Development of a predictive model for polymer/solvent diffusion coefficient calculations

A new calculation procedure for free‐volume parameters is considered in this work by using viscosity prediction methods and the Levenberg‐Marquardt calculation scheme. All parameters used in the Vrentas–Duda free‐volume theory can be estimated from pure component properties. The prediction results are compared with experimental data for some polymer/solvent systems. The diffusion coefficient calculated by Vrentas–Duda theory can be used in the modeling of membrane separation processes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of polyurethane resins and its improvement on dimensional stability and finishing performances of medium‐ and small‐diameter softwoods

This study analyzed the effects of polyurethane (PU) resin treatments on surface homogeneity, dimensional stability, and finishing performances of medium‐ and small‐diameter softwoods produced in Taiwan. Two‐pack PU resins were prepared by combing short castor oil‐modified alkyd resin serving as a polyol with polymeric 4,4′‐diphenymethane diisocyanate (PMDI) serving as a hardener, by the molar ratio of NCO/OH+COOH of 1.2. Four types of short oil‐modified alkyd resins with different polyhydric alcohols (glycerin and pentaerythritol) and polybasic acids (phthalic anhydride and isophthalic acid) were synthesized. Three kinds of medium‐ and small‐diameter softwoods, including China fir, Taiwanina, and Japanese fir with a diameter of 10–15 cm were obtained from Hui‐Sun Forest Station, Taiwan. The wood coating of nitrocellulose (NC) lacquer including sanding sealer and top clear was used. Results show that the surface hardness, homogeneity, moisture excluding efficiency, and antiswelling efficiency of woods were enhanced by PU resin treatments. Among all the PU resins, the isophthalic acid and pentaerythritol‐containing PU resin (IPA‐P‐MDI) achieved the best improved efficiency on dimensional stability of woods. Results of two types of finishing procedure, i.e. NC lacquer sanding sealer plus top clear and top clear only, applied onto the PU‐treated woods revealed that the hardness, adhesion, and durability of NC lacquer films on the PU‐treated wood were superior to those of untreated one, especially for top clear finishing alone. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of poly(methyl methacrylate)/silica nanocomposite through emulsion polymerization using dimethylaminoethyl methacrylate

Polymer/Silica nanocomposite latex particles were prepared by emulsion polymerization of methyl methacrylate (MMA) with dimethylaminoethyl methacrylate (DM). The reaction was performed using a nonionic surfactant and in the presence of silica nanoparticles as the seed. The polymer‐coated silica nanoparticles with polymer content and number average particle sizes ranged from 32 to 93 wt % and 114–310 nm, respectively, were obtained depending on reaction conditions. Influences of some synthetic conditions such as MMA, DM, surfactant concentration, and the nature of initiator on the coating of the silica nanoparticles were studied. Electrostatic attraction between anionic surface of silica beads and cationic amino groups of DM is the main driving force for the formation of the nanocomposites. It was demonstrated that the ratio of DM/MMA is important factor in stability of the system. The particle size, polymer content, efficiency of the coating reaction, and morphology of resulted nanocomposite particles showed a dependence on the amount of the surfactant. Zeta potential measurements confirmed that the DM was located at the surface of the nanocomposites particles. Thermogravimeteric analysis indicated a relationship between the composition of polymer shell and polymer content of the nanocomposites. The nanocomposites were also characterized by FTIR and differential scanning calorimetry techniques. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of novel amphiphilic sulfated ionomers by the ring‐opening reaction of an epoxidized styrene–butadiene–styrene triblock copolymer

A method for the synthesis of novel sulfated ionomer of styrene–butadiene–styrene triblock copolymer (SBS) was developed. SBS was first epoxidized by performic acid in the presence of a phase‐transfer catalyst; this was followed by a ring‐opening reaction with an aqueous solution of alkali salt of bisulfate. The optimum conditions for the ring‐opening reaction of the epoxidized SBS with an aqueous solution of KHSO₄ were studied. During the ring‐opening reaction, both phase‐transfer catalyst and ring‐opening catalyst were necessary to enhance the conversion of epoxy groups to ionic groups. The products were characterized with Fourier transform infrared spectrophotometry and transmission electron microscopy (TEM). After the potassium ions of the ionomer were substituted with lead ions, the lead sulfated ionomer exhibited dark spots under TEM. Some properties of the sulfated ionomer were studied. With increasing ionic groups or ionic potential of the cations, the water absorbency and emulsifying volume of the ionomer and the intrinsic viscosity of the ionomer solution increased, whereas the oil absorbency decreased. The sulfated ionomer possessed excellent emulsifying properties compared with the sulfonated SBS ionomer. The sodium sulfated ionomers in the presence of 10% zinc stearate showed better mechanical properties than the original SBS. When the ionomer was blended with crystalline polypropylene, a synergistic effect occurred with respect to the tensile strength. The ionomer behaved as a compatibilizer for blending equal amounts of SBS and oil‐resistant chlorohydrin rubber. In the presence of 3% ionomer, the blend exhibited much better mechanical properties and solvent resistance than the blend without the ionomer. SEM photographs indicated improved compatibility between the two components of the blend in the presence of the ionomer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The application of microencapsulated phase‐change materials to nylon fabric using direct dual coating method

The fabrication of functional textiles able to provide thermal regulation and comfort for the body has attracted increasing interest in recent years. This research investigated fabric coatings containing energy absorbing, temperature stabilizing, phase‐change material microcapsules (PCMMcs), and their methods of application. Specifically, a coated fabric was directly prepared by a dual‐type coating method, in which the PCMMcs were dispersed in a polyurethane coating solution with no binder. The thermal performances of the dual‐coated samples were evaluated by differential scanning calorimetry, and their physical characteristics were examined by scanning electron microscopy, thermal vision camera, porosity, water vapor transmission rate (WVTR), and water entry pressure (WEP) analyses. Furthermore, the microclimate characteristics of the thermally enhanced fabrics were investigated under experimental conditions using a human‐clothing‐environment (HCE) simulator system. The study results confirmed the superior performance of the dual‐coated fabrics in terms of thermal regulation and body comfort, compared with those coated by the dry or wet coating method, because of the improved WEP, WVTR, and thermal performance. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of a novel proton‐exchange membrane for fuel cells operating at high temperatures and low humidities

The synthesis of a p‐toluidine/formaldehyde (PTF) resin was performed, and the effects of the molar ratio of the individual monomers and the polymerization conditions on the structure of the PTF resin were studied. Fourier transform infrared and ¹³C‐NMR spectra were used to characterize the PTF. Wide‐angle X‐ray diffraction patterns revealed the crystalline structures of various PTFs. Polarized optical microscopy revealed that the molar ratio of the monomers had a strong effect on the crystalline morphologies. A longer polymerization time turned out a polymer with a higher intrinsic viscosity and molecular weight, which led to differences in the proton conductivity. All of the PTFs showed a higher proton conductivity than a commercial Nafion membrane at 90–100°C and 0% relative humidity. The proton conductivity of the PTF series could be improved by sulfonation with sulfuric acid and could be maintained after blending with polyurethane. Pure methanol could be used as a fuel source because of the insolubility and nonwetting properties of PTF in methanol to increase the output current density for a PTF membrane electrode assembly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Potentiometric studies of oxidation–reduction reactions with redox copolymers

Polymeric oxidants in the bead form that were macroporous styrene/divinylbenzene copolymers containing N‐chlorosulfonamide functional groups (in sodium or hydrogen form) or N‐bromosulfonamide groups (in sodium form) were synthesized and investigated to determine their oxidizing powers. The redox potentials of the N‐chlorosulfonamide/sulfonamide and N‐bromosulfonamide/sulfonamide systems were determined by potentiometric studies at different pH values with aqueous solutions of Na₂SO₃, KCN, and KSCN as reducers. The formal redox potentials of the N‐chlorosulfonamide copolymers were 0.79, 0.44, and ?0.12 V at pH's of 1.8, 8.45, and 13.6, respectively. The formal redox potential of the N‐bromosulfonamide copolymer was about 100 mV higher in comparable conditions and in solutions over pH = 5 (e.g., 0.56 V at pH = 8.56). The comparatively higher oxidizing power of the N‐bromosulfonamide copolymer was particularly evident in a strong alkaline medium (in which the N‐chlorosulfonamide copolymer was not reactive). In contrast, the N‐chlorosulfonamide copolymer showed strong oxidative properties in acidic media (in which the N‐bromosulfonamide copolymer decomposed itself). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Water and salt permeability of reinforcement polymer‐gel composite membrane

The charged mosaic polymer membrane (CMM) without reinforcement and the composite charged mosaic polymer membrane (CCMM) with reinforcement were investigated in terms of salt and water transport (permeability). The composite charged mosaic polymer membrane (CCMM) with reinforcement showed a unique transport behavior such as preferential material transport L_p and ω. Water permeability coefficient, L_p and salt permeability coefficient, ω were estimated by taking account of active layer thickness of composite polymer gel. The L_p and ω values of CCMM with reinforcement were larger than those of CMM without reinforcement. On the other hand, the reflection coefficient of CCMM, σ, showed negative value, which suggested preferential material transport to solvent transport. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of post‐treatments on the properties of porous poly(vinyl alcohol) membranes

Porous poly(vinyl alcohol) (PVA) membranes were prepared by a phase‐inversion method. The influence of chemical crosslinking and heat treatments on the swelling degree, resistance to compaction, mechanical strength, and morphology of porous PVA membranes was extensively studied. The crosslinking degree and crystallinity of the membranes, calculated from IR spectra, increased with the treatment time. The porosity, calculated on the basis of swelling experiments, showed a decreasing trend for heat‐treated membranes but remained almost at a constant value for crosslinked membranes. Such a change was further proved with scanning electron microscopy pictures. The behavior was explained by the rearrangement of PVA chains during the heat‐treatment process, which led to morphological changes in the membranes. The mechanical properties of the porous membranes in dry and wet states were measured, and a great difference was observed between crosslinked and heat‐treated membranes in the dry and wet states. The crosslinked membranes showed good mechanical properties in the dry state but became fragile in the wet state. On the contrary, the heat‐treated membranes were more flexible in the wet state than in the dry state. This change was explained by the turnaround of inner stress in the systems during the swelling process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Intercalated clays from pentaerythritol stearate for use in polymer nanocomposites

Smectite clays treated with quaternary ammonium salts have been utilized for decades in paints, greases, cosmetics, and personal care products as rheological modifiers. They have also been used in industrial wastewater treatment extensively. In more recent times these surface modified clays have demonstrated benefits in polymer/clay nanocomposites. The use of quaternary ammonium modifiers limits the usefulness of these composites in food packaging because they are not approved for direct food contact. It would be advantageous to have surface modifying chemicals acceptable for direct food contact in these composites. This article reports research conducted on a promising surface modifier pentaerythritol stearate (PS), which is approved by the FDA for inclusion in food as a preservative. The surface modification of montmorillonite with PS is reported in detail as well as the production of nanocomposites with selected polymers made with the modified clay. Molecular modeling and purification of commercial PS samples indicate that the mono‐ and diesters are the critical surface modifiers, although the as received commercial material works well in forming intercalated clay complexes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008