A water‐soluble self‐doped conducting polypyrrole‐based copolymer

A water‐soluble self‐doped conducting polypyrrole‐based copolymer was synthesized via the grafting of pyrrole onto the p‐aminodiphenylamine moieties of a water‐soluble copolymer. The conductive copolymer exhibited a conductivity as large as 3.4 S/cm. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 86–89, 2001     

Synthesis and characterization of water‐soluble conducting polyaniline by enzyme catalysis

Enzymatic synthesis of a water‐soluble, conducting polyaniline (PANI) was studied, using horseradish peroxidase as the biocatalyst and H₂O₂ as the initiator, in the presence of a poly(vinylsulfonic acid, sodium salt) (PVS) polyanion template. The effects of the buffer, concentration of H₂O₂, and the molar ratio of aniline to PVS on the polymerization were particularly investigated. The products were characterized by UV–vis/near‐IR and FTIR spectroscopy, thermogravimetric analysis, and four‐point probe conductivity measurement. The results showed that PVS could be chosen as a new template in the synthesis of PANI. The proper conditions of polymerization were obtained as follows: pH of the buffer was pH 4.0–5.0, the concentration of H₂O₂ was around 20 mM, and the molar ratio of PVS to aniline was 1–1.5. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 814–817, 2005     

Synthesis and characterization of novel water‐soluble polyesters for electrical insulation

Polyesters based on poly(alkyl anhydride), aromatic anhydrides, and polyglycols were synthesized by thermal and catalytic condensation polymerization techniques. The polymerization conditions were optimized by the variation of the monomer concentration, reaction temperature, and so on to achieve the desired properties. The reaction was monitored by the measurement of the acid values at different stages of the polymerization reaction. The water solubility of these polyesters was achieved by the termination of the reaction with the addition of ammonia. These polyester resins were characterized with IR and viscosity measurements. The electrical properties of polyester resins coated and cured on glass cloth were measured with the idea of using them as impregnating varnishes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Retention properties of arsenate anions of water‐soluble polymers by a liquid‐phase polymer‐based retention technique

The retention properties of arsenic ions from an aqueous solution by water‐soluble cationic polymers and cationic–anionic copolymers were investigated. Poly[(3‐methacryloylamine)propyl]trimethylammonium chloride [P(ClMPTA)] and poly[(3‐methacryloylamine)propyl]trimethylammonium chloride–co–acrylic acid [P(ClMPTA‐co‐AA] were synthesized by radical polymerization. The copolymers were prepared with feed mole ratios of ClMPTA to AA of 1 : 1, 1 : 2, and 2 : 1. The copolymer compositions were evaluated by FTIR spectroscopy, TG‐DSC, and elemental analysis. The liquid‐phase polymer‐based retention (LPR) technique was used. This technique consists of retention of arsenate anions by the quaternary ammonium salt of a water‐soluble polymer in a filtration membrane cell. It was shown that the polymers could bind H₂AsO species from an aqueous solution more selectively at pHs of 6 and 8, than at a pH of 4. An increase in the polymer concentration was associated with increased retention capacity but not linearly. At the highest concentration the influence of pH was better observed. Investigation of copolymers showed the concerted action of polycations and polyanions on the ability to retain arsenic. At the lowest pH, the role of ionic strength of the media had a remarkable effect on the retention ability, independently of copolymer composition. At a pH of 6 a copolymer polycation/polyanion composition of 2 : 1 had the highest selective effect. At a pH of 8, a nonequimolar copolymer composition showed the same efficiency for the retention of arsenate species. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2677–2684, 2006     

Fate of horseradish peroxidase during oxidation of monobrominated phenols

BACKGROUND: Peroxidase‐catalyzed polymerization of phenols is accompanied by substantial enzyme precipitation with reaction products. The enzyme fate during the polymerization of monobromophenols by horseradish peroxidase (HRP) was studied. Enzyme fate was simultaneously monitored by protein, total nitrogen mass balance and gel electrophoresis (SDS‐PAGE) analysis of both soluble and precipitate fractions. RESULTS: SDS‐PAGE analysis revealed that molecular weight bands of protein in the precipitate shifted upwards toward higher molecular weights, compared with protein control. When co‐polymerization was practiced higher HRP precipitation occurred compared with polymerization of a single substrate, regardless of substrate combination applied. Addition of polyethylene glycol (PEG) to the reaction mixture decreased the extent of HRP precipitation. At 2 mmol L^?1 H₂O₂, corresponding to the stoichiometric equivalent concentration, 50% precipitation occurred after 1 h (～70% after 24 h) compared with 97–98% (～100% after 24 h) without PEG. Nevertheless, further increase of H₂O₂ increased HRP precipitation regardless of PEG (85% at 4 mmol L^?1 and 95% at 5 mmol L^?1). The lowest degree of enzyme inactivation was observed for metabromophenol, which displayed the lowest transformation yield, compared to the other congeners. CONCLUSIONS: Results from SDS‐PAGE indicate that an interaction stronger than hydrophobic, resisting the denaturative conditions, may take place between HRP and the reaction products, suggesting the occurrence of a covalent link between them. Oxidation was enhanced by inclusion of PEG, which partially suppressed product‐dependent inactivation. The extent of enzyme inactivation depends on the substrate used, while highest inactivation occurred when co‐polymerization was practiced. Copyright © 2009 Society of Chemical Industry     

Synthesis of water‐soluble polyphenol‐graft‐poly(ethylene oxide) copolymers via enzymatic polymerization and anionic polymerization

Water‐soluble polyphenol‐graft‐poly(ethylene oxide) (PPH‐g‐PEO) copolymers were prepared using grafting‐through methodology. Polyphenol chains were synthesized via enzymatic polymerization of phenols, and the graft chains were synthesized via living anionic polymerization of ethylene oxides. The polymers were characterized using gel permeation chromatography, static light scattering and ¹H NMR, infrared and ultraviolet spectroscopies. The PPH‐g‐PEO graft copolymers are soluble in several common solvents, such as water, ethanol, N,N‐dimethylformamide, tetrahydrofuran and methylene dichloride. The solubility of the PPH‐g‐PEO graft copolymers is improved significantly compared with that of polyphenol. Copyright © 2009 Society of Chemical Industry     

The use of lignosulfonic acid in the synthesis of water‐dispersible polyaniline

Polyaniline was synthesized in the presence of lignosulfonic acid to yield a product (LIGNO‐PANI) that is water‐dispersible. Several samples ranging from 0 to 70% lignosulfonate (LS) were prepared. These samples were then evaluated for differences in dispersibility and conductivity. As the percent of LS in the samples was increased, the water‐dispersibility of the LIGNO‐PANI also increased. The particle size of the samples as well as the conductivity of the samples decreased with increasing percentages of LS in the samples. After extensive washings, however, the conductivity remained fairly constant (～ 0.4 S/cm) regardless of the amount of LS in the samples. Additionally, elemental analysis, TGA, and IR data were used to demonstrate that the LS is grafted to polyaniline during the synthesis of LIGNO‐PANI. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

A water‐soluble acrylate/sulfonate copolymer. I. Its synthesis and dispersing ability on cement

A new water‐soluble methacrylate/2‐acrylamido‐2‐methylpropane sulfonate copolymer (PMAMP) was synthesized and evaluated as a dispersion agent for cement particles. PMAMP was prepared from methacrylic acid and 2‐acrylamido‐2‐methylpropane sulfonic acid (AMP). The structure of the prepared polymer was verified by its NMR and IR spectra. The dispersing properties of PMAMP were evaluated by a minislump test on cement pastes. The test results indicated that this copolymer could disperse the cement particles and improve the minislump of cement pastes. Compared with a commercial superplasticizer (sulfonated naphthalene formaldehyde condensates), PMAMP performed better in enhancing the fluidity of the cement pastes. The polymer with about 40–50% AMP and a weight‐average molecular weight of about 5 × 10⁴ was most effective in dispersing cement particles and promoting the fluidity of cement pastes. Nevertheless, PMAMP with a higher AMP content or a higher molecular weight appeared to cause less slump loss. This was related to the interaction of this admixture with the cement particles and its adsorption behavior onto the cement particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2490–2496, 2006     

Enzymatic oxidation of alkoxyanilines for preparation of conducting polymers

A biomimetic route for synthesis of a conducting molecular complex between polyalkoxyanilines and a polyelectrolyte, poly (sodium 4‐styrenesulfonate) (SPS) is presented. Horseradish peroxidase (HRP) was used to catalyze the polymerization of alkoxyanilines. A few of water‐soluble ring‐substituted polyalkoxyanilines have been enzymatically synthesized with variation of groups, such as ortho‐methoxy, meta‐methoxy, ortho‐ethoxy, and meta‐ethoxy to form polyalkoxyanilines/SPS complexes. The presence of alkoxy substituents affects the polymerization reactions. These enzymatic oxidation reactions occur in a different potential range to that observed for the chemical polymerization. Similar electrochemical and optical properties were obtained for every pair of ortho‐ and meta‐alkoxy substituted polyanilines. For comparing, polyalkoxyanilines were also prepared by chemical polymerization in the presence of SPS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 103: 3724–3729, 2007     

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     

Direct formation of emulsions using water‐soluble porous polymers as sacrificial scaffolds

BACKGROUND: Emulsions are traditionally formed from two immiscible liquids by mechanical stirring, homogenization, or ultrasonication. For the use of emulsions, stability during storage and transport has been an issue which needs to be addressed. Here, a novel method is proposed to form emulsions instantly by hand shaking from porous polymeric materials. RESULTS: The porous materials were prepared by a freeze‐drying method and then soaked in an oil phase. The oil was absorbed into the micron‐sized pores. The oil‐soaked composites were then placed in water. The dissolution of polymer led to the formation of emulsions by gentle hand shaking within 2 min. Mineral oil, soy oil with drug molecules, and perfluorodecalin were tested as the model oil phases. In each case, stable emulsions with high ratios of oil to water were formed instantly. CONCLUSIONS: A novel route is reported to produce emulsions instantly by hand shaking from porous polymeric materials. Using this method, emulsions could be formed instantly on the site just before application, thus avoiding the cost and stability concerns during transport and storage of emulsions. The method also has the advantages of easy operation and scale‐up possibility. Copyright © 2010 Society of Chemical Industry     

Synthesis in inverse emulsion and properties of water‐soluble associating polymers

An inverse, free‐radical emulsion polymerization technique was designed for the preparation of copolymers of acrylamide and sodium acrylate modified with low amounts (<0.5 mol %) of a series of amphiphilic comonomers, the isooctylphenoxy–poly(oxyethylene)(n) methacrylates (1 ≤ n ≤ 12). The products of the reaction were hydrophobically modified water‐soluble polymers (HMWSPs) of high molecular weight encapsulated within water droplets dispersed in an organic medium. Kinetic studies showed that the full‐conversion samples were rather homogeneous in composition because of the specificity of the process. A mechanistic scheme is proposed that accounts for the incorporation level of the amphiphilic comonomer as a function of its hydrophile–lipophile balance and the nature of the redox initiator (hydrophilic or lipophilic). The rheological properties of the HMWSPs in aqueous solutions were investigated as a function of the comonomer content and the nature of the initiator with steady‐flow experiments. The thickening properties were directly correlated to the conditions of synthesis and were optimal when the initiator and the amphiphilic comonomer were located in two distinct phases. A maximum in viscosity was observed for a hydrophobe content of about 0.3 mol %. An examination of the viscosity as a function of the shear rate and time showed that these solutions had all the characteristics of associating polymers. The complex rheological behavior was the result of the balance between interchain and intrachain hydrophobic liaisons and the kinetics of disorganization and reorganization of the network structure. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1418–1430, 2002; DOI 10.1002/app.10337     

Facile preparation and potential application of water‐soluble polymeric temperature/pH probes bearing fluorescein

An unsaturated monomer bearing xanthene groups and allyloxyfluorescein (Al‐Flu), was synthesized from fluorescein and allyl bromide by etherification. The structure of the monomer was confirmed by IR and mass spectroscopy and ¹H‐NMR, and ¹³C‐NMR spectroscopy. With azobisisobutyronitrile as a thermal initiator in tetrahydrofuran under 65–70°C, a copolymer of allyloxyfluorescein and acrylamide [poly(Al‐Flu‐co‐AM)] was obtained and was characterized by the methods of IR spectroscopy, ultraviolet–visible spectroscopy, and differential scanning calorimetry. The experimental results show that the fluorescence spectra of water‐soluble poly(Al‐Flu‐co‐AM) was dependent on the pH and temperature in the solution. Moreover, poly(Al‐Flu‐co‐AM) had an excellent linear response between the relative fluorescence intensity and temperature in the range 0–60°C and had a nonlinear response from pH 0.00 to 12.85 between the relative fluorescence intensity and pH. The pH and temperature sensitivities of the fluorescence could be advantageous for it as a multifunctional material to probe pH and temperature. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Preparation and properties of novel water‐soluble surfactants. I. Synthesis and surface activity of polycarboxylated multihydrophilic surfactants

A series of novel surfactants containing multianionic and nonionic hydrophilic moieties were prepared by reacting fumaric acid with polyoxyethylenated stearyl ether in the presence of a peroxy‐type free radical initiator to form a carboxylic‐acid‐group‐containing addition product. The structure of these surfactants was confirmed by infrared, nuclear magnetic resonance, and elemental analysis. These surfactants exhibit excellent functional properties of self‐sequestering. This means that besides good surfactant properties, including surface tension, foaming, and wetting, they possess autonomous sequestering ability without any help of additional sequestering agent. When used in cotton bleaching procedures, these surfactants increase the penetration of the fibers of gray fabrics and increase the whiteness of bleached cotton. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3559–3564, 2006     

Synthesis and characterization of a water‐soluble sulfonates copolymer of acrylamide and N‐allylbenzamide as enhanced oil recovery chemical

A novel water‐soluble polymer was prepared by copolymerization and sulfomethylation using acrylamide (AM) and N‐allylbenzamide (NABI) as raw materials under mild conditions. The effects of ratio of AM to NABI, initiator concentration, reaction temperature, pH, and monomer concentration on the copolymerization were studied. The sulfonates copolymer was characterized by infrared (IR) spectroscopy, ¹H NMR spectroscopy, elemental analysis, and atomic force microscopy (AFM). It was found that the sulfonates copolymer could achieve up to 25%, 30% retention rate of the viscosity at a high temperature (120°C) and a vigorous shear condition (1000 s^?1). It was also found that the sulfonates copolymer had moderate salt tolerance (NaCl, CaCl₂, and MgCl₂·6H₂O) and its viscosity could be restored to the original value when the shear rate changed from 170 to 510 s^?1 and 510 to 170 s^?1. At last, the enhanced oil recovery (EOR) of the sulfonates copolymer was tested by core flood, and with up to 10.6% EOR was afforded in presence of 5000 mg/L NaCl brine at 60°C. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Conduction mechanism in H‐type polysiloxane‐polypyrrole block copolymers

Conducting polymers of polysiloxane‐polypyrrole were synthesized by electropolymerization of the pyrrole monomer through pyrrole moieties in N‐pyrrole‐terminated polysiloxanes. Sodium paratoluene sulfonate was used as the electrolyte. Scanning electron microscopy (SEM) was used to determine the surface morphology of the films. The room‐temperature conductivity values of the films were found to be in the range of 1.9–4.4 × 10^?4 (Ω cm)^?1, depending on the supporting electrolyte concentration. The temperature dependence of the dc conductivities of the copolymers having different dopant concentrations was investigated within the temperature range of 100–320 K. The evaluated parameters showed that the electrical transport is dominated by variable range hopping. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 52–56, 2002     

Properties of water‐soluble acrylic copolymer/montmorillonite nanocomposites for warp sizing

Acrylic copolymer/montmorillonite (MMT) nanocomposites for warp sizing were prepared in the presence of Na⁺‐MMT by the in situ intercalative polymerization of acrylic acid, acrylamide, and methyl acrylate in water solution. The properties of the solution and cast film were tested according to an application in sizing process of the nanocomposite size with various MMT contents. The results indicate that, for an exfoliated structure corresponding to the MMT content increasing to 7 wt %, the performance parameters of solution viscosity, glass‐transition temperature, and tensile strength of the film increased and the moisture sorption, abrasion loss, and elongation at break of the film decreased. When the intercalated structure of MMT was 9 wt %, the gathered MMT layers acted as a common inorganic filler in the copolymer matrix, with limited contribution to the properties of the composite. The adhesion work of the nanocomposite solution was calculated by use of the Young–Dupre relation, which showed maximum values at an MMT content of 3 wt % on the surfaces of both the polyester and cellulose films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Formation of thermosensitive water‐soluble copolymers with phosphinic acid groups and the thermosensitivity of the copolymers and copolymer/metal complexes

Thermosensitive and water‐soluble copolymers were prepared through the copolymerization of acryloyloxypropyl phosphinic acid (APPA) and N‐isopropyl acrylamide (NIPAAm). The thermosensitivity of the copolymers and copolymer/metal complexes was studied. The APPA–NIPAAm copolymers with less than 11 mol % APPA moiety had a lower critical solution temperature (LCST) of approximately 45°C, but the APPA–NIPAAm copolymers with greater than 21 mol % APPA moiety had no LCST from 25 to 55°C. The APPA–NIPAAm copolymers had a higher adsorption capacity for Sm³⁺, Nd³⁺, and La³⁺ than for Cu²⁺, Ni²⁺ and Co²⁺. The APPA–NIPAAm (10:90) copolymer/metal (Sm³⁺, Nd³⁺, or La³⁺) complexes became water‐insoluble above 45°C at pH 6–7, but the APPA–NIPAAm (10:90) copolymer/metal (Cu²⁺,Ni²⁺, or Co²⁺) complexes were water‐soluble from 25 to 55°C at pH 6–7. The temperature at which both the APPA–NIPAAm copolymers and the copolymer/metal complexes became water‐insoluble increased as the pH values of the solutions increased. The APPA–NIPAAm copolymers were able to separate metal ions from their mixed solutions when the temperature of the solutions was changed; this was followed by centrifugation of the copolymer/metal complexes after the copolymers were added to the metal solutions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 116–125, 2004     

Arsenite retention properties of water‐soluble metal–polymers

The properties of water‐soluble metal–polymers to retain As(III) from aqueous solution are investigated. Poly(acrylic acid)s with different tin contents are prepared. Amounts of 3, 5, 10, and 20 wt % of tin are added to the polymer. The metal compositions are evaluated by thermogravimetry (TG‐DSC) and atomic absorption spectroscopy. Structural properties are analyzed by infrared and ¹H nuclear magnetic resonance spectroscopy, and X‐ray diffraction. Additionally, specific surface area was measured using CO₂ as adsorbate. Arsenic retention properties are studied using the liquid‐phase polymer‐based retention (LPR) technique. The polymers can bind arsenic species from an aqueous solution in the pH range 4–8. The studies show that the retention capacity is a function of tin content and polymer concentration. At pH 8, the following mol ratios poly(AA)‐Sn : As(III) are analyzed: 600 : 1, 400 : 1, 200 : 1, 100 : 1, and 20 : 1. The highest retention, 80%, is obtained with poly(AA)‐Sn at 10 and 20 wt % of tin at mole ratios 400 : 1, and at nearly to 20 : 1 or 40 : 1 Sn‐As(III). The highest retention is observed at pH 8 and 4. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of water‐soluble thermosensitive polymers having phosphonium groups from methacryloyloxyethyl trialkyl phosphonium chlorides–N‐isopropylacrylamide copolymers and their functions

Water‐soluble thermosensitive polymers having phosphonium groups were synthesized by the copolymerization of N‐isopropylacrylamide (NIPAAm) with methacryloyloxyethyl trialkyl phosphonium chlorides (METRs) having varying alkyl lengths. The relative viscosities of the copolymer solutions increased with increasing content of phosphonium groups in the copolymers and decreased with increasing chain length of alkyl chains in the phosphonium groups. However, the copolymers of METR with octyl groups in phosphonium groups (METO) and NIPAAm became water insoluble with increasing contents of METO moieties in the copolymers. The transmittance at 660 nm of the copolymer solutions above the lower critical solution temperature (LCST) decreased gradually with increasing temperature and decreased with increasing chain length of alkyl chains in the phosphonium groups. The transmittance at 660 nm of the copolymer solutions above the LCST was greatly affected by the addition of neutral salts such as KCl. The copolymers of METR with ethyl groups in phosphonium groups and NIPAAm and those of METR with butyl groups in phosphonium groups and NIPAAm had high flocculating abilities against bacterial suspensions. The METO–NIPAAm copolymer was found to have a high antibacterial activity. The flocculating ability and the antibacterial activity of the copolymers were affected by not only the content of phosphonium groups but also the alkyl chain length in the phosphonium groups in the copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 386–393, 2003