Thermal stabilization effect of biphenol monoacrylate on polyamide 6

Biphenol monoacrylate (AL) was combined with a traditional hindered phenolic‐based binary antioxidant system to form a ternary stabilization system for the purpose of further improving the thermal–oxidative stability of polyamide 6 (PA6). The thermal stabilization effect of the antioxidant AL on PA6 was studied in terms of the reduced viscosity, the chemical structure, the yellow index, and the mechanical properties. The results showed that the antioxidant AL, with the proper chemical structure, could improve the thermal stability of PA6 effectively through a unique bifunctional stabilizing mechanism. The interaction of the molecules of PA6 with the antioxidant AL was investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Restraining the associations of anthracene fluorophore by chemically linking to poly(methyl methacrylate)

Associations (dimer or aggregate) of anthracene (An) fluorophores tend to interrupt the monomer emission and reduce the quantum yield (Φ_PL); therefore, poly(methyl methacrylate) (PMMA) chain was used in this study to chemically link to anthracene and to block the mutual associations among the anthracene fluorophores. With this aim, the target polymers were prepared by anionic polymerizations with 9,10‐dibromoanthracene/s‐butyllithium as initiating system to proceed polymerizations of methyl methacrylate (MMA) directly or in the presence of 1,1‐diphenylethylene (DPE). Use of DPE before addition of MMA produces stable initiating anionic species and avoids potential side reactions during polymerization; however, it also introduces four β‐phenylene rings around the central anthracene ring, which interfere with the corresponding emission pattern and reduce the Φ_PL (32%) value due to potential interactions between phenylene rings and anthracene. On the contrast, polymerization without participation of DPE results in polymer with central anthracene ring directly connected to two PMMA chains, which gives clean vibronic emission pattern with limited association emissions and enhanced Φ_PL (52%) value. Physical blending of anthracene by PMMA is less efficient to restrain the associations and results in a film of lower Φ_PL (20%). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of metal-complex imprinted PVDF hollow fiber membranes

Using nickel-2,2′-dipyridyl complex as a template, N-vinyl-2-pyrrolidone as the metal coordination functional monomer, and ethylene glycol dimethacrylate as the crosslinker, polyvinylidene fluoride (PVDF) hollow fiber ultrafiltration membrane as the supported membrane, metal complex imprinted polymeric membranes were prepared. The association constant of template-monomer interaction in the prepolymerization solution was estimated to be 4.38 × 10⁴ (L/mol)² by spectrophotometric titration analysis. The attenuated total reflection Fourier transform infrared spectroscopy and scanning electron micrograph characterization indicated that the surface of the support PVDF membrane was completely coated by the imprinted polymer layer after modification. The imprinted membranes exhibited the selective permeability for the template in certain nickel acetate solution. The molecularly imprinted membranes gave higher permeation separation factors at about pH 6, whereas increasing pressure would lower the separation ability. The effects of ion concentration, cations and counterions, ligand selectivity, pH, and trans-membrane pressure were investigated and the permeation performances of the imprinted membranes could be regarded as facilitated transport mechanism. © 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 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     

Synthesis and magnetic properties of novel fully conjugated polymeric complexes containing 1,10‐phenanthroline

A novel fully conjugated polymer containing 1,10‐phenanthroline (DAPcDOD) was first synthesized by the polycondensation of 2,7‐dimethyl‐2,4,6‐octatriene‐1,8‐dial with 5,6‐diamine‐1,10‐phenanthroline. Three polymeric complexes were first prepared by the reaction of DAPcDOD with NiSO₄, CoCl₂, and FeSO₄, respectively. The structures of the polymer and the complexes were characterized by IR, ¹H‐NMR, and elemental analysis. The magnetic behaviors of these complexes were measured as a function of magnetic field strength (0–50 kOe) at 5 K and as a function of temperature (5–300 K) at a magnetic field strength of 30 kOe. The results show that DAPcDOD–Ni²⁺ and DAPcDOD–Co²⁺ were soft ferromagnets, whereas DAPcDOD–Fe²⁺ exhibited the features of an antiferromagnet. © 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     

Synthesis and structural characterization of methacrylic acid/octadecyl acrylate‐graft‐poly(methylhydrosiloxane) by hydrosilylation

Methylmethacrylate (MMA) and octadecyl acrylate (OA) were grafted to poly(methylhydrosiloxane) (PMHS) by hydrosilylation, respectively, with hexachloroplatinic acid as catalyst, and the former was further hydrolyzed to prepare methacrylic acid (MAA)‐graft‐PMHS under the alkaline condition. Through orthogonal experiment, main factors affecting the graft reaction between OA and PMHS were discussed and arranged in a decreasing order according to their abilities of the effect on the hydrosilylation of OA with PMHS: catalyst dosage, reaction temperature, reaction time, material ratio, and solvent dosage. It was found that the hydrosilylation of OA with PMHS was easier to that of MMA with PMHS. Under optimal conditions, the grafting ratios of MMA with PMHS and OA with PMHS reached about 90 and 95%, respectively. FTIR and ¹H NMR spectra indicated that the hydrosilylation reactions followed the Markovnikov's rule and played a strong preference toward β‐1,2‐addition. The test of contact angle indicated that surface energy of a system was mainly dependent on the polar groups. The surface energy of OA‐graft‐PMHS (35.07 mN/m) was similar to those of PMHS (35.62 mN/m) and polyoctadecyl acrylate (36.57 mN/m), and lower than that of MAA‐graft‐PMHS (43.50 mN/m). © 2007 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