A high-resolution MAS NMR study on the potential catalysts Mo/HBeta for olefin metathesis: The interaction of Mo species with HBeta zeolite

The interfacial interaction of Mo species with the HBeta zeolite was studied by multinuclear MAS NMR, XRD and N₂ adsorption. As proved by the quantitative ²⁷Al MAS NMR, this interaction is so strong as to dealuminate the framework of HBeta, and leads to a new peak appearing at −14 ppm, which indicates the formation of crystalline Al₂(MoO₄)₃. This can also be detected by XRD measurements when the Mo loading is as high as 9.0 wt.%. The corresponding quantitative ²⁹Si and ¹H MAS NMR spectra show that the amount of silanols and Brønsted acidic sites decrease obviously with increasing Mo loading. This also reveals an interaction between Mo species and HBeta support through an oxygen bridge resulting from condensation with the hydroxyls on the support. At higher Mo loadings, the interaction is so strong that it results in an extraction of aluminum from the zeolite framework, and subsequently appearance of Al₂(MoO₄)₃ and loss of Brønsted acidic sites. These can be correlated to the low catalytic activity of Mo/HBeta in metathesis of ethylene and 2-butylene to propylene.     

Ethylene–propylene copolymerization with bis(β‐enaminoketonato) titanium complexes activated with modified methylaluminoxane

Ethylene–propylene copolymerization, using [(Ph)NC(R₂)CHC(R₁)O]₂TiCl₂ (R₁ = CF₃, Ph, or t‐Bu; R₂ = CH₃ or CF₃) titanium complexes activated with modified methylaluminoxane as a cocatalyst, was investigated. High‐molecular‐weight ethylene–propylene copolymers with relatively narrow molecular weight distributions and a broad range of chemical compositions were obtained. Substituents R₁ and R₂ influenced the copolymerization behavior, including the copolymerization activity, methylene sequence distribution, molecular weight, and polydispersity. With small steric hindrance at R₁ and R₂, one complex (R₁ = CF₃; R₂ = CH₃) displayed high catalytic activity and produced copolymers with high propylene incorporation but low molecular weight. The microstructures of the copolymers were analyzed with ¹³C NMR to determine the methylene sequence distribution and number‐average sequence lengths of uninterrupted methylene carbons. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5846–5854, 2006     

Crosslinked epoxy materials exhibiting thermal remendablility and removability from multifunctional maleimide and furan compounds

Crosslinked polymeric materials, which exhibit thermal remendability and removability through Diels–Alder (DA) and retro‐DA reactions, were obtained from using multifunctional maleimide and furan compounds as monomers. The synthesized monomers possess low melting points and good solubility in organo solvents to show excellent processing properties. The performance of DA and retro‐DA reactions were demonstrated with DSC and FTIR measurements. High performance of thermal remendablility and removability of the crosslinked materials were observed with SEM and solvent tests. These materials were applicable in advanced encapsulants and structural materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 905–913, 2006     

Synthesis and characterization of polyimides derived from (3‐amino‐2,4,6‐trimethylphenyl)‐(3′‐aminophenyl)methanone and aromatic dianhydrides

A series of new polyimides were prepared via the polycondensation of (3‐amino‐2,4,6‐trimethylphenyl)‐(3′‐aminophenyl)methanone and aromatic dianhydrides, that is, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride. The structures of the polyimides were characterized by Fourier transform infrared and NMR measurements. The properties were evaluated by solubility tests, ultraviolet–visible analysis, differential scanning calorimetry, and thermogravimetric analysis. The two different meta‐position‐located amino groups with respect to the carbonyl bridge in the diamine monomer provided it with an unsymmetrical structure. This led to a restriction on the close packing of the resulting polymer chains and reduced interchain interactions, which contributed to the solubility increase. All the polyimides except that derived from BPDA had good solubility in strong aprotic solvents, such as N‐methyl‐2‐pyrrolidinone, N,N′‐dimethylacetamide, N,N‐dimethylformamide, and dimethyl sulfone, and in common organic solvents, such as cyclohexanone and chloroform. In addition, these polyimides exhibited high glass‐transition values and excellent thermal properties, with an initial thermal decomposition temperature above 470 °C and glass‐transition temperatures in the range of 280–320 °C. The polyimide films also exhibited good transparency in the visible‐light region, with transmittance higher than 80% at 450 nm and a cutoff wavelength lower than 370 nm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1291–1298, 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     

Vinyl copolymers containing pendant 1,4‐distyrylbenzene and 1,3,4‐oxadiazole chromophores: Preparation and optoelectronic properties

We prepared two vinyl copolymers P1 and P2 containing pendant distyrylbenzene and aromatic 1,3,4‐oxadiazole derivatives, respectively, from their precursor poly(styrene‐ran‐4‐vinylbenzyl chloride) (M_w = 11,400, PDI = 1.18), which had been prepared by the controlled radical polymerization (RAFT). Two main chain polymers containing similar isolated distyrylbenzene ( P3) and aromatic 1,3,4‐oxadiazole ( P4 ) chromophores were also synthesized for comparative study. The resulted copolymers ( P1 – P4 ) are soluble in common organic solvents and are basically amorphous materials with 5% weight‐loss temperature higher than 360 °C. The PL spectral results reveal that the architecture of P1 prevents the formation of inter‐ or intramolecular interaction. The HOMO and LUMO levels of P2 , estimated from cyclic voltammetric data, are ?5.96 and ?3.81 eV, respectively, which are much lower than those of P1 (?5.12 and ?3.11 eV). The emission of blend from P1 and P2 are contributed mainly from distyrylbenzene fluorophore (～450 nm) owing to efficient energy transfer. Moreover, the blend exhibits three kinds of redox behavior depending on their weight ratios. The luminance and current efficiency of the EL device lpar;ITO/PEDOT/ MEH ‐ PPV + P2 /Al) are 503 cd/m² and 0.11 cd/A, which can be improved to 1285 cd/m² and 0.44 cd/A, respectively, as the weight ratio of P2 increases from 0 to 20%. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5362–5377, 2006     

Investigation of sulfonated poly(ether ether ketone sulfone)/heteropolyacid composite membranes for high temperature fuel cell applications

The sulfonated poly(ether ether ketone sulfone) (SPEEKS)/heteropolyacid (HPA) composite membranes with different HPA content in SPEEKS copolymers matrix with different degree of sulfonation (DS) were investigated for high temperature proton exchange membrane fuel cells. Composite membranes were characterized by Fourier transfer infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). FTIR band shifts suggested that the sulfonic acid groups on the copolymer backbone strongly interact with HPA particles. SEM pictures showed that the HPA particles were uniformly distributed throughout the SPEEKS membranes matrix and particle sizes decreased with the increment of copolymers' DS. The holes were not found in SPEEKS‐4/HPA30 (consisting of 70% SPEEKS copolymers with DS = 0.8 and 30% HPA) composite membrane after composite membranes were treated with boiling water for 24 h. Thermal stabilities of the composite membranes were better than those of pure sulfonated copolymers membranes. Although the composite membranes possessed lower water uptake, it exhibited higher proton conductivity for SPEEKS‐4/HPA30 especially at high temperature (above 100 °C). Its proton conductivity linearly increased from 0.068 S/cm at 25 °C to 0.095 S/cm at 120 °C, which was higher than 0.06 S/cm of Nafion 117. In contrast, proton conductivity of pure SPEEKS‐4 membrane only increased from 0.062 S/cm at 25 °C to 0.078 S/cm at 80 °C. At 120 °C, proton conductivity decreased to poor 0.073 S/cm. The result indicated that composite membranes exhibited high proton conductivity at high temperature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1967–1978, 2006     

Viscometric study of gelatin in dilute aqueous solutions

The viscosities of aqueous solutions of gelatin at different temperatures were carefully measured in a common glass‐capillary Ubbelohde viscometer at dilute to extremely dilute concentrations. The adsorption effect that occurred in the viscosity measurements was theoretically analyzed and discussed. A theory based on Langmuir isotherms could adequately describe the existing data. Some structural information was obtained by the use of an iterative fitting procedure to treat the reduced viscosity data, which disclosed that individual gelatin chains underwent a coil‐to‐helix transition as the solution cooled from 40 to 15 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1804–1812, 2006     

Crystal structure and morphology of phenyl‐capped tetraaniline in the leucoemeraldine oxidation state

A series of crystals of phenyl‐capped tetraaniline in the leucoemeraldine oxidation state were obtained at different isothermal temperatures and were observed directly under transmission electron microscope. The crystals obtained at higher temperatures exhibit more perfect structures than those obtained at lower temperatures. Both the lamella thickness and the crystal size increase with crystallization temperature. The tetraaniline is apt to form larger scale crystals under lower degree of supercooling. However, their crystal structures keep steady with the crystallization temperature. The tetramer was found to adopt a monoclinic lattice with unit cell parameter of a = 13.93 Å, b = 8.82 Å, c = 23.20 Å, and β = 95.03°, as determined using electron diffraction tilting method combined with wide‐angle X‐ray diffraction experiment. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 764–769, 2006     

Further study of the viscoelastic phase separation of cyanate ester modified with poly(ether imide)

In this study, the viscoelastic phase separation process was studied further by time‐resolved light scattering, differential scanning calorimetry, and scanning electron microscopy in the system of poly(ether imide)‐modified bisphenol‐A dicyanate. It was observed that the evolution time of phase structure and relaxation time of diffusion flow of the bisphenol‐A dicyanate were similar with the phase diagram of curing conversion versus content of PEI. The results suggested that the viscoelastic phase separation was affected by the curing conversion of the system at the onset point of phase separation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 517–523, 2006