Synthesis of new thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing epoxide pendant groups

A new class of thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing pendant epoxide groups were synthesized and characterized. These new epoxy polymers were prepared through the bromination of poly(2,6‐dimethyl‐1,4‐phenylene oxide) in halogenated aromatic hydrocarbons followed by a Wittig reaction to yield vinyl‐substituted polymer derivatives. The treatment of the vinyl‐substituted polymers with m‐chloroperbenzoic acid led to the formation of epoxidized poly(2,6‐dimethyl‐1,4‐phenylene oxide) with variable pendant ratios, and the structures and properties were studied with nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The ratios of pendant functional groups were tailored for the polymer properties, and the results showed that the glass‐transition temperatures increased as the benzylic protons were replaced by bromo‐, vinyl‐, or epoxide‐functional groups, whereas the thermal stability decreased in comparison with the original polymer. Within a molar fraction of 20–50%, the degree of functionalization had little effect on the glass‐transition temperature; however, it correlated inversely with the thermal stability of each functionalized polymer. The thermal curing behavior of the epoxide‐functionalized polymer was enhanced by the increment of the pendant functionality, which resulted in a significant increase in the glass‐transition temperature as well as the thermal stability after the curing reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5875–5886, 2006     

Synthesis of TiO2–SiO2/polymer core–shell microspheres with a microphase‐inversion method

A novel microphase‐inversion method was proposed for the preparation of TiO₂–SiO₂/poly(methyl methacrylate) core–shell nanocomposite particles. The inorganic–polymer nanocomposites were first synthesized via a free‐radical copolymerization in a tetrahydrofuran solution, and the poor solvent was added slowly to induce the microphase separation of the nanocomposite and result in the formation of nanoparticles. The average particle sizes of the microspheres ranged from 70 to 1000 nm, depending on the reaction conditions. Transmission electron microscopy and scanning electron microscopy indicated a core–shell morphology for the obtained microspheres. Thermogravimetric analysis and X‐ray photoelectron spectroscopy measurements confirmed that the surface of the nanocomposite microspheres was polymer‐rich, and this was consistent with the core–shell morphology. The influence of the synthetic conditions, such as the inorganic composition and the content of the crosslinking monomer, on the particle properties was studied in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3911–3920, 2006     

Highly substituted poly(2,3‐diphenyl‐1,4‐phenylenevinylene) derivatives having bulky phenyl and fluorenyl pendant groups: Synthesis,characterization, and electro‐optical properties

Two series of poly(2,3‐diphenyl‐1,4‐phenylenevinylene) (DP‐PPV) derivatives containing multiple bulky substituents were synthesized. In the first series, two different groups were incorporated on C‐5,6 positions of the phenylene moiety to increase steric hindrance and to obtain blue‐shifted emissions. In the second series, bulky fluorenyl groups with two hexyl chains on the C‐9 position were introduced on two phenyl pendants to increase the solubility as well as steric hindrance to prevent close packing of the main chain. Polymers with high molecular weights and fine‐tuned electro‐optical properties were obtained by controlling the feed ratio of different monomers during polymerization. The maximum photoluminescent emissions of the thin films are located between 384 and 541 nm. Cyclic voltammetric analysis reveals that the band gaps of these light‐emitting materials are in the range from 2.4 to 3.3 eV. A double‐layer EL device with the configuration of ITO/PEDOT/P4/Ca/Al emitted pure green light with CIE′1931 at (0.24, 0.5). Using copolymer P6 as the emissive layer, the maximum luminescence and current efficiency were both improved when compared with the homopolymer P4. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6738–6749, 2006     

Surface characterization and barrier properties of plasma‐modified polyethersulfone/layered silicate nanocomposites

This study describes the preparation of polyethersulfone (PES)/layered silicate nanocomposites (PLSNs) by mixing PES polymer chain into organically‐modified layered silicate in 1‐methyl‐2‐pyrrolidinone (NMP) solution. Both X‐ray diffraction data and transmission electron microscopy images of PLSNs indicate that the silicate layers were almost exfoliated and randomly distributed into the PES matrix. The mechanical and barrier properties of PLSNs show remarkable enhancement in the storage modulus and water/oxygen permeability when compared with that of neat PES matrix. Surfaces modification of PES and PLSN films with various treated times, system pressures, and radio frequency (RF) powers were performed using a mixture of oxygen (O₂) and nitrogen (N₂) plasmas. The topographical and physical properties of plasma‐modified PES and PLSN surfaces were investigated using scanning probe microscopy (SPM), contact‐angle measurements, and X‐ray photoelectron spectroscopy (XPS). These results indicate that the surface roughness of PLSNs with the same condition of plasma modification is lower than that of neat PES matrix and is probably due to the increase of stiffness with the presence of inorganic layered silicates in PES matrix. The surface properties of the PES and PLSNs are also changed from hydrophobic to hydrophilic. The XPS spectra suggest that the exposure of the PES and PLSNs to the plasmas led to the combination of etching reactions of polymer surface initiated by plasma and the following addition reactions of new oxygen‐ and nitrogen‐containing functional groups onto polymer surfaces to change their surface properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3185–3194, 2006     

Independence of the brittle–ductile transition from the rubber particle size for impact‐modified poly(vinyl chloride)

A series of acrylic impact modifiers (AIMs) with different particle sizes ranging from 55.2 to 927.0 nm were synthesized by seeded emulsion polymerization, and the effect of the particle size on the brittle–ductile transition of impact‐modified poly(vinyl chloride) (PVC) was investigated. For each AIM, a series of PVC/AIM blends with compositions of 6, 8, 10, 12, and 15 phr AIM in 100 phr PVC were prepared, and the Izod impact strengths of these blends were tested at 23 °C. For AIMs with particle sizes of 55.2, 59.8, 125.2, 243.2, and 341.1 nm, the blends fractured in the brittle mode when the concentration of AIM was lower than 10 phr, whereas the blends showed ductile fracture when the AIM concentration reached 10 phr. It was concluded that the brittle–ductile transition of the PVC/AIM blends was independent of the particle size in the range of 55.2–341.1 nm. When the particle size was greater than 341.1 nm, however, the brittle–ductile transition shifted to a higher AIM concentration with an increase in the particle size. Furthermore, the critical interparticle distance was found not to be the criterion of the brittle–ductile transition for the PVC/AIM blends. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 696–702, 2006     

Chiral separation of synthetic vicinal diol compounds by capillary zone electrophoresis with borate buffer and beta-cyclodextrin as buffer additive.

The investigation on capillary electrophoretic enantioseparation of six synthetic compounds containing vicinal diol groups has been undertaken to acquire the optimum conditions using native beta-cyclodextrin (beta-CD) as chiral selector and borate as a background electrolyte. The separation was carried out in an uncoated capillary (58.5 cm x 75 microm i.d., effective length 48.5 cm) and the effects of several important factors were investigated in detail. The results showed that beta-CD as a chiral selector exhibited good enantioselectivity and that the enantioseparation was greatly influenced by the structure of the diols, the borate concentration and the buffer pH. The optimum performance was obtained for the chiral vicinal diols under the conditions of 200 mM borate buffer of pH 9.8 containing 1.7% beta-CD at an applied voltage of 15 kV and a capillary temperature of 20 degrees C. Under the conditions, four diols were baseline separated with fast analysis time and the good theoretical plate numbers (above 10 x 10(4)) and favorable migration-time reproducibilities (RSDs below 3.0%) were obtained. The separation results were satisfactory.     

Preparation of AgBiVMoO/-Al2O3 Catalysts for the Partial Oxidation of Propane

A novel mixed sol method was developed for the preparation of supported catalysts. Analyses by means of XRD and BET show that a 40%AgBiVMoO/γ-Al2O3 catalyst prepared by this method possessed high specific surface area and high dispersion of the active phase. As a result, high acrylic acid selectivity of 8.5% was obtained when the catalyst was used in the reaction of propane partial oxidation to acrylic acid in a fixed-bed reactor.     

Density functional study of the l-proline-catalyzed α-aminoxylation of aldehydes reaction: The reaction mechanism and selectivity

The reaction mechanism of the l-proline-catalyzed α-aminoxylation reaction between aldehyde and nitrosobenzene has been investigated using density functional theory (DFT) calculation. Our calculation results reveal following conclusions [1]. The first step that corresponds to the formation of C–O bond, is the stereocontrolling and rate-determining step [2]. Among four reaction channels, the syn-attack reaction channel is more favorable than that of the anti one, and the TS-ss channel dominates among the four channels for this reaction in the step of C–O bond formation [3]. The intermolecular hydrogen bond between the acidic hydrogen of l-proline and the N atom of the nitrosobenzene in an early stage of the process catalyzes very effectively the C–O bond formation by a large stabilization of the negative charge that is developing at the O atom along the electrophilic attack [4]. The effect of solvent decreases the activation energy, and also, the calculated energy barriers are decrease with the enhancement of dielectric constants for C–O bond formation step. These results are in good agreement with experiment, and allow us to explain the origin of the catalysis and stereoselectivity for l-proline-catalyzed α-aminoxylation of aldehyde reaction. The addition of H₂O to substituted imine proline, intermolecular proton-transfer steps, and the l-proline elimination process were also studied in this paper.