Didecyl ester of 4‐sulfophthalic acid as a plast dopant and emulsifier in the chemical polymerization of aniline into polyaniline salt

Polyaniline salt was synthesized through the chemical oxidation of aniline with sodium persulfate as the oxidant and didecyl ester of 4‐sulfophthalic acid via three different polymerization pathways (aqueous, emulsion, and interfacial). In these polymerization processes, the ester acted as a novel plast dopant and as an emulsifier. The yield, conductivity, and number of ester units present in the polyaniline salts were determined. A polyaniline salt prepared by emulsion polymerization was soluble in chloroform and showed excellent solution‐processing properties. Polyaniline samples prepared by aqueous or interfacial polymerization were not soluble in chloroform. A soluble polyaniline salt was successfully synthesized through the washing of an organic layer containing the polyaniline salt with water in emulsion polymerization. X‐ray diffraction spectra of polyaniline salts prepared by the three different methods showed an ordered, layer‐type supramolecular structure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and properties of 8‐hydroxyquinoline aluminum quinoline/polyaniline core–shell composite

Polyaniline (PANI) as an excellent conducting polymer material has been used to synthesize 8‐hydroxyquinoline aluminum quinoline/polyaniline (Alq₃/PANI) composites with core‐shell structure which is expected to form ultra‐conjugated system between core/shell and be used as organic electronic material. Alq₃ was coated by sodium dodecyl benzene sulfonate doped PANI via in situ polymerization of aniline on the surface of Alq₃. The morphology, structure crystallinity, and thermal stability of synthesized composite were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, and thermal gravimetric analysis. Results indicated that the composite is core‐shell structure and exhibits good thermal stability. Conductivity of composite was investigated and showed that Alq₃ as core in composite which improved the conductivity of pristine PANI, indicating that electronic interactive effect was formed between core and shell. POLYM. COMPOS., 36:272–277, 2015. © 2014 Society of Plastics Engineers     

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     

多功能性聚苯胺/聚合物纳米复合材料的制备及应用

基于国内外最新研究文献及本课题组的研究,综述了多功能性聚苯胺/聚合物纳米复合材料的制备方法、性能及应用前景。聚苯胺/聚合物纳米复合材料可以由机械共混法、涂布法和原位聚合法,如分散聚合法、模板诱导聚合法及电化学聚合法制备得到。聚苯胺/聚合物纳米复合材料在透明导电塑料薄膜、防静电涂料、导电纤维、电致发光器件、电磁屏蔽材料等领域有着广阔的应用前景。     

Preparation and characterization of a type of ladder‐like poly(phenyl silsesquioxane) based hybrid star‐shaped copolymer of ε‐caprolactone

Combination of the organic–inorganic hybrid such as silsesquioxane with ε‐caprolactone will lead to materials expected to be environmentally friendly and applicable to biomedical usages. A ladder‐like poly(phenyl silsesquioxane) based hybrid star‐shaped copolymer of ε‐caprolactone was prepared by ring opening polymerization of ε‐caprolactone catalyzed by Sn(Oct)₂ with hydroxyl terminated ladder‐like poly(phenyl silsesquioxane) as initiator. The copolymers were characterized by proton nuclear magnetic resonance (¹H‐NMR), silicon nuclear magnetic resonance (²⁹Si‐NMR), Fourier‐transform infrared spectrometer (FT‐IR), size exclusion chromatography (SEC), thermo gravimetric analysis (TGA), and differential scanning calorimetry (DSC) in detail. Furthermore, the enzymatic degradation property of the copolymers was also investigated. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42335.     

Preparation of unsaturated poly(ε‐caprolactone) with a new titanium alkoxide initiator

Titanium alkoxides are widely used in the ring‐opening polymerization of ε‐caprolactone. In this study, functional poly(ε‐caprolactone) was synthesized with a new titanium initiator by a two‐step procedure: First, the titanium initiator, with an unsaturated group, was prepared by a classical organic reaction between 2‐hydroxyethylmethacrylate or 2‐allyloxyethanol with titanium tetrapropoxide; then, we initiated the polymerization of the ε‐caprolactone monomer in a glass reactor or twin‐screw extruder. By means of NMR spectroscopy, the structures of the initiators and polymers were determined. When 2‐hydroxyethylmethacrylate was used, there was a side reaction (transesterification) during the preparation of the initiator, and so it was impossible to obtain the expected product. With 2‐allyloxyethanol, the designed titanium initiator was synthesized with high purity, and the allyl moiety remained intact after the polymerization of ε‐caprolactone. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Kinetic and thermodynamic considerations in the synthesis of a new three‐arm poly(ε‐caprolactone)

A new high‐molecular‐weight three‐arm poly(ε‐caprolactone) (PCL) polymer was synthesized in bulk (in the absence of any solvent) by using aluminum tri‐sec butoxide as a tri‐functional initiator. The ring‐opening polymerization of ε‐caprolactone occurs via a coordination‐insertion mechanism that links three growing polyester chains to the Al central atom via metal alkoxide bonds. The global kinetics of the bulk polymerization was determined, and a kinetic model based on monomer‐polymer equilibrium was developed to predict the fractional extent of monomer conversion. Monomer conversions in excess of 95% to form high‐molecular‐weight PCL were achieved. Polym. Eng. Sci. 44:1491–1497, 2004. © 2004 Society of Plastics Engineers.     

Synthesis,characterization and (electro)chemical polymerization of triphenylamine‐end‐functionalized poly(ε‐caprolactone)

Triphenylamine‐based oligomers and polymers with linear, hyperbranched, star‐shaped or dendrimer architectures have been synthesized and studied due to their interesting electro‐optical properties. In many cases insoluble materials are obtained. In this study, we report the synthesis of grafted polytriphenylamine by chemical and electrochemical polymerization of triphenylamine‐end‐functionalized poly(ε‐caprolactone). Functionalized ε‐caprolactone oligomers were obtained by ring‐opening polymerization of ε‐caprolactone initiated by 4‐hydroxymethyltriphenylamine/stannous octanoate (tin 2‐ethylhexanoate). The ring‐opening polymerization of ε‐caprolactone using 4‐hydroxymethyltriphenylamine/stannous octanoate as initiating system provided ε‐caprolactone oligomers, with well‐defined molecular weights, containing a triphenylamine terminal group. Chemical and electrochemical coupling oxidation of the triphenylamine ends allowed the formulation of polyarylamines with ε‐caprolactone oligomers as grafts. Graft copolymers with an aryleneamine backbone and short poly(ε‐caprolactone) grafts were obtained by (electro)chemical oxidation of oligomers containing triphenylamine terminal groups. Copyright © 2009 Society of Chemical Industry     

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     

Characterization and electrical properties of honeycomb‐patterned poly(ε‐caprolactone)/reduced graphene oxide composite film

A novel biocompatible composite of poly(ε‐caprolactone) (PCL) was synthesized via in situ ring‐opening polymerization method of ε‐caprolactone in the presence of reduced graphene oxide (RGO). Fourier transform infrared (FTIR) and X‐ray photoelectron spectroscopy (XPS) studies support a strong interaction between PCL and RGO. The crystallization behavior and thermal stability of these composites were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. Honeycomb‐patterned thin films with regular structures were fabricated by casting the composite solution under humid conditions. The temperature‐dependent DC conductivity of the honeycomb‐patterned composite films was studied in the range of 290−330 K, which revealed a semiconducting behavior in the transport properties of the composite films. DC conductivity of the patterned films was increased by increasing the concentration of RGO in the composites and in the increased temperature. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

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     

Mechanistic study of boron trifluoride catalyzed ε‐caprolactone polymerization in the presence of glycerol

Boron trifluoride catalyzed ε‐caprolactone polymerization in the presence of glycerol can produce poly(ε‐caprolactone) with a high weight‐average molecular weight and a broad molecular weight distribution. This article reports an investigation of the polymerization mechanism to determine the formation of these molecular weight features through a study of the polymerization kinetics and the molecular structure with NMR. The polymerization proceeds via an activated monomer mechanism, resulting in polymer molecules with hydroxyl chain ends. The broad molecular weight distribution can be attributed to the etherification reactions between hydroxyl chain ends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3900–3906, 2006     

Polyaniline and polypyrrole prepared in the presence of surfactants: a comparative conductivity study

Polyaniline and polypyrrole have been prepared by chemical oxidative polymerization of the corresponding monomers in an aqueous medium containing an anionic surfactant—sodium bis(2-ethylhexyl) sulfosuccinate, dodecylbenzenesulfonic acid and its sodium salt, and sodium dodecyl sulfate. Determination of the yield, elemental composition and density proved, and FTIR spectroscopy confirmed, that the anionic surfactants become incorporated in the conducting polymers. The polymerizations in the presence of a cationic surfactant, tetradecyltrimethylammonium bromide, were carried out for comparison. While the conductivity of polypyrrole became enhanced after the introduction of an anionic surfactant, the changes in the conductivity of polyaniline were marginal. The conductivity changes in both polymers during thermal ageing were measured at 175 °C. The electrical stability of polyaniline was better than that of polypyrrole. The presence of a surfactant improved the stability of conductivity of polypyrrole but reduced the electrical stability of polyaniline.     

Synthesis,self‐assembly,and drug release behavior of star‐shaped poly(ε‐caprolactone)‐b‐poly(ethylene oxide) block copolymer with porphyrin core

A serial of star‐shaped poly(ε‐caprolactone)‐b‐poly(ethylene oxide) (SPPCL‐b‐PEO) block copolymers with porphyrin core were successfully synthesized from ring‐opening polymerization (ROP) of ε‐caprolactone (CL) initiated with porphyrin core, followed by coupling reaction with a hydrophilic polymer poly(ethylene oxide) (PEO) shell. The structure of this novel copolymer were synthesized and thoroughly characterized by Nuclear Magnetic Resonance (NMR), Gel Permeation Chromatography (GPC), Fourier Transform Infrared Spectroscopy (FTIR). Notably, the as‐prepared porphyrin‐cored star‐shaped copolymer could self‐assembly into different structures determined by transmission electron microscopy (TEM) and dynamic lighting scattering (DLS), which provides the great potential of using this well‐defined photodynamic therapy material for drug delivery system. Particularly, the doxorubicin‐loaded SPPCL‐b‐PEO nanosphere exhibits property of pH‐induced drug release. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40996.     

Synthesis of poly(ε‐caprolactone)/clay nanocomposites using polyhedral oligomeric silsesquioxane surfactants as organic modifier and initiator

Poly(ε‐caprolactone)/clay nanocomposites were synthesized by in situ ring‐opening polymerization of ε‐caprolactone in the presence of montmorillonite modified by hydroxyl functionalized, quaternized polyhedral oligomeric silsesquioxane (POSS) surfactants. The octa(3‐chloropropyl) polyhedral oligomeric silsesquioxane was prepared by hydrolytic condensation of 3‐chloropropyltrimethoxysilane, which was subsequently quaternized with 2‐dimethylaminoethanol. Montmorillonite was modified with the quaternized surfactants by cation exchange reaction. Bulk polymerization of ε‐caprolactone was conducted at 110°C using stannous octoate as an initiator/catalyst. Nanocomposites were analyzed by X‐ray diffraction, transmission electron microscopy, thermo gravimetric analysis, and differential scanning calorimetry. Hydroxyl functionalized POSS was employed as a surface modifier for clay which gives stable clay separation for its 3‐D structure and also facilitates the miscibility of polymer with clay in the nanocomposites due to the star architecture. An improvement in the thermal stability of PCL was observed even at 1 wt % of clay loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polyaniline–vanadium oxide hybrid hierarchical architectures assembled from nanoscale building blocks by homogeneous polymerization

BACKGROUND: Polyaniline–vanadium oxide hybrid materials have been much researched due to their potential applications in lithium batteries. Although many methods have been reported for the fabrication of conventional polyaniline–vanadium oxide hybrid materials by in situ oxidative polymerization/intercalation of aniline in V₂O₅ and by layer‐by‐layer approaches, studies on polyaniline–vanadium oxide hybrid nanostructures have been rare. RESULTS: Polyaniline–vanadium oxide hybrid hierarchical architectures assembled from nanoscale building blocks, such as nanoplates and nanobelts, have been synthesized by a one‐step hydrothermal homogeneous reaction between aniline and peroxovanadic acid without the aid of any surfactant or template. The influences of synthesis parameters, i.e. reaction time, temperature and medium, on the morphologies of the polyaniline–vanadium oxide hybrid nanostructures have been investigated. With increasing reaction time/temperature, the alignment of nanoplates in the hierarchical architectures becomes gradually dense. CONCLUSION: The formation mechanism of the polyaniline–vanadium oxide hybrid hierarchical architectures involves a one‐step precipitation–polymerization–assembly process. The method may be applicable for the synthesis of other conducting polymer–vanadium oxide hybrid nanostructures. Copyright © 2009 Society of Chemical Industry     

Fully degradable antibacterial poly(ester‐phosphoester)s by ring‐opening polymerization, “click” chemistry,and quaternization

Fully degradable cationic poly(ester‐phosphoester)s with antibacterial properties were prepared by a combination of ring‐opening polymerization (ROP) and “click” reaction. First, poly(ester‐phosphoester)s‐bearing alkynyl groups were synthesized by the ring‐opening copolymerization of 2‐(2‐propynyloxy)?2‐oxo‐1,3,2‐dioxaphospholane (propynyl ethylene phosphate, PEP) and ε‐caprolactone (CL) using lanthanum tris(2,6‐di‐tert‐butyl‐4‐methylphenolate)s (La(DBMP)₃) as the catalyst. 2‐Azido‐N,N‐dimethylethanamine (DMEAN₃) was then attached to the copolymers by “click” reaction, resulting in poly(ester‐phosphoester)s with pendant tertiary amines. After the quaternization reactions between the copolymer and various alkyl bromides, cationic poly(ester‐phosphoester)s containing ammonium groups were obtained. Optical density (OD) measurement shows that the cationic copolymers have excellent antibacterial activity, which makes them potential candidates as biomaterials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42647.     

Synthesis of a Graphite Oxide Polyaniline Nano‐Composite by an Electrochemical Method

In order to produce a polyaniline graphite oxide nano‐composite, electro‐polymerization of aniline was performed within the graphite oxide layers via electrochemical treatment of aniline‐intercalated graphite oxide in the supporting electrolyte. It was found that graphite oxide has special electro‐active properties. Therefore, electrochemical polymerization of aniline was performed on a Pt substrate in the presence of graphite oxide that had been dispersed in the electrolyte solution by the cyclic voltammetric method. Formation of polyaniline within the layers of graphite oxide occurred during electro‐polymerization. This mechanism affects the polyaniline morphology and leads to the formation of well‐defined concrete microstructures differing from the pure graphite oxide. Moreover, the results of the thermogravimetric analysis showed that graphite oxide and the polyaniline graphite oxide nano‐composite electrodeposited on the Pt substrate have different weight loss behaviors. This confirms that intercalation of the polyaniline improved the oxidation stability of graphite oxide, along with the fact that the polyaniline graphite oxide nano‐composite was successfully synthesized by an electrochemical method.     

Esterification on solid support by surface‐initiated ring‐opening polymerization of ε‐caprolactone from benzylic hydroxyl‐functionalized Wang resin bead

Biodegradable poly(ε‐caprolactone) (PCL) was formed on benzylic hydroxyl‐functionalized Wang resin surface by surface‐initiated ring‐opening polymerization (SI‐ROP). The SI‐ROP of ε‐caprolactone was achieved first by treating Wang resin with Tin(II) 2‐ethylhexanoate [Sn(Oct)₂] to form Tin(II) complex, and then followed by polymerization of ε‐caprolactone in anhydrous toluene at 60°C. Thus, the polymer‐grafted Wang resin was characterized by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), optical microscopy (OM), and field‐emission scanning electron microscopy (FE‐SEM). The FTIR spectroscopic analysis of polymer‐grafted Wang resin (Wang‐g‐PCL) reveals the formation of ester linkage between PCL and hydroxyl‐terminated Wang resin. The DSC thermogram shows melting peak corresponding to PCL polymer on Wang resin surface. Thermogravimetric investigation shows increase in PCL content on the Wang resin surface in terms of percentage of weight loss with increase in reaction time. The formation of polymeric layers on the Wang resin surface can be directly visualized from OM and SEM images. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009