Self-immobilized catalysts for ethylene polymerization: neutral, single-component salicylaldiminato phenyl nickel(II) complexes bearing allyl substituents

A new family of self-immobilized ethylene polymerization catalysts, derived from neutral, single-component salicylaldiminato phenyl nickel complexes, is described.

Synthesis of C-1 bridge-containing metallocene catalysts and their catalytic activities for olefin polymerization

The synthesis and characterization of metallocene complexes which can be used as catalysts in the presence of MAO for olefin polymerization were discussed in the present paper. The metallocene complexes have been characterized by IR, H-1 NMR, EI-MS spectra and element analyses; The catalytic features of Olefin polymerization were studied under different conditions. Metallocenes in which metals is Ti had no activity for ethylene polymerization, Polymers with different features can be obtained by using different catalysts.

Pentamethylcyclopentadienyl halfsandwich rhodium complexes containing 1,1 '-ferrocene dichalcogenido chelate ligands

The heterobimetallic complexes Cp * Rh(CN Bu-t)(EC5H4)(2)Fe [E = S(2),Se(3), Te(4)] have been synthesized by the reaction of halfsandwich rhodium complex Cp * Rh(CNtBu) Cl-2 with Fe(C5H4ELi)(2). 2THF. Oxidation of 2,3 by AgBF4 to give ferrocenium - type salts [Cp * Rh(CNtBu) (EC5H4)(2)Fe] (+) [BF4] (-) [E = S(5),Se(6)] also occurs readily. The new complexes have been characterized by MS IR, H-1 and C-13 NMR spectroscopy and elemental analysis.

Low-temperature oxidation of methane to form formaldehyde: role of Fe and Mo on Fe-Mo/SiO2 catalysts, and their synergistic effects

The partial oxidation of methane with molecular oxygen was performed on Fe-Mo/SiO2 catalysts. Iron was loaded on the Mo/SiO2 catalyst by chemical vapor deposition of Fe-3(CO)(12). The catalyst showed good low-temperature activities at 723-823 K. Formaldehyde was a major condensable liquid product on the prepared catalyst. There were synergistic effects between iron and molybdenum in Fe-Mo/SiO2 catalysts for the production of formaldehyde from the methane partial oxidation. The activation energy of Mo/SiO2 decreased with the addition of iron and approached that of the Fe/SiO2. The concentration of isolated molybdenum species (the peak at 1148 K in TPR experiments) decreased as the ion concentration increased and had a linear relationship with the selectivity of methane to formaldehyde. The role of Fe and Mo in the Fe-Mo/SiO2 catalyst was proposed: Fe is the center for the C-H activation to generate reaction intermediates, and Mo is the one for the transformation of intermediates into formaldehyde. Those phenomena were predominant below 775 K.

Syntheses and crystal structures of novel di- and trinuclear rhodium complexes bridged by pyrazine

Never di- and trinuclear Rh complexes, [Rh-2(PPh3)(4)(H)(4)(Me2CO)(2)(mu -pyz)](ClO4)(2). EtOH and [Rh-3(PPh3),(mu -pyz)(3)](ClO4)(3). EtOH were selectively isolated from the reaction of [Rh(PPh3)(2)(H)(2)(Me2Co)(EtOH)]ClO4 with pyrazine (pyz) in Me2CO and THF, respectively. Their structures were crystallographically characterized.

Polymerization of methyl methacrylate with organolanthanides as single-component catalysts

It was first found that Ind(2)Y(mu -Et)(2)AlEt2 and Ind(2)LnN(i-Pr)(2) (Ln = Y, Yb) exhibit extremely high catalytic activity in the polymerization of methyl methacrylate. The reactions can be carried out over a quite broad range of polymerization temperatures from -30 to 50 degreesC. PMMA with high molecular weight (7.8 x 10(-5)) and high isotacticity (94%) can be obtained by using Ind(2)Y(mu -Et)(2)AlEt2, and narrow molecular weight distribution (M-w/M-n < 1.5) can be obtained by using Ind(2)LnN(i-Pr)(2) (Ln = Y, Yb).

Polymerization of acrylonitrile with organolanthanides as single-component catalysts

Ind(2)Y(mu -Et)(2)AlEt2 and Ind(2)LnN(i-Pr)(2) (Ln = Y, Yb) were used as a single-component catalyst for the polymerization of acrylonitrile (AN) respectively. The regularity of polymerization of AN and stereoregularity of polyacrylonitrile (PAN) were also studied in both cases. Both catalysts can produce PAN with molecular weight from 10,000 to 30,000. In addition, the catalytic activity and molecular weights were increased by the addition of PhONa.

Binuclear lanthanide complexes as catalysts for the hydrolysis of double-stranded DNA

The efficient cleavage of plasmid DNA ( pCAT) by binuclear lanthanide complexes was investigated. At 37 degrees C and neutral pH, both Ho23+L and Er23+L promoted 100% conversion of supercoiled plasmid to the nicked circular form and linear form in 1 h. The corresponding saturation kinetics curve of cleavage of pCAT plasmid by binuclear lanthanide complexes showed the expected increase with catalyst concentration. (C) 1999 Elsevier Science S.A. All rights reserved.

Preparation of polymer-supported zirconocene catalysts and olefin polymerization

A novel polymer-supported metallocene catalyst with crosslinked poly(styrene-co-acrylamide) (PSAm) as the support has been prepared and characterized. The probability of long sequences of acrylamide (Am) in PSAm is still low even at an Am amount of 32.8 mol %, implying the relatively homogeneous distribution of Am. The infrared spectra of PSAm and the supported catalyst substantiate that an amide group in PSAm coordinates with methylaluminoxane through both oxygen and nitrogen atoms. Ethylene/alpha-octene copolymerization showed that the catalytic activity is not markedly affected by adding alpha-octene. C-13 NMR analysis of the ethylene/alpha-octene copolymer indicated that the composition distribution of the copolymer is uniform. (C) 1999 John Wiley & Sons, Inc.

Reactivity of Pt/Al2O3 and Pt/CeO2/Al2O3 catalysts for partial oxidation of methane to syngas

The ceria modified Pt/CeO2/Al2O3 and Pt/Al2O3 catalysts were studied in the partial oxidation of methane to syngas. The SEM, XRD, TPR and TPD techniques were used for the catalyst characterization. The addition of ceria could enhance the Pt dispersion and decrease the Pt crystallise size; the activity and selectivity of catalyst for partial oxidation were improved significantly, and the methane total oxidation was suppressed sharply. The ceria effect was also discussed in a detailed way.

Isobutane/butene alkylation over supported heteropoly acid catalysts: I. Influence of the structure of silica

Catalysts consisting of heteropoly acids (HPAs) supported on different silica and mesoporous molecular sieves have been prepared by impregnation and the sol-gel method, respectively, and their catalytic behavior in fixed-bed alkylation of isobutane with butene has been investigated. The activity, selectivity and stability of the supported-HPA catalysts could be correlated with the surface acidity of the catalysts, the structure of supports as well as the time on stream (TOS). In the fixed-bed reactor, the acidity of the heteropoly acid is favorable to the formation of dimerization products (C-8(=)); especially, the pore size of supports was seen to have an important effect on activity and product distribution of the catalysts. Contrary to the traditional solid-acid catalysts, the supported-HPA catalysts own an excellent stability for alkylation, which makes it possible for these supported catalysts to replace the liquid-acid catalysts used in industry.

Preliminary investigations on polymerization catalysts composed of lanthanocene and methylaluminoxane

The polymerization of butadiene(Bd), isoprene(Ip) and styrene(St) has been examined using the six catalyst systems composed of lanthanocene, (C5H9Cp)(2)NdCl(I), (C5H9Cp)(2)SmCl(II), (MeCp)(2)SmOAr'(III), (Ind)(2)NdCl(IV), Me2Si(Ind)(2)NdCl(V) and (Flu)(2)NdCl(VI), and methylaluminoxane(MAO) respectively. All of them can be used to form the polyisoprene with molecular weights of 1 to 10 thousand and cis-1,4-unit contents of 41 to 47%. (I), (II) and (III) of them can be also used to form the polybutadiene with molecular weights of 10 to 20 thousand and cis-1,4-unit contents of 62 to 78%. In addition, the catalysts from (II) to (V) are still active for St polymerization and (II) of them gives a syndio -rich random polystyrene. It is noteworthy that (II) and (III) are active for homopolymerization of Bd, Ip and St in the same polymerization condition.

Studies on the elimination of NO over the La-Ba-Cu mixed oxide catalysts with perovskite structure

The mixed oxides, including YBa2Cu3O7, LaBa2Cu3O7, LaBaCu2O5, La2BaCu3O7, La4BaCu5O12 with perovskite structure, were prepared. The catalysts were characterized by means of chemical analysis, XRD, TPD and TPR method. It was found that they were the active catalysts for the NO decomposition and NO reduction by CO. The existance of Cu3+ is an important factor to give the catalysts a high activity for the NO reduction by CO.

Polymerization of ethylene by zirconocene-B(C6F5)(3) catalysts with aluminum compounds

Ethylene polymerization by zirconocene-B(C6F5)(3) catalysts with various aluminum compounds has been investigated. It is found that the catalytic activity depended on zirconocenes used, and especially on the type of aluminum compounds. For Et(H(4)Ind)(2)ZrCl2 (H(4)Ind : tetrahydroindenyl), the activity decreases in the following order: Me3Al > i-Bu3Al > Et3Al much greater than Et2AlCl. While for Cp2ZrCl2(Cp : cyclopentadienyl), it varies as follows: i-Bu3Al > Me3Al much greater than Et3Al. Furthermore, the activity is significantly affected by the addition mode of the catalytic components, which may imply that the formation of active centers is associated with an existing concentration of catalytic components. Results of thermal behavior of polyethylene (PE) studied by differential scanning calorimetry(DSC) show that crystallinity of the polymer prepared with Et3Al is higher than that with Me3Al or i-Bu3Al. It is also found that the number-average molecular weight ((M) over bar) of the polymers prepared with Me3Al or i-Bu3Al is much higher than that with Et3Al. H-1-NMR studies substantiate that i-Bu3Al is a more efficient alkylation agent of Cp2ZrCl2 in comparison with Me3Al. (C) 1997 John Wiley & Sons, Inc.

Studies of catalyzed reaction mechanism between co-polyether (THF/EO) and N-100 by NMR - Interaction and complex formation between reactants and catalysts

To elucidate the mechanism of the catalyzed reaction of co-polyether (EO/THF) with N-100, the interaction and complex formation between reactants and catalysts were investigated by means of NMR spectroscopy. It is shown that the resonance peak of isocyanate carbon splits into two parts when the solutions of N-100 and co-polyether were mixed. The disappearing of proton resonance peak of hydroxyl group in NMR spectra when dibutyltin dilaurate(DBTDL) were added to the copolyether(THF/EO) solution indicates the complex formation, This interaction appears to be a bonding of tin to the oxygen of hydroxyl and make the hydrogen of the hydroxyl group very mobile and active, then exchange with other protons, In the case of triphenyl bismuth(TPB), the high field shift and intensity enhancement of proton peak were observed, which suggest a nucleophilic attack of the bismuth to the hydroxyl hydrogen.