Synthesis and aqueous solution behaviors of sodium sulfonate‐terminated dendritic poly(ester‐amine)

Sodium sulfonate‐terminated dendritic poly(ester‐amine) (SPEA) was synthesized by sulfonation of acrylic double bond‐terminated dendritic poly(ester‐amine) (APEA) with sodium hydrogen sulfite (NaHSO₃) in mixture of diglycol and 2‐butanone under normal pressure. The structure of SPEA was characterized by IR, ¹H‐NMR, and elemental analysis. SPEA was water‐soluble. 1.0–40.0% (mass) SPEA aqueous solutions appeared as dilatant fluid. When pH value varied from 1.5 to 12.0, the viscosity of 1–5% (mass) SPEA aqueous solutions changed very small, and the electric conductivity almost kept stable within pH 3.0–10.0. The relationship between the viscosity and the concentration of SPEA water solutions was similar to that of NaCl water solutions. The surface tension of SPEA water solutions was lower than that of polyethylene glycol 2000 water solutions with the same concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

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 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     

Preparation and adsorption behavior of a cellulose‐based,mixed‐mode adsorbent with a benzylamine ligand for expanded bed applications

A novel mixed‐mode expanded bed adsorbent with anion‐exchange properties was explored with benzylamine as the functional ligand. The cellulose composite matrix, densified with stainless steel powder, was prepared with the method of water‐in‐oil suspension thermal regeneration. High activation levels of the cellulose matrix were obtained with allyl bromide because of the relative inertness of the allyl group under the conditions of the activation reaction. After the formation of the bromohydrin with N‐bromosuccinimide and coupling with benzylamine, the activated matrix was derived to function as a mixed‐mode adsorbent containing both hydrophobic and ionic groups. The protein adsorption capacity was investigated with bovine serum albumin as a model protein. The results indicated that the prepared adsorbent could bind bovine serum albumin with a high adsorption capacity, and it showed salt tolerance. Effective desorption was achieved by a pH adjustment across the isoelectric point of the protein. The interactions between the cell and adsorbent were studied, and the bioadhesion was shielded by the adjustment of the salt concentration above 0.1M. Stable fluidization in the expanded bed was obtained even in a 2% (dry weight) yeast suspension. The direct capture of target proteins from a biomass‐containing feedstock without extra dilution steps could be expected with the mixed‐mode adsorbent prepared in this work, and this would be especially appropriate for expanded bed adsorption applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects and properties of poly(arylene ether benzonitrile)s of various molecular weights blended with sulfonated poly(ether ether ketone)

Poly(arylene ether benzonitrile) (PAEBN) was synthesized with 2,6‐dichlorobenzonitrile and biphenol. PAEBNs with various molecular weights (MWs), 1,640,000 and 185,000 g/mol, were synthesized by control of the stoichiometry of the monomers and were blended with sulfonated poly(ether ether ketone) (SPEEK). The effects of MW on the water uptake, swelling, methanol permeability, and proton conductivity of the SPEEK/PAEBN blend membranes were investigated. The molecular mobility of the SPEEK/PAEBN blends was also examined in this study. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

EPR kinetics in irradiated syndiotactic polystyrene at elevated temperatures

Free radicals are formed upon irradiation of polymers. The annealing of γ-ray irradiated syndiotactic polystyrene (sPS) with doses 10, 23 and 36 kGy was studied with electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra are possibly attributed to three types of radicals, (a) the benzyl radical Ra, (b) resonance structure of the phenyl radical Rb, and (c) carbon-superoxide-centered radical Rc with three-, four-, and single-line features, respectively. Radical Ra can be easily formed by the removal of the proton from the tertiary carbon; radical Rb is created from delocalization of the spin of the radical Ra onto the benzene ring; and radical Rc may be generated from the interaction of a carbon-centered radical with dioxygen from the air which forms a carbon-superoxide center. By comparing EPR spectra of the radicals with a DPPH standard, the spin numbers of the radicals can be calculated. The spin number of all radicals decreases exponentially with time in the temperature range of 60-90 °C regardless of dose of the irradiation. The annealing of Ra, Rb, and Rc follows first-order kinetics. The activation energies of the annihilation are determined to be 15.8-19.0, 16.0-19.5, and 23.2-26.6 kJ/mol for radicals Ra, Rb, and Rc, respectively. The kinetic study presented herein can serve as a criterion for γ-ray irradiation process in various applications, such as sterilization of polymer materials and devices.     

Authors' reply

Presents the authors reply to comments by Tong, Li and Wei (ibid. p.703-5). For original paper see ibid., vol. 10, p. 39-49, Feb.2002.