Self-immobilized titanium and zirconium catalysts with phenoxy-imine ligands for ethylene polymerization. X-ray crystal structure of bis(N-(3-tert-butylsalicylidene)-4 '-allyloxyanilinato) zirconium(IV) dichloride

Four self-immobilized FI catalysts with allyl substituted phenoxy-imine ligands [{4-(CH2=CHCH2O)C6H5N=CH-C6H3(3-tert-C4H9)O}(2) MCl2] (1: M = Ti: 2: M = Zr), [{3-(CH2=CHCH2O)C6H5N=CH-C6H3(3-tert-C4H9)O}(2)MCl2] (3: M = Zr), [{4-(CH2=CHCH2-2,6-(iso-C3H7)(2))C6H5N=CH-C6H3(3,5-(NO2)(2))O}(2)MCl2] (4: M = Zr) have been synthesized and characterized. The molecular structure of 2 has been determined by X-ray crystallographic analysis. The results of ethylene polymerization showed that the self-immobilized titanium (IV) and zirconium (IV) catalysts 1-3 kept high activity for ethylene polymerization and 4 showed no activity. SEM showed the immobilization effect could greatly improve the morphology of polymer particles to afford micron-granula polyolefin as supported catalysts.

Ethylene-propylene copolymerization with bis(beta-enaminoketonato) titanium complexes activated with modified methylaluminoxane

Ethylene-propylene copolymerization, using [(Ph)NC(R-2)CHC(R-1)O](2)TiCl2 (R-1 = CF3, Ph, or t-Bu; R-2 = 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 R-1 and R-2 influenced the copolymerization behavior, including the copolymerization activity, methylene sequence distribution, molecular weight, and polydispersity. With small steric hindrance at R-1 and R-2, one complex (R-1 = CF3; R-2 = CH3) displayed high catalytic activity and produced copolymers with high propylene incorporation but low molecular weight. The microstructures of the copolymers were analyzed with C-13 NMR to determine the methylene sequence distribution and number-average sequence lengths of uninterrupted methylene carbons.

Syntheses, structure and ethylene polymerization behavior of beta-diiminato titanium complexes

A series of new titanium complexes bearing beta-diiminato ligands [(Ph)NC(R-1)CHC(R-2)N(Ph)](2)TiCl2 (4a: R-1 = R-2 = CH3; 4b: R-1 = R-2 = CF3; 4c: R-1 = Ph, R-2 = CH3; 4d: R-1 = Ph, R-2 = CF3) has been synthesized and characterized. X-ray crystal structures reveal that complexes 4a and 4c adopt distorted octahedral geometry around the titanium center. With modified methylaluminoxane (MMAO) as a cocatalyst, complexes 4a-d are active catalysts for ethylene polymerization, and produce high molecular weight polyethylenes. Catalyst activities and the molecular weights of polymers are considerably influenced by the steric and electronic effects of substituents on the catalyst backbone under the same polymerization condition. With the strong electron-withdrawing groups (CF3) at R-1 or/and R-2 position, complexes 4b and 4d show higher activities than complexes 4a and 4c, respectively.

Titanium complexes with novel triaryl-substituted phosphinimide ligands: Synthesis, structure and ethylene polymerization behavior

A series of titanium phosphinimide complexes [Ph2P(2-RO-C6H4)(2)TiCl2 (7, R = CH3; 8, R = CHMe2) and (PhP(2-Me2CHOC6H4)][THF]TiCl3 (9) have been prepared by reaction of TiCl4 with the corresponding phosphinimines under dehalosilylation. The structure of complex 9 has been determined by X-ray crystallography, and a solvent molecule THF was found to be coordinated with the central metal and the Ti-O bond was consistent with the normal Ti-O (donor) bond length. The complexes 7 and 8 displayed inactive to ethylene polymerization, and the complex 9 displayed moderate activity in the presence of modified methylaluminoxane (MMAO) or i-BU3Al/Ph3CB(C6F5)(4), and this should be partly attributed to coordination of THF with titanium and the steric effect of two iso-propoxyl. And catalytic activity up to 32.2 kg-PE/(mol-Ti h bar) was observed.

Titanium and zirconium complexes with aminoiminophosphorane ligands

A series of titanium and zirconium complexes based on aminoiminophosphorane ligands [Ph2P(Nt-Bu)(NR)](2)MCl2 (4, M = Ti, R = Ph; 5, M = Zr, R = Ph; 6, M = Ti, R = SiMe3; 7, M = Zr, R = SiMe3) have been synthesized by the reaction of the ligands with TiCl4 and ZrCl4. The structure of complex 4 has been determined by X-ray crystallography. The observed very weak interaction between Ti and P suggests partial pi-electron delocalization through both Ti and P. The complexes 4-7 are inactive for ethylene polymerization in the presence of modified methylaluminoxane (MMAO) or i-Bu3Al-Ph3CB(C6F5)(4) under atmospheric pressure, and is probably the result of low monomer ethylene concentration and steric congestion around the central metal.

Sol-gel-derived titanium oxide/copolymer composite based glucose biosensor

A new type of sol-gel-derived titanium oxide/copolymer composite material was developed and used for the construction of glucose biosensor. The composite material merged the best properties of the inorganic species, titanium oxide and the organic copolymer, poly(vinyl alcohol) grafting 4-vinylpyridine (PVA-g-PVP). The glucose oxidase entrapped in the composite matrix retained its bioactivity. Morphologies of the composite-modified electrode and the enzyme electrode were characterized with a scanning electron microscope. The dependence of the current responses on enzyme-loading and pH was studied. The response time of the biosensor was < 20 s and the linear range was up to 9 mM with a sensitivity of 405 nA/mM. The biosensor was stable for at least I month. In addition, the tetrathiafulvalene-mediated enzyme electrode was constructed for the decrease of detection potential and the effect of three common physiological sources that might interfere was also investigated.

Preparation and properties of polyimide films codoped with barium and titanium oxides

Polyimide hybrid films containing bimetalic compounds were obtained by codoping poly(amic acid) with a barium and titanium precursor prepared from BaCO3, Ti(OBu)(4), and lactic acid followed by casting and thermal curing. FTIR, WAXD, and XPS measurements showed that barium and titanium precursor could be transformed to BaTiO3 at a temperature above 650 degreesC, while the mixed oxides were only found in hybrid films. The measurements of TEM and AFM indicated a homogeneous distribution of inorganic phase with particle sizes less than 50 nm. The hybrid films exhibited fairly high thermal stability, good optical transparency, and promising mechanical properties. The incorporation of 10 wt % barium and titanium oxide lowered surface and volume electrical resistivity by 2 and 5 orders, respectively, increasing dielectric constant from 3.5 to 4.2 and piezoelectric constant from 3.8 to 5.2 x 10(-12) c/N, relative to the nondoped polyimide film.

Studies on electrocatalytic performance of titanium oxide electrode modified with Pt toward the oxidation of methanol

Electrocatalytic performance of the Pr-TiOx/Ti electrode prepared with electrochemical reduction-oxidation method toward the oxidation of methanol has been studied, The experimental results showed that the Pt-TiOx/Ti electrode has a high electrocatalytic activity and good stability for the electrocatalytic oxidation of methanol, By means of electrochemical, XPS, STM and in-situ FTIR techniques, it was found that one reason for the electrode to exhibit an excellent performance is attributed to the high dispersion between nanosized Pt and TiOx particles, The low adsorption ability of the intermediate derived from methanol, such as linearly adsorbed CO species on the electrode surface due to the interaction between Pt and TiOx, also results in the excellent performance.

X-ray crystal structure and molecular mechanics calculations of (2,6-iso-dipropyl-phenylamide) dimethyl (tetra-methylcyclopenta-dienyl) silane titanium dichloride

Crystal and molecular structure of (2.6-dipropylphenylamide) dimethyl (tetra-methyl cyclopentadienyl) silane titanium dichloride (I) was fully characterized by X-ray diffraction. The crystal is obtained from a mixture of ether/hexane as orthorhombic. with a = 12.658 (3) Angstrom. b = 16.62 (3) Angstrom. c = 11.760 (2) Angstrom. V = 2474.2 (9) Angstrom(3). Z = 4, space group Pnma. R = 0.0399; Componud I compose of the pi-bounded ring with its dimethylsilyl-dipropyl phenyl amido group and the two terminal chloride atoms coordinated to central metal to form a so-called constrained geometry catalyst (CGC) structure. The result of molecular mechanics (MM) calculations on compound I shows that bond lengths and bond angles from the MM calculation are comparable to the data obtained from the X-ray diffraction study. The relation of the structure of CGCs and their catalytic activity by MM calculations is also discussed.

Amperometric tyrosinase biosensor based on a sol-gel-derived titanium oxide-copolymer composite matrix for detection of phenolic compounds

A new type of tyrosinase biosensor was developed for the detection of phenolic compounds, based on the immobilization of tyrosinase in a sol-gel-derived composite matrix that is composed of titanium oxide sol and a grafting copolymer of poly(vinyl alcohol) with 4-vinylpyridine. Tyrosinase entrapped in the composite matrix can retain its activity to a large extent owing to the good biocompatibility of the matrix. The parameters of the fabrication process and the variables of the experimental conditions for the enzyme electrode were optimized. The resulting sensor exhibited a fast response (20 s), high sensitivity (145.5 muA mmol(-1) 1) and good storage stability. A detection limit of 0.5 muM catechol was obtained at a signal-to-noise ratio of 3.

Electrocatalytic oxidation of methanol at the titanium oxide electrode modified with Pt microparticles

The electrocatalytic oxidation of methanol at the Titanium oxide (TiOx, x<2) film modified with Pt microparticles has been studied. The results show that the modified electrodes exhibit a significant electrocatalytic activity and good stability for the oxidation of methanol. Under the optimal conditions, the peak current density at 0.58 V for the oxidation of methanol in the positive-going sweep is about 526 mA/cm(2) at the scan rate of 5 mV/s in 0.5 mol/L CH3OH and 0.5 mol/L H2SO4 solution and the over potential of the methanol oxidation at the modified electrode increases about 30 similar to 40 mV after 70 minutes at the current density of 100 mA/cm(2) and 50 mA/cm(2). The enhanced electrocatalytic activity and good stability are ascribed to the high dispersion of Pt microparticles in and on the TiOx film and the synergistic effect between Pt microparticles and TiOx.

Synthesis, properties and crystal structure of a heteropoly compound containing titanium

K4H2CoW12O40. 2Ti02 . 9H(2)O crystallizes from an aqueous solution of Na2WO4, Co(OAc)(2) and Ti(SO4)(2). The compound has very similar i.r. and u.v. spectra to those of [CoW12O40](6-) and [CoW11TiO40](8-) but its polarographic behaviour is different from that of [CoW11TiO40](8-) and exhibits only reduction of tungsten(VI). A single crystal structural analysis indicates that this compound consists of the heteropolyanion [CoW12O40](6-), titanium-oxygen chain, potassium ions and water molecules.

Preparation of TiO2 Film through Hydrolysis of Titanium Butoxide and Interaction between Sensitizing Dyes and the Film

A method of preparation of stable, homogeneous and controlled thickness TiO2 film through hydrolysis of Ti(OC4H(9))(4) is introduced in detail. The structure and property of the film have been investigated by means of SEM and FT-IR techniques. The strong quenching effect between sensitizing dyes and TiO2 film is observed in their fluorescence spectra.

Polymer-supported titanium catalysts for syndiotactic polymerization of styrene

Poly(styrene-co-acrylamide) (PSAm)-titanium complexes (PSAm . Ti) were prepared and characterized. It is found that the coordination number of acrylamide (Am) to Ti in the complexes is strongly dependent on Am content in PSAm, but not on [Am]/[Ti] ratio in the feed. The infrared and x-ray photoelectron spectra suggest that the polymer-supported complexes possess the structure [GRAPHICS] The catalytic behavior of the complexes in styrene polymerization is described. The catalytic activity is markedly affected by [Al]/[Ti] ratio in the complexes. C-13 NMR, IR, and DSC data indicate that the polystyrene obtained with PSAm . Ti/MAO (MAO = methylaluminoxane) is highly syndiotactic. Use of Et(3)Al and i-Bu(3)Al in place of MAO gives atactic polystyrene. The activities of the various aluminum compounds used as the cocatalysts decrease in the order: MAO > Et(3)Al > i-Bu(3)Al. The polymer-supported complexes show relatively high activity even after the complexes had been exposed to air for 19 h or higher polymerization temperature. (C) 1996 John Wiley & Sons, Inc.

DICHLORO(ETA(5)-CYCLOPENTADIENYL)([1-(4-METHOXYPHENYL)CYCLOHEXYL]-ETA(5)-CYCLOPENTADIENYL)TITANIUM(IV)

The title molecule, [TiCl2(C5H5)(C18H21O)], has a pseudotetrahedral bent metallocene structure in which the cyclopentadienyl ring is symmetrically bonded to Ti [range of Ti-C distances 2.36(1)-2.41(1)Angstrom], but the substituted cyclopentadienyl ring adopts asymmetrical bonding [Ti-C 2.33(1)-2.48(1)Angstrom] due to the interaction of the large substituent with the Cl(2) atom. The angle C(11)-C(1)-C(21) is 111.1(8)degrees with the large substituent occupying a cis position with respect to the substituted ring.