Alkylation of aldehydes with methanol over titanium oxide catalysts

The methylation of various aldehydes, such as acetaldehyde, propionaldehyde, and phenylacetaldehyde over titanium oxidesupported vanadium oxide was studied under atmospheric pressure and temperatures of 250–400°C. The catalyst properties of titanium oxide can be enhanced only by addition of a fairly small amount of vanadium. High-temperature treatment transforms titanium oxide, the support, from anatase to rutile, which causes the catalysts to lose their catalytic properties. The reactivity of these can be ranked in the following order: acetaldehyde > propionaldehyde > phenylacetaldehyde. The steric effect of the substituted groups in propionaldehyde or phenylacetaldehyde may prevent self-condensation to form oligomers and to give a high selectivity of alkylated products.     

Graft polymerization of vinyl acetate onto granular starch: Comparison on the potassium persulfate and ceric ammonium nitrate initiated system

This work was undertaken to discuss in depth the vital differences in the morphological development during synthesis, and properties of starch‐g‐poly‐(vinyl acetate) copolymers using two different initiators, potassium persulfate (KPS) and ceric ammonium nitrate (CAN). KPS‐initiated system gave relatively low values of grafting ratio and grafting efficiency, indicating a great tendency for the formation of poly(vinyl acetate) homopolymer (PVAc). Yet, higher values were seen for the CAN‐initiated system. Transmission electron microscope observations indicated a relatively broad distribution of latex particles for the KPS‐initiated system. The surface potential of latex particles was about ?3.5 mV, which turned out to be insufficient to maintain stability of latex particles. On the other hand, a uniform particle size distribution was found for the CAN‐initiated system, as the surface potential of latex particles was 21.5 mV. Moreover, radicals on starch molecules were generated directly through a redox reaction with positively charged ceric ion. The hydrophobic PVAc chains were thus grafted on starch, resulting in an amphiphilic graft copolymer, which provides a sufficient stabilization degree as a role of surfactant to render a relatively uniform distribution of latex particles. The synthesized starch‐g‐poly(vinyl acetate) copolymers were further converted to starch‐g‐poly(vinyl alcohol) through saponification, which were subjected to evaluations regarding the biodegradation and cell culture capability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3017–3027, 2006     

Thermooxidative degradation of natural rubber/clay composite

The clay is treated with a reducing agent and an acid so as to obtain a clay containing various metal components with a variable‐valence state. Then, the clay is coprecipitated with natural rubber (NR) latex to prepare a vulcanized NR/clay composite. The degradation process of the NR/clay composite under hot air condition was studied dynamically by using a Fourier transform infrared spectrometer attaching an in situ sample cell and was also investigated using the TGA method. The test result obtained from the infrared spectrometry indicated that under low decomposition temperature, the decomposition products of the test samples mainly are ethylene, low molecular olefinic hydrocarbon, and carbonyl compounds. As the decomposition temperature rises, the low molecular olefinic hydrocarbon content decreases, the olefine with longer chain is formed, and a lot of alkane decomposition products are formed at the same time. When the content of the metal components with a variable‐valence state in clay such as Cu, Mn, Co, and Fe increases, the oxidation products containing the carbonyl group, the olefinic hydrocarbon, and CO₂ in the decomposition product of the test sample also increase. The TGA result clearly shows a shoulder peak that appears by the side of the main peak on the DTG curve of NR/clay composite. With the increase in the content of metal components with variable‐valence state in clay, the initial degradation temperature of the test sample (T₀), the degradation peak temperature (T_p1), and the final degradation temperature (T_f1) in first‐stage reaction, as well as the degradation peak temperature (T_p2) and the last final degradation temperature (T_f) in second‐stage reaction of all the test samples more or less shift to the direction of low temperature; besides, the activation energy (E) of the reaction of the test samples more or less decreases. This means that the metal components with variable‐valence state promote the oxidative degradation of the clay–rubber masterbatch. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3809–3815, 2006     

Enhanced corrosion prevention effect of polysulfone–clay nanocomposite materials prepared by solution dispersion

A series of polymer–clay nanocomposite (PCN) materials containing polysulfone (PSF) and layered MMT clay were successfully prepared by effectively dispersing inorganic nanolayers of MMT clay in an organic PSF matrix via a solution dispersion technique. The synthesized PCN materials were subsequently investigated with a series of characterization techniques, including Fourier transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The prepared PCN coatings with low clay loading (1 wt %) on cold‐rolled steel (CRS) were found to be superior in corrosion prevention to those of bulk PSF, based on a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and electrochemical impedance spectroscopy (EIS) in a 5 wt % aqueous NaCl electrolyte. The effects of material composition on the molecular barrier, mechanical strength and optical clarity of PSF and PCN materials, in the form of membranes, was also studied by molecular permeability analysis (GPA), dynamic mechanical analysis (DMA) and UV‐Visible transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 631–637, 2004     

Morphology and characterization of conductive films based on polyaniline‐coated polystyrene latexes

The polyaniline (PANI)‐coated polystyrene (PS) latexes were synthesized, and the electrically conductive films were prepared thereafter. The weight ratio of PANI was 5%. Thermal analysis of the latices was performed using DSC and TGA. In this study, the electrically conductive films were prepared above the PS glass transition temperature (T_g). During the film formation, the effects of the annealing temperature and atmosphere (air or N₂) on the film resistance were investigated. In addition, the film morphology was observed utilizing scanning electron microscopy. The film resistance decreased in the initial heating stage due to the increasing temperature and the compaction of film. Then the film resistance increased with further annealing due to the aging of PANI. Typically, the film resistance was about 6000 Ω/sq, and the conductivity was 0.3 S/cm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5406–5413, 2006     

Solvent fractionation of petroleum pitch for mesophase formation

Petroleum pitch (Ashland A240) has been subjected to thermal treatment and solvent fractionation to produce refined pitches to be evaluated as impregnants for C-C composites. The solvent fractions were obtained by sequential Soxhlet extraction with solvents such as hexane, benzene, and pyridine. Thermal treatment to 408 °C produced a mesophase pitch (≈50% mesophase); an appreciable portion of the mesophase was soluble in strong solvents. There were substantial differences in chemical composition and in pyrolysis behaviour of the fractions. As the depth of fraction increased, the pyrolysis yield and bloating increased, and the microstructure of the coke became finer until glassy microconstituents were formed in the deepest fractions.     

Synthesis and self-assembly of comb oligomers having rigid racemic or chiral binaphthyl macrocyclic pendant groups

In this article, we described the synthesis of comb oligomers having rigid racemic or chiral binaphthyl macrocyclic pendant groups via the free radical polymerization. Oligomers obtained were well characterized by MALDI-TOF-MS, ¹H NMR, FT-IR, UV, CD and SEC. These comb oligomers having macrocyclic pendant groups showed very good solubility in common organic solvents at room temperature. Furthermore, the oligomers could self-assemble into different morphologies by dropping their THF solutions of different concentrations on the surface of water. At a relatively low concentration, the oligomers self-aggregated into hollow spheres. When the concentration was increased, the aggregates changed into solid spheres. The morphologies of the hollow or solid spheres were observed by TEM and ESEM.     

Adsorption properties of a chelating resin containing hydroxy group and iminodiacetic acid for copper ions

A chelating resin, PSGI, was synthesized by the radical polymerization of GMA‐IDA, DVB, and styrene for the removal of Cu(II), Co(II), and Cd(II) from an aqueous solution. The characteristic functional groups and chemical composition of PSGI were analyzed by Fourier transform infrared spectroscopy and elemental analysis of C, H, and N. The equilibrium adsorption capacities of PSGI from their single‐metal ion solutions were 1.46 mmol/g for Cu(II), 1.02 mmol/g for Co(II), and 1.10 mmol/g for Cd(II). The adsorption isothermal of Cu(II) by PSGI followed the Langmuir isotherm. Increasing the concentration (0–0.1 M) of KCl in Cu(II) solution affected the adsorption behavior slightly. Within the pH range of 2–5.5, decreasing the pH of the Cu(II) solution did not produce remarkable changes in the equilibrium adsorption capacities. The adsorption capacities of PSGI for Cu(II) did not cause significant change during the repeated adsorption–desorption operations. The competitive adsorption tests verified that this resin had good adsorption selectivity for Cu(II) with the coexistence of Co(II) and Cd(II). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2123–2130, 2004     

Properties of modified polyacrylonitrile membranes prepared by copolymerization with hydrophilic monomers for water–ethanol mixture separation

A new kind of terpolymer membrane was employed to separate a permselective water–alcohol mixture. This membrane was prepared via the copolymerization of acrylonitrile, sodium salt styrene sulfonic acid (SStSA), and hydroxyethyl methacrylate in dimethylsulfoxide with azobisisobutyronitrile as an initiator. The reaction mechanism, resultant structure, and polymer composition were confirmed by IR and elemental analysis. The effects of the feed composition on the polymer composition, mechanical properties, thermal properties, and degree of swelling were investigated. It was found that water permeated through the membrane preferentially in a water/alcohol system. The flux increased with the increase of SStSA, but the separation factor decreased drastically with higher SStSA. For a 50 wt % water–ethanol mixture, a flux of 0.65 kg/m² h and a separation factor of 212 were obtained at 30°C when the membrane containing the highest SStSA content was used. The capacities of the metal ions absorbed by the membranes were investigated in the study. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 244–250, 2003     

Biodegradation of catechol by Pseudomonas fluorescens isolated from petroleum‐impacted soil

Bioremediation strategies have been applied to clean up petroleum hydrocarbon (PHC) impacted sites. Introducing PHC degrading microorganisms (bioaugmentation) and enhancing the in‐situ nutrients availability (biostimulation) are widely used strategies. These strategies can be combined to lead to a better bioremediation performance. In this work, Pseudomonas fluorescens was isolated from a PHC impacted site. Through a 2³ factorial design plan, the effect of various combinations of nitrate, sulphate, and phosphate ions on the PHC bioremediation performance by P. fluorescens was investigated using catechol, an essential metabolic intermediate of BTEX degradation, as the sole carbon source. The maximum specific catechol degradation rate was chosen as the response to evaluate the catechol bioremediation performance. The ANOVA results indicated that the presence of nitrate ions alone lowered the maximum specific catechol degradation rate, which can be explained by the accumulation of nitrites and ammonia during the denitrification process by P. fluorescens. It was noted that dosing sulphate ions alone did not affect the bioremediation performance, which indicates P. fluorescens can grow in a sulphur‐limited environment. In contrast, the presence of sulphate and nitrate ions together can lead to a higher specific catechol degradation rate. This may be caused by the presence of sulphate that can suppress the production of nitrites. The importance of phosphate ions on catechol biodegradation was investigated. The absence of phosphate led to incomplete biodegradation. Introducing phosphate ions can accelerate catechol degradation, which can be explained by the secretion of organic acids.