structure

Higher soluble nanostructured polyaniline was prepared by vapor‐phase polymerization after passing aniline vapor through an aqueous acidic solution of ammonium persulfate (PANI‐V). Polyaniline was also synthesized by the conventional oxidative polymerization method (PANI‐C) in an aqueous medium for the comparison of its properties with PANI‐V. PANI‐V exhibited lower conductivity but higher hydrophilicity and higher solubility (2–3 times) in different solvents, such as tetrahydrofuran, N‐methyl‐2‐pyrrolidone, dimethylsulfoxide, N,N‐dimethyl formamide, and m‐cresol at room temperature compared with that of PANI‐C. The thermal stability of PANI‐V was higher than that of PANI‐C. In‐depth investigations of the crystal structures of PANI‐C and PANI‐V were performed through powder X‐ray diffraction analysis. The PANI‐V showed a less ordered structure with a lower crystallinity and crystallite size and with a higher d‐spacing and interchain separation compared with PANI‐C. The unit cell volume of PANI‐V was significantly higher with a greater number of atoms in the unit cell than that of PANI‐C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

显微红外技术研究聚苯胺涂层防腐蚀性能

聚苯胺是一种导电高分子,聚苯胺涂料因其性价比较高而被看作是新一代环境友好型的高效防腐涂料.本研究以过硫酸铵为引发剂,十二烷基苯磺酸钠为乳化剂,采用乳液聚合法制备丙烯酸树脂乳液.分别采用乳液互穿网络聚合法和乳液共混法制备聚苯胺--丙烯酸树脂防腐蚀涂料,并利用红外显微镜技术分析聚苯胺在聚苯胺--丙烯酸树脂防腐蚀涂料中的分散性.涂层在马口铁上腐蚀电位和极化曲线的测试结果表明,采用乳液互穿网络聚合法制备的聚苯胺--丙烯酸树脂防腐蚀涂层在ω(NaCl)为3.5%的NaCl溶液中的开路电位比乳液共混法升高了0.596V,自腐蚀电流降低了1个数量级.     

Waterborne acrylic–polyaniline nanocomposite as antistatic coating: preparation and characterization

An antistatic and electrically conductive acrylic–polyaniline nanocomposite coating was successfully synthesized by interfacial polymerization of aniline in the presence of acrylic latex. The acrylic latex was prepared through emulsion polymerization, and aniline was polymerized by in situ interfacial polymerization at the interface of acrylic latex/chloroform phase. Fourier transform infrared spectroscopy (FTIR), UV–Vis spectroscopy and CHNS elemental analysis revealed the existence of 6.24 wt% emeraldine salt of polyaniline (PAni) in the dried film of the nanocomposite. Scanning electron microscopy (SEM) confirmed the presence of colloidal polymer particles in the aqueous phase which was confirmed to have some advantages, including prevention of aggregation of particles, dispersibility improvement and enhancement of the PAni nanofibers aspect ratio in the acrylic polymer matrix. According to SEM results, PAni fibers with the length ranging from 12 to 67 µm and diameters between 0.078 and 1 µm, highly dispersed in the acrylic polymer matrix, were successfully synthesized. Thermal, electrical and mechanical properties of the acrylic copolymer were significantly affected by PAni incorporation. The onset degradation temperature in thermogravimetric analysis revealed that the thermal stability of the nanocomposite was improved compared to that of the pure acrylic copolymer. The nanocomposite film showed electrical conductivity of about 0.025 S/cm at room temperature, along with satisfactory mechanical properties, attractive as an antistatic material in coating applications.     

有机磷酸掺杂聚苯胺的乳液聚合

以水 -二甲苯 (配比为 1 50 /50 )为分散相、环状有机磷酸为掺杂剂 ,采用乳液聚合法合成了电导率达 8.4 2 S/cm的聚苯胺。将所得产物与盐酸水溶液体系所得产物的色泽、外观、微观形貌、导电性能、溶解性能进行了对比 ,乳液聚合所得产物的溶解性能明显优于盐酸水溶液体系所得产物。     

合成条件对聚苯胺成纤性能的影响

以苯胺为单体、过硫酸铵为氧化剂、在盐酸水溶液中化学法合成聚苯胺 ,研究的重点是确立一个能够适合纺丝要求的合成参数体系。合成的聚苯胺重均相对分子质量达 2 9× 10 4。以不同条件下合成的聚苯胺为原料湿法纺制了聚苯胺导电纤维。     

Characterization of polyaniline/Ag nanocomposites using H2O2 and ultrasound radiation for enhancing rate

Polyaniline/Ag nanocomposites have been synthesized via in situ chemical oxidation polymerization of aniline in silver salt by sonochemical method using H₂O₂ as an external medium. H₂O₂ was used to reduce AgNO₃ to Ag nanoparticles as well as to polymerize aniline to polyaniline in the same pot. The ultrasound radiation as an energy source was applied to facilitate the reaction by reducing the reaction time. Reduction of the silver salt in aqueous aniline leads to the formation of silver nanoparticles which in turn catalyze oxidation of aniline to polyaniline. The research on the structures and properties of the composites showed the individual or aggregated silver nanoparticles are dispersed in the matrix of polyaniline. The composites possess a higher degradation temperature than polyaniline alone, and their electrical conductivity are raised morethan 200 times. The cyclic voltammetry and impedance spectroscopy results showed that the polyaniline/Ag film exhibits considerably higher electroactivity compared with polyaniline film without Ag particles. POLYM. COMPOS., 31:1662–1668, 2010. © 2009 Society of Plastics Engineers     

Carbon nanotube–polyaniline composites

The last decade has seen a growing interest in hybrid electrically conducting nanocomposites. This article aims to provide a detailed overview of the present status of research in carbon nanotube–polyaniline (CNT/PANI) composites, from processing to structural and property evaluations. CNT/PANI are synthesized by electrochemical and chemical processing. When chemical methods are used, the main challenge is to obtain processable CNT/PANI in the emeraldine salt (ES) form composites. Stable dispersions of ES–CNT in organic media are prepared using the post doping method, inverse emulsion polymerization, or ex situ polymerizations. On the contrary, stable water dispersions of CNT/ES are prepared using hydrophilization of a preformed CNT/ES composite, direct synthesis of micelle–CNT hybrid templates, interfacial polymerization, covalent functionalization of CNT with a water soluble polymer, or using electrostatic interactions between two oppositely charged ES and CNT aqueous colloids. Moreover, the strategies for the synthesis of ternary CNT/PANI composites incorporating noble metal nanoparticles, metal oxide, or graphene sheets are also presented and analyzed in depth. Finally, we give a review of potential applications, including chemical sensors, capacitors, fuel cells and electronic devices.     

Preparation of nanosize polyaniline by solid‐state polymerization and determination of crystal structure

BACKGROUND: Nanosize polyaniline has several advantages in both the fabrication of nanodevices and for preparing nanoscale electrical connections in highly conducting polymer composites. RESULTS: Nanosize polyaniline with a diameter of 30–60 nm was prepared using a solid‐state polymerization process (PANI‐S) by mixing an equimolar quantity of ammonium persulfate and anilinium chloride crystals with a mortar and pestle. Polyaniline was also synthesized using a conventional oxidative polymerization method (PANI‐C) in an aqueous medium for comparison. Conductivity and contact angle measurements, infrared spectroscopy, ultraviolet spectroscopy, transmission electron microscopy and thermogravimetric analysis were carried out. An in‐depth investigation of the crystal structure of these polymers was carried out through powder X‐ray diffraction analysis. CONCLUSION: PANI‐S exhibited lower conductivity due to the presence of less emeraldine base form, lower crystallinity, greater d‐spacing and greater inter‐chain separation than PANI‐C. The hydrophilicity and thermal stability of PANI‐S were higher than those of PANI‐C. The unit cell volume of PANI‐S was much higher, resulting in a larger crystallite size and a greater number of atoms in the unit cell than PANI‐C. Copyright © 2009 Society of Chemical Industry     

Exploration of the morphological transition phenomenon of polyaniline from microspheres to nanotubes in acid‐free aqueous 1‐propanol solution in a single polymerization process

Polyaniline micro‐ or nanostructures have been widely investigated due to their unique physical and chemical properties. Although several studies have reported the synthesis of polyaniline microspheres and nanotubes, their mechanisms of formation remain controversial. This study reports our observation of the morphological transition of polyaniline from microspheres to nanotubes in a single polymerization process and also tries to propose their mechanisms of formation. The polymerization of aniline monomer in acid‐free aqueous 1‐propanol solutions (1 and 2 mol L^?1) produces polyaniline microspheres and nanotubes at different reaction stages through a morphology transition process with treatment using ultrasound. In the initial reaction stage, Fourier transform infrared spectra indicate that the aniline monomers form phenazine‐like units, producing polyaniline microspheres with an outside diameter of 1–2 µm. The hydrogen bonds between 1‐propanol and polyaniline serve as the driving force for the polyaniline chains to build microspheres. As the reaction continues, observation indicates the microspheres decompose and reform one‐dimensional nanotubes. In this stage, a structure consisting of a head of phenazine‐like units and a tail of acid‐doping para‐linked aniline units develops. The protonation of the para‐linked aniline units provides the driving force for the formation of nanotubes through a self‐curling process. We report here the unique morphology transition of polyaniline from microspheres to nanotubes in a single polymerization process. The results indicate that the structural change of polyaniline leads to this morphological change. The mechanisms of formation of the microspheres and nanotubes in a polymerization process are also well explained. Copyright © 2010 Society of Chemical Industry     

Synthesis of water‐soluble and conducting polyaniline by growing of poly (N‐isopropylacrylamide) brushes via atom transfer radical polymerization method

Polyaniline‐graft‐Poly(N‐isopropylacrylamide) copolymers were synthesized by atom‐transfer radical polymerization (ATRP) of N‐isopropylacrylamide using polyaniline macro‐initiators. Polyaniline‐chloroacetylchloride and polyaniline‐chloropropionylchloride macroinitiators were obtained by the reaction of amine nitrogens of polyaniline with chloroacetyl chloride and 2‐choloropropionyl choloride, respectively. Both macroinitiators and graft copolymers were characterized by FT‐IR and ¹H‐NMR spectroscopy. The cyclic voltammetry (CV) and UV‐Vis spectroscopy studies showed that these copolymers are electroactive. The solubility test revealed that the polyaniline‐graft‐poly (N‐isopropylacrylamide) copolymers are water soluble or water/methanol soluble. The Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) images showed the growing of poly (N‐isopropylacrylamide) chains on polyaniline backbone. Investigation of thermal behavior of graft copolymers by thermal gravimetry analysis (TGA) confirmed the results obtained from AFM and SEM images. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Comparative study of conducting polyaniline/copper and polyaniline/nickel composites in the presence of surfactants

Polyaniline/copper and polyaniline/nickel composites were synthesized in the presence and absence of surfactants using ammonium persulfate as an initiator. The structural and surface characteristics of the composites were studied and compared using different techniques. The interfacial interactions and thermal stability of the composites were characterized using X‐ray diffraction and thermogravimetric analysis. Surface properties were investigated using scanning electron microscopy and energy‐dispersed X‐ray spectroscopy. The results indicate significant changes in the morphological and physicochemical properties of the composites when incorporating surfactants. The surfactant‐induced surface characteristics also have an effect on conductivity. Copyright © 2010 Society of Chemical Industry