Electrochemical preparation of poly(o‐toluidine) film and its application as a permselective membrane

Poly(o‐toluidine) films were electrochemically synthesized on Pt electrodes at a constant potential (0.75 V versus Ag/AgCl) from a deoxygenated aqueous solution of 0.1M toluidine dissolved in 0.1M KCl. To form permselective polymeric film electrodes, poly(o‐toluidine) films at different thicknesses were prepared by varying the amount of charge consumed during electrochemical polymerization. Then, experimental parameters (e.g., concentrations of monomer and electrolyte and pH of the phosphate buffer salt solution) affecting the polymeric film thickness were optimized. Permeation of the various electroactive and nonelectroactive species such as ascorbic acid, oxalic acid, hydrogen peroxide, lactose, sucrose, and urea through the optimized poly(o‐toluidine)‐coated electrodes was investigated using a chronoamperometric technique. From experimental results, it was found that a poly(o‐toluidine)‐coated electrode permitted the oxidation of hydrogen peroxide and prevented the permeation of the mentioned electroactive and nonelectroactive species. In other words, it was seen that this polymeric electrode responded to only hydrogen peroxide selectively. Thus, it has been claimed that a poly(o‐toluidine)‐coated Pt electrode can be used as a permselective polymeric membrane to overcome interference problems occurring in the hydrogen peroxide‐based biosensor applications. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2141–2146, 1999     

Emulsion polymerization of styrene with amphiphilic random copolymer as surfactant: Predominant droplet nucleation

Amphiphilic random copolymer consisting of monomeric units of poly (butyl acrylate) and poly (maleic acid salt) was synthesized and characterized. The emulsion polymerization kinetics of styrene stabilized by this copolymer was investigated. The influencing factors, including polymeric surfactant concentration, initiator concentration and polymerization temperature, were systematically studied. The kinetic data show that the polymerization rate (R_P) increased with the increase of the polymeric surfactant concentration ([S]) and polymerization temperature (T). At the higher [S], droplets nucleation and micelle nucleation coexisted in the polymerization system; at the lower [S], only the droplets nucleation process existed. The polymerization did not follow Smith‐Ewart Case II kinetics. Dynamic light scatter and transmission electron microscope were utilized to measure the sizes and shapes of the particles, respectively. It would be speculated that a kind of large heterogeneous particles with multiple‐active‐sites was formed in the polymerization system. The increasing of R_P with increasing initiator concentration ([KPS]) was rapid at a medium [KPS], but the slowly increasing was observed at a lower or higher [KPS]. It was attributed to the barrier effect of the polymeric surfactant around the monomer droplets. The polymerization activation energy was 60.29 kJ/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Spider-net within the N6, PVA and PU electrospun nanofiber mats using salt addition: Novel strategy in the electrospinning process

Electrospun nanofibers are promising candidates in the nanotechnological applications due to the advantages of the nanofibrous morphology. Therefore, many attempts were reported to modify the electrospun mats to gain more beneficial properties. In the present study, we are introducing a strategy to synthesize electrospun polymeric nanofiber mats containing spider-net binding the main nanofibers. Addition with long stirring time of a metallic salt having tendency to ionize rather than formation of sol–gel in the host polymer solution reveals to synthesize a spider-net within the electrospun nanofibers of the utilized polymer. Nylon6, polyurethane and poly(vinyl alcohol) have been utilized; NaCl, KBr, CaCl₂ and H₂PtCl₆ have been added to the polymeric solutions. In the case of nylon6 and poly(vinyl alcohol), addition of the inorganic salts resulted in the formation of multi-layers spider-network within the electrospun nanofibers mats. The synthesized spider-nets were almost independent on the nature of the salt; the optimum salt concentration was 1.5 wt%. The metallic acid led to form trivial spider-nets within both of nylon6 and poly(vinyl alcohol) nanofibers. In a case of polyurethane, few spider-nets were formed after salt addition due to the low polarity of the utilized solvents. According to TEM analysis, the synthesized spider-net consisted of joints; the later issued from the main nanofibers at Taylor's cone zone. The spider-net improved the mechanical properties and the wetability of the nylon6 nanofiber mats, accordingly a mat having amphiphilic feature has been prepared.     

Poly(aspartic‐acid) derivatives as polymeric micelle drug delivery systems

A novel amphiphilic biodegradable graft copolymer based on poly(aspartic acid) (PASP) was prepared by coupling monomethoxy poly(ethylene glycol) as the hydrophilic segment with PASP‐g‐octadecyl (PASP‐g‐OD) as the hydrophobic backbone. The critical micelle concentration of the copolymer was obtained by measuring the conductivity and fluorescence spectroscopy. Polymeric micelles were prepared with the solvent evaporation method, and the size distribution and morphology of the polymeric micelles were characterized by dynamic light scattering and transmission electron microscopy. The ability of the PASP derivatives to solubilize hydrophobic drugs was investigated using methotrexate (MTX), oleanolic acid, and podophyllotoxin (PODO) as models. The results demonstrated that drug solubility depends on the copolymer concentration, copolymer composition, as well as the physicochemical property of the drug. A stability study performed with PODO loaded by polymeric micelle solution demonstrated that the micelle carrier could protect the drug from being destroyed in a pH 7.4 buffer solution; however, the micelle did not protect it in a pH 9.5 buffer solution. Pharmacokinetic studies were carried out by intravenous administration of MTX loaded by polymeric micelle solution and MTX solution. The results demonstrated that the polymeric micelle prolonged the drug permanence in blood circulation with a mean residence time of about 2.37 times and increased the systemic bioavailability with the area under the drug concentration–time curve by about 2.34 times. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2871–2878, 2006     

Novel Poly(linolenic acid) Graft Copolymers: Synthesis,Characterization and Electrical Properties

A poly(linolenic acid)‐g‐poly(tert‐butyl acrylate) graft copolymer was synthesized from polymeric linolenic acid peroxide possessing peroxide groups in the main chain by free radical polymerization of tert‐butyl acrylate. Graft copolymers having structures of poly(linolenic acid)‐g‐poly(caprolactone)‐g‐poly(tert‐butyl acrylate) were synthesized from polymeric linolenic acid, possessing peroxide groups on the main chain by the combination of free radical polymerization of tert‐butyl acrylate and ring‐opening polymerization of ε‐caprolactone in one‐pot. The obtained graft copolymers were characterized by proton nuclear magnetic resonance, gel permeation chromatography, thermal gravimetric analysis, differential scanning calorimetry, and scanning electron microscopy techniques. Furthermore, Au/n‐Si diodes were fabricated with and without poly(linolenic acid)‐g‐poly(caprolactone)‐g‐poly(tert‐butyl acrylate)‐4 to form a new interfacial polymeric layer for the purpose of investigating this polymer's conformity in electronic applications. Some main electrical characteristics of these diodes were investigated using experimental current–voltage measurements in the dark and at room temperature.     

Comparative studies of electrochemically deposited poly(o-toluidine) and poly(m-toluidine) films

Under galvanostatic deposition conditions poly(o-toluidine) exhibits a higher rate of polymerization than poly(m-toluidine). This observation is supported by results obtained by different characterization techniques such as spectrophotometry, scanning electron microscopy and thermogravimetric analysis. The monomer concentration was found to be the predominant parameter in obtaining selectively a conducting salt phase in both cases. However, the morphology of these polymeric films does not reveal any particular relationship with monomer concentration; instead a mixed morphology, i.e. a combination of granules and fibres, is observed. Finally, the thermal stability of poly(m-toluidine) is lower than that of poly(o-toluidine) with a shift of 190°C in the final decomposition temperature.     

Polymer micellar aggregates of novel amphiphilic biodegradable graft copolymer composed of poly(aspartic acid) derivatives: Preparation,characterization, and effect of pH on aggregation

Novel amphiphilic biodegradable graft copolymer based on poly(aspartic acid) was prepared by attaching monomethoxy polyethylene glycol (mPEG) as hydrophiphic segment to poly(aspartic acid‐g‐octadecylamine) (PASP‐g‐ODA) as hydrophobic backbone. The chemical structures of amphiphilic copolymers were confirmed by FTIR and ¹H NMR spectroscopy. The polymeric micelles were prepared with solvent evaporation and their physicochemical properties in aqueous media were characterized by dynamic light scattering (DLS) and fluorescence spectroscopy. These micelles were confirmed to be pH‐sensitive by measuring optical transmittance of micelle solution and the size of micellar aggregates. The number average diameter of polymeric micelles prepared in medium at pH 2.5 was larger than that in neutral and basic medium and showed a bimodal size distribution because of the protonation of carboxyl groups in backbone. Furthermore, the polymeric micelle can load water‐insoluble drug (podophyllotoxin), and the drug release from micelles showed a pH‐dependency. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Poly(sulfobetaine)s and corresponding cationic polymers. VIII. Synthesis and aqueous solution properties of a cationic poly(methyl iodide quaternized styrene–n,n‐dimethylaminopropyl maleamidic acid) copolymer

A cationic poly(methyl iodide quaternized styrene–N,N‐dimethylaminopropylmaleamidic acid) copolymer was synthesized through amidoacidification reaction of styrene‐maleic anhydride copolymer with N,N‐dimethylaminopropylamine (ring‐opening reaction). Its properties in various aqueous salt solutions and pH solutions were studied by measurements of reduced viscosity and intrinsic viscosity. The results indicated that the reduced viscosity and intrinsic viscosity of this cationic polyelectrolyte were related to the type and concentration of the added salts and the results also showed a contrary tendency in some salts with monovalent acid groups to polyelectrolyte. At the same time, some salt ions were observed to strongly attract the quaternary ammonium group of the cationic polymeric side chain and resulted in agglomeration of the polymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1619–1626, 2001     

Functional polymers for colloidal applications. XIV. Syntheses of styrene–maleic anhydride copolymers with different charges and their ability to disperse kaolinite particles

Four kinds of styrene/maleic–anhydride (SMA) copolymer‐derived dispersants with different charged forms were synthesized and characterized with ¹H‐NMR. These four different dispersants contained carboxylic acid groups and exhibited characteristics indicative of anionic, cationic, zwitterionic, or nonionic surfactants as pH was changed. The charge properties of these copolymers changes with pH, and their ability to disperse clay particles under low and high pH were assessed by measuring viscosity or sedimentation, as well as Scanning Electron Microscopy (SEM). The results showed that the dispersing abilities are functions of pH of the system. It was found that SMA‐N [Poly(styrene‐co‐β‐N,N‐dimethylpropylamino) maleic acid, sodium salt)] exhibits the best dispersing ability, the fastest rate of sedimentation, and the smallest sedimentation volume at pH = 2, and SMA‐Na [poly(styrene‐co‐maleic acid, disodium salt)] exhibits the better dispersing ability at pH = 7 and 12. In addition, the aggregation behavior of the dispersants characterized by fluorescence spectroscopy revealed that the degree of aggregation for all dispersants at high concentration increases in the order: SMA‐Na < SMA‐B [poly(styrene‐co‐B‐imino‐propyl‐N‐trimethylammonium acetate) maleic acid, disodium salt)] < SMA‐N < SMA‐Q [poly(styrene‐co‐β‐imino‐propyl‐N‐trimethylammonium sulfate) maleic acid, sodium salt)]. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 592–602, 2000     

Synthesis and characterization of cassava starch graft poly(acrylic acid) and poly[(acrylic acid)‐co‐acrylamide] and polymer flocculants for wastewater treatment

Starch‐g‐poly(acrylic acid) and poly[(acrylic acid)‐co‐acrylamide] synthesized via chemically crosslinking polymerization were then each mixed with inorganic coagulants of aluminum sulfate hydrate [Al₂(SO₄)₃·18H₂O], calcium hydroxide [Ca(OH)₂], and ferric sulfate [Fe₂(SO₄)₃] in a proper ratio to form complex polymeric flocculants (CPFs). All CPFs exhibited low water absorbency than those of the uncomplexed superabsorbent copolymers. The color reduction by the CPFs was tested with both synthetic wastewater and selected wastewater samples from textile industries. The synthetic wastewater was prepared from a direct dye in a concentration of 50 mg dm^?3 at pH 7. The CPFs of poly[(acrylic acid)‐co‐acrylamide] with calcium hydroxide at a ratio of 1:2 is the most effective CPF for the wastewater color reduction. The CPF concentration of 500 mg dm^?3 could reduce the color of the synthetic wastewater containing the direct dye solution by 95.4% and that of the industrial wastewater by 76%. Starch‐g‐poly(acrylic acid)/Ca(OH)₂ CPF can reduce the synthetic direct dye and the industrial wastewater by 74% and 18%, respectively. Chemical oxygen demand, residual metal ion concentrations, pHs, turbidity of the wastewater were also investigated and the potential use of the complex polymer flocculants for textile wastewater treatment was indicated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2915–2928, 2006     

Grafting reactions onto poly(organophosphazenes). IV. Light-induced graft copolymerization of organic polymers containing free acid or basic functionalities onto poly[bis(4-benzylphenoxy)phosphazene]

The light-induced graft copolymerization of acrylic acid, methacrylic acid, and 4-vinylpyridine onto poly[bis(4-benzylphenoxy)phosphazene] films to prepare new grafted phosphazene copolymers containing acid and basic functionalities is reported. The process was carried out in monomer/methanol mixtures in the presence of benzophenone or benzoin ethyl ether as photosensitizers by selective excitation of these last species. The yield of the grafting processes was evaluated as a function of the monomer concentration in the reaction medium, type of photoinitiator, and characteristics of the grafted organic monomers. The acid functions inserted in poly[bis(4-benzylphenoxy)phosphazene]-g-poly(meth)acrylic acid grafted copolymers, and the basic groups of the poly[bis(4-benzylphenoxy)phosphazene]-g-poly-4-vinylpyridine substrates were allowed to interact with basic and acid dyes, respectively, to form permanently colored polymeric films. The photoactivity of these films as substrates for the photosensitized production of singlet oxygen was tested. © 1995 John Wiley & Sons, Inc.     

Swelling and diffusion characteristics of novel semi‐interpenetrating network hydrogels composed of poly[(acrylamide)‐ co‐(sodium acrylate)] and poly[(vinylsulfonic acid), sodium salt]

A series of novel semi‐interpenetrating polymer networks (IPNs) composed of poly[(acrylamide)‐co‐(sodium acrylate)] with varying amounts (5, 10, and 15 wt%) of poly[(vinylsulfonic acid), sodium salt] was synthesized. The semi‐IPN hydrogels were characterized by infrared spectroscopy. The swelling behavior of these IPNs was studied in distilled water/physiological solutions/buffer solutions/salt solutions. As the amount of poly[(vinylsulfonic acid), sodium salt] increased in the network, the swelling capacity of the semi‐IPNs increased considerably. The swelling and diffusion characteristics such as water penetration velocity (v), diffusion exponent (n), and diffusion coefficient (D) were calculated in distilled water, as well as in other physiological solutions. The highest swelling capacity was noted in urea and glucose solutions. The semi‐IPN hydrogels followed non‐Fickian diffusion behavior in water and physiological fluids, whereas Fickian behavior was observed in buffer solutions. The stimuli‐responsive characteristics towards physiological fluids, salt concentration, and temperature of these semi‐IPN hydrogels were also investigated. The swelling behavior of the semi‐IPNs decreased markedly with an increase of the concentration of the salt solutions. Copyright © 2006 Society of Chemical Industry     

Synthesis and solution properties of novel nonionic functional polyurethane surfactants

A series of novel nonionic functional polyurethane surfactants were synthesized by the polycondensation of 2,4‐toluene diisocyanate with poly(propylene oxide) (weight‐average molecular weight = 400, 1000, or 2000) and monoallyl‐end‐capped poly(ethylene oxide). The chemical structure of the polyurethane surfactants was determined by Fourier transform infrared and ¹H‐NMR, and the effects of the concentration, salt, rest time, and temperature on the surface tension were investigated. These polymeric surfactants exhibited excellent surface activity. Sample III, which was synthesized with monoallyl‐end‐capped poly(ethylene oxide) (number‐average molecular weight = 1000), poly(propylene oxide) (number‐average molecular weight = 2000), and tolylene diisocyanate, could reduce the surface tension to 37.6 mN/m at a concentration of 0.06 mol/L at 25°C. All polyurethane surfactants synthesized in this study had low critical micelle concentrations (ca. 10^?4 to 10^?5 mol/L) and could reduce the surface tension even at very low concentration levels. Moreover, the surface tension decreased with an increase in the temperature or the concentration of the polyurethane surfactants. The addition of salt resulted in a decrease in the surface tension, and it took some time for the polyurethane surfactants to reach a constant surface tension value. UV spectra were found to be very useful for determining the critical micelle concentration. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2956–2962, 2006     

Dynamic deposition of polyacids on porous membrane supports

Poly(acrylic acids), poly(styrenesulfonic acid), and their block and random copolymers were tested for their ability to form dynamic membranes on partially cured asymmetric cellulose acetate. Chemically modified porous polypropylene (Celgard) was also used as a support for poly(acrylic acid). Salt rejections, water fluxes, and streaming potentials of membranes were tested under hyperfiltration conditions. Sorption of the polyelectrolytes by the cellulose acetate supports was studied using spectrophotometric, ²²Na tracer, and electron microscopy techniques. The dynamic membrane formation was noted only for poly(acrylic acid) and for its 1:4:1 block copolymer with poly(styrenesulfonic acid). The uneffectiveness of other polyelectrolytes was discussed in terms of a negative zeta potential of cellulose acetate. The increase in salt rejection (R) due to the polyelectrolyte is strongly dependent on the initial R_i of the support. Sharp maxima in the ΔR -versus-R_i curves have been noted for R_i in the range of 40–55%. The most significant improvement in the hyperfiltration characteristics of cellulose acetate was attained with the 1:4:1 block copolymer. Flux of 17 gfd at 350 psi and R = 93% was obtained in short-term tests for a 0.1N feed solution. Long-term tests did not reveal any flux or salt rejection decline for membranes in which poly(acrylic acid) was complexed with phosphoramidic groups grafted onto Celgard.     

Factors affecting the adsorption of cationic dyes on polymeric hydrogels prepared by gamma irradiation

The adsorption of the cationic dyes Rhodamine B (RB) and Crystal Violet (CV) on polyacrylamide/poly(acrylic acid) (poly(AAm/AAc), 25:25 % weightwise) and polyacrylamide/poly(sodium acrylate) (poly(AAm/AAcNa), 25:25 % weightwise) hydrogels was studied, employing the Langmuir and Freundlich isotherms. The results of swelling tests at pH 5.5 indicate that poly(AAm/AAcNa) hydrogel shows maximum percentage swelling (%S) was 4400 %. Moreover, the results show that the adsorption capacity is pH‐ and concentration‐dependent. At pH >5 adsorption of RB and CV increases due to ionization of ? COOH and ? COONa groups of (poly(AAm/AAc) and (poly(AAm/AAcNa) and interactions with the cationic groups of the dyes. However, at pH lower than 5, adsorption is still high, which can be explained by considering the formation of hydrogen bonds between the amino groups of the dyes and the ? COOH groups of the polymeric hydrogels. Moreover, the kinetics of adsorption follows a first‐order equation. Furthermore, scanning electron microscopy (SEM) micrographs of polymeric hydrogels doped with CV and RB have morphological differences from the pure form. Our data show that Rhodamine B adsorbs more efficiently on both polyacrylamide/poly(acrylic acid) and polyacrylamide/poly(sodium acrylate) hydrogels than CV. Copyright © 2004 Society of Chemical Industry     

Influence of potassium humate on the swelling properties of a poly(acrylic acid‐co‐acrylamide)/ potassium humate superabsorbent composite

A novel superabsorbent composite, poly(acrylic acid‐co‐acrylamide)/potassium humate (PAA‐AM/KHA), was prepared by aqueous solution polymerization from acrylic acid, acrylamide, and potassium humate (KHA) with N,N′‐methylenebisacrylamide as a crosslinker and potassium peroxydisulfate as an initiator. The effects of incorporated KHA on the water absorbency, swelling rate, and reswelling capability were investigated. The swelling property of PAA‐AM/KHA in various saline solutions was studied systematically. The results show that the comprehensive properties and especially salt‐resistant ability of PAA‐AM/KHA were enhanced. There was a linear relationship between the saturated water absorbency and the minus square root of the ionic strength of the external medium, and the water absorbency of PAA‐AM/KHA in various salt solutions had the following order: NH₄Cl_(aq) = KCl_(aq) = NaCl_(aq) > MgCl_2(aq) > CaCl_2(aq) > AlCl_3(aq) > FeCl_3(aq). Moreover, the polymeric net structure of PAA‐AM/KHA was examined with respect to that of poly(acrylic acid‐co‐acrylamide). The results indicate that the polymeric net of PAA‐AM/KHA was improved by the introduction of a moderate amount of KHA into the superabsorbent composite and made more suitable for agriculture and horticulture applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation and properties of water‐soluble polyester surfactants. I. Preparation and surface activity of poly(ethylene glycol)‐dimethyl 5‐sulfo‐isophthalate sodium salt polyester surfactants

The reaction of poly(ethylene glycol) (PEG, number‐average molecular weight M_n = 400‐2000) and dimethyl 5‐sulfoisophthalate sodium salt (SIPM) synthesized a series of anionic polymeric surfactants having a range of molecular weights. ¹H‐NMR, FTIR, and elemental analysis were employed to characterize the structures of these compounds. Also, the influences of the PEG segment lengths of PEG/SIPM copolymers on the surface tension, foaming properties, wetting power, and dispersant properties were investigated. The experimental results indicated that the solution that contained the PEG/SIPM copolymer surfactants exhibited excellent surface‐active properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2727–2731, 2002     

Characteristics of PPG-based thermoplastic polyurethane doped with lithium perchlorate

Segmented thermoplastic polyurethane (TPU) was synthesized from methylene bis(cyclohexyl isocyanate) (H₁₂MDI), ethylenediamine (EDA), and poly(propylene glycol) (PPG) with a molecular weight of 1000. The ratio of hard segment to soft segment (NCO/OH) is changed to test the chemical and physical properties. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and impedance spectroscopy (IS) were utilized to monitor the phase change of these TPU samples with various lithium perchlorate (LiClO₄) concentrations. Significant changes occur in the FTIR spectrum of the TPU with LiClO₄ concentration above 0.5 mmol/g TPU, indicating that an interaction existed between the lithium cation and the hard segment or soft phase. The soft-segment T_g increased with increasing LiClO₄ concentration through the examination of DSC. IS results indicate an increase in bulk conductivity as the salt concentration is increased. Electrochemical stability of the TPU sample was studied by cyclic votammetry (CV). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 389–399, 2001     

Effect of chain rigidity on block copolymer micelle formation and dissolution as observed by 1H-NMR spectroscopy

Amphiphilic copolymers poly(methyl methacrylate-b-acrylic acid), poly(methyl methacrylate-b-methacrylic acid), poly(methyl acrylate-b-acrylic acid) and poly(methyl acrylate-b-methacrylic acid) were prepared by reversible addition fragmentation chain-transfer (RAFT) polymerization. The hydrophilic polyacid blocks were either synthesized directly or formed by the hydrolysis of poly(tert-butyl acrylate) or poly(tert-butyl methacrylate) blocks. The hydrophobic blocks consisted of either the more rigid, high glass transition temperature (T _g ) poly(methyl methacrylate) or more flexible, low T _g poly(methyl acrylate) material. The hydrophilic blocks were either poly(methacrylic acid) (rigid, high T _g ) or poly(acrylic acid) (flexible, low T _g ). The micellization behavior of the polymers was studied by proton nuclear magnetic resonance (¹H-NMR) spectroscopy in mixtures of 1,4-dioxane-d₈ and D₂O. All four polymers were soluble in neat dioxane. In solutions of higher water content, the polymers with the more rigid hydrophobic blocks formed into micelles as was evidenced by broadening of the resonances resulting from the protons in those blocks. At moderate water concentration (25–50%), dissolution of the micelles was observed upon heating the solution. No micellization was observed in polymers containing the less rigid poly(methyl acrylate) hydrophobic block regardless of the identity of the hydrophilic block. As further evidence of micellization formation and dissolution, the spin-lattice (T ₁) and spin-spin (T ₂) relaxation times of protons in the hydrophobic and hydrophilic blocks were measured. Significant differences in the relaxation times as functions of temperature and solvent concentration were observed between the hydrophilic and hydrophobic blocks of the micelle-forming polymers.     

Acetic acid-doped poly(ethylene oxide)-modified poly(methacrylate): a new proton conducting polymeric gel electrolyte

A proton conducting polymeric gel membrane was first developed from poly(ethylene oxide)-modified poly(methacrylate) (PEO-PMA) containing poly(ethylene glycol) dimethylether (PEGDE). Acetic acid (HAc) was doped by immersing the polymeric film directly in the aqueous solution of HAc. Characterization by FT-IR, XRD and AC conductivity measurements were carried out on the film electrolytes consisting of different gel compositions. The ionic conductivity of the membrane showed a sensitive variation with the immersion time and concentration of the acid in the doping solution through the changes in the contents of acid and water in the gel. The ionic conductivity also depended on the PEGDE content in the polymer. The proton conductivity was 6.2×10⁻⁴ S cm⁻¹ at 20 °C and 1.0×10⁻³ S cm⁻¹ at 80 °C for the gel prepared from HAc concentration of 3.0 mol l⁻¹. The temperature dependence of the conductivity was found to be consistent with Arrhenius-type relationship at a temperature range from 20 to 80 °C, except for the films with low PEGDE contents. The apparent activation energy for the proton conduction was in the range of 5-30 kJ mol⁻¹, depending on the HAc concentration and the polymer matrix composition. The FT-IR spectra of the polymeric membranes showed that HAc does not protonate the carbonyl or ester groups of the polymer matrix, but interacts with them by the hydrogen bonding interaction or weak molecular interactions.