Search results for "Methylaluminoxane"
showing 9 items of 19 documents
Syndiospecific polymerization of styrene using methylaluminoxane-activated bis(phenolato)titanium complexes
1998
Styrene was polymerized using a series of methylaluminoxane-activated bis(phenolato)titanium complexes of the type ((OC 6 H 2 -4-Me-6- 1 Bu) 2 Z)TiX 2 (X = Cl, O 1 Pr, η 5 -C 5 Me 5 ) to give syndiotactic polystyrene. Catalyst activity was found to depend on the nature of the bridging group Z, where Z = CH 2 , CH 2 CH 2 , S, S=O. Activity was found to be highest for Z = S.
Copolymerization of ethylene with 1‐hexene over metallocene catalyst supported on complex of magnesium chloride with tetrahydrofuran
2004
The study of ethylene/1-hexene copolymerization with the zirconocene catalyst, bis(cyclopentadienyl)zirconium dichloride (Cp 2 ZrCl 2 )/methylaluminoxane (MAO), anchored on a MgCl 2 (THF) 2 support was carried out. The influence of 1-hexene concentration in the feed on catalyst productivity and comonomer reactivity as well as other properties was investigated. Additionally, the effect of support modification by the organoaluminum compounds [(MAO, trimethylaluminum (AlMe 3 ), or diethylaluminum chloride (Et 2 AlCl)] on the behavior of the MgCl 2 (THF) 2 /Cp 2 ZrCl/MAO catalyst in the copolymerization process and on the properties of the copolymers was explored. Immobilization of the Cp 2 ZrC…
Complexes of titanium and zirconium containing a tridentate linked amido–cyclopentadienyl ligand with a soft donor group: synthesis, structure, and e…
1999
Abstract Group 4 metal complexes M(η5:η1-C5R4SiMe2NCH2CH2SMe)Cl2 (R=H, M=Ti; R=Me, M=Ti, Zr) containing the thioether-functionalized linked amido–cyclopentadienyl ligand were synthesized and characterized by 1H- and 13C-NMR spectroscopy, mass spectrometry, and elemental analysis. The crystal structures of the complexes Ti(η5:η1-C5H4SiMe2NCH2CH2SMe)Cl2 and Zr(η5:η1:η1-C5Me4SiMe2NCH2CH2SMe)Cl2 were determined by single-crystal X-ray diffraction studies. The titanium complex is a conventional three-legged piano-stool molecule without an intramolecular interaction between the sulfur donor group and the titanium center, whereas the zirconium complex adopts a trigonal bipyramidal structure, with …
Ethylene polymerization with FI complexes having novel phenoxy-imine ligands: Effect of metal type and complex immobilization
2011
A series of bis(phenoxy-imine) vanadium and zirconium complexes with different types of R3 substituents at the nitrogen atom, where R3 = phenyl, naphthyl, or anthryl, was synthesized and investigated in ethylene polymerization. Moreover, the catalytic performance was verified for three supported catalysts, which had been obtained by immobilization of bis[N-(salicylidene)-1-naphthylaminato]M(IV) dichloride complexes (M = V, Zr, or Ti) on the magnesium carrier MgCl2(THF)2/Et2AlCl. Catalytic performance of both supported and homogeneous catalysts was verified in conjunction with methylaluminoxane (MAO) or with alkylaluminium compounds (EtnAlCl3−n, n = 1–3). The activity of FI vanadium and zirc…
2-Chloro/phenyl-7-arylimino-6,6-dimethylcyclopenta[b]pyridylnickel chlorides: Synthesis, characterization and ethylene oligomerization
2017
Abstract 2-Chloro/phenyl-7-arylimino-6,6-dimethylcyclopenta[b]pyridylnickel chlorides (Ni1–Ni8) were synthesized from the respective ligands L1–L8 and characterized. Upon activation with either methylaluminoxane (MAO) or ethylaluminium sesquichloride (EASC), they show high catalytic activity of up to 10.84 × 106 g(oligomer) mol− 1(Ni) h− 1 in ethylene oligomerization. The products range from butenes to dodecenes for Ni1–Ni4, but are limited to butenes and hexenes in the case of Ni5–Ni8. DFT calculations indicate that the Ni C bond length in the model alkyl complexes depends both on the nature of the substituents at the heterocycles and the kind of the alkyl group, shedding some light on the…
Pyrrolide-imine benzyl complexes of zirconium and hafnium: synthesis, structures, and efficient ethylene polymerization catalysis
2004
Abstract A series of pyrrolyl-imines HL1–6 was prepared by the condensation of pyrrole-2-carboxyaldehyde with different amines. The reaction of 2 equiv of pyrrolyl-imine with tetrabenzyl complexes of hafnium and zirconium M(CH2Ph)4 (M=Hf or Zr) gave dibenzyl complexes (L3–6)2M(CH2Ph)2, which were characterized by NMR spectroscopy and crystal structure analysis. NMR spectra of the complexes with secondary alkyl substituents at the imine nitrogen (isopropyl: 3a, 4-tert-butylcyclohexyl: 4a and 4b) suggest that rapid racemization between Δ and Λ configurations occurs in solution on the NMR time scale. The complexes with pyrrolide-imine ligands with a tertiary alkyl group such as tert-butyl (5a …
Tailoring polymers through interplay of ligands within precatalysts: 8-(Nitro/benzhydryl-arylimino)-7,7-dimethyl-5,6-dihydroquinolylnickel halides in…
2017
A series of 8-(nitro/benzhydryl-substituted arylimino)-7,7-dimethyl-5,6-dihydroquinolines and the corresponding nickel halide complexes were synthesized and characterized. Molecular structures of representative nickel complexes were determined by single crystal X-ray diffraction, showing the dinuclear dimers with distorted square-pyramidal geometry around the nickel center. The binding energies determined by X-ray photoelectron spectroscopy (XPS) indicate the effective coordination between the sp2-nitrogen and nickel atoms as well as the influence of both the halogen ligands and the substituents within dihydroquinolines on the strength of the NiN bond. Ethylene polymerization with the nicke…
Synthesis of branched polyethylenes by the tandem catalysis of silica-supported linked cyclopentadienyl-amido titanium catalysts and a homogeneous di…
2003
The synthesis of branched polyethylenes by ethylene polymerization with new tandem catalyst systems consisting of methylaluminoxane-preactivated linked cyclopentadienyl-amido titanium catalysts [Ti(η5:η1-C5Me4SiMe2NR)Cl2 (R = Me or tBu)] supported on pyridylethylsilane-modified silica (PySTiNMe and PySTiNtBu) and homogeneous dibromo nickel catalyst having a pyridyl-2,6-diisopropylphenylimine ligand (PyminNiBr2) in the presence of modified methylaluminoxane was investigated. Ethylene polymerization with only PyminNiBr2 yielded a mixture of 1- and 2-olefin oligomers with methyl branches [weight-average molecular weight (Mw) ∼ 460)] with a ratio of about 1:7. By the combination of this nickel …
Effect of sample preparation on gel permeation chromatography results of determination of molecular weight of polyethylene obtained with using of zir…
2003
Molecular weights of polyethylene (PE) obtained with using of zirconocene catalyst activated with large excess of methylaluminoxane (MAO) were determined by gel permeation chromatography (GPC) method. It was found that repeatability of the measurements is strongly influenced by MAO remained in PE samples as well as time of sample keeping in the apparatus (dissolution + measurement time) at temp. 142 °C. A method of MAO removing from PE samples, before GPC measurement, based on additional washing of the sample with HF in methanol solution has been proposed. This modification leads to better both authenticity and repeatability of the results. Studies on the influence of time of sample keeping…