Catalysis
Tatiana B. Mikenas; A. V. Sholma; Vladimir A. Zakharov; Mikhail Matsko
Abstract
The paper presents data on the effect exerted by magnesium dichloride in Ziegler-Natta catalysts on the activity and molecular weight of polyethylene (PE) produced by ethylene polymerization in the absence or presence of hydrogen. It was found that ethylene polymerization in the absence of hydrogen over ...
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The paper presents data on the effect exerted by magnesium dichloride in Ziegler-Natta catalysts on the activity and molecular weight of polyethylene (PE) produced by ethylene polymerization in the absence or presence of hydrogen. It was found that ethylene polymerization in the absence of hydrogen over titanium-magnesium catalysts (TMCs) with different ratio of titanium chloride and magnesium dichloride (Ti/Mg = 0.5 and 0.07), oxidation state of titanium (TiCl3 or TiCl4) and structural characteristics of the catalysts leads to the formation of PE with a close molecular weight. At the same time, PE obtained over a δ-TiCl3 catalyst has a much (threefold) higher molecular weight. The introduction of hydrogen during polymerization for decreasing the molecular weight of PE is accompanied by a sharp drop in activity of the δ-TiCl3 catalyst, in distinction to the highly active supported TMC containing 3 wt. % Ti. Data about the effect of hydrogen content during polymerization on the molecular weight of PE were used to calculate the ratio of rate constants for polymer chain transfer with hydrogen (KtrH) and polymer chain propagation reaction (Кр). This value was close for TMCs of different composition containing magnesium dichloride. In the case of δ-TiCl3, the KtrH/Кр value was approximately two times lower compared to TMCs.
Catalysis
Nina V. Semikolenova; Valentina N. Panchenko; Mikhail A. Matsko; Vladimir A. Zakharov
Abstract
For preparation of highly active supported catalyst with bis(imino)pyridyl Fe(II) complexes (Fe1, Fe2) and N,N-α-diimine complex of Ni (Ni3), silica modified with alumina (SiO2 (Al)) was used as a support. Data on the possibility to regulate molecular weight (MW) and molecular weight distribution ...
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For preparation of highly active supported catalyst with bis(imino)pyridyl Fe(II) complexes (Fe1, Fe2) and N,N-α-diimine complex of Ni (Ni3), silica modified with alumina (SiO2 (Al)) was used as a support. Data on the possibility to regulate molecular weight (MW) and molecular weight distribution (MWD) of polyethylene (PE), produced over the supported catalyst Fe1/SiO2 (Al)+TIBA by variation of polymerization temperature and the addition of hydrogen and hexene-1, are obtained. The prepared PE samples were characterized by Mw values varied from 80 to 350 kg/mol and various MMD (Mw/Mn=4.6-11.7).By grafting on SiO2(Al) of two different iron bis(imino)pyridyl complexes, producing PE with diverse MW, bi-component catalyst was prepared. This catalyst generates linear PE with broad and bimodal MWD (Mw/Mn=33). Fixation on SiO2(Al) of α-diimine Ni(II) pre-catalyst (Ni3), yielding high molecular weight branched PE at the ethylene homopolymerization, and bis(imino)pyridyl Fe(II) complex (Fe2) that forms lower molecular weight linear PE, affords formation of a new bi-component catalyst. The catalyst produces PE with broad MWD and high content of branches concentrated in high molecular weight PE fraction.
Catalysis
Zenghui Zhao; Tatiana Mikenas; Vladimir Aleksandrovich Zakharov; Marina Nikolaeva; Mikhail Matsko; Elena Bessudnova; Wei Wu
Abstract
The new highly active supported vanadium-magnesium catalyst (VMC) has been studied in α-olefin (1-butene, 1-hexene)/ ethylene copolymerization in the presence of hydrogen. Data on the effect of α-olefin/ethylene ratio in copolymerization on the content of branchings in copolymers, kinetic ...
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The new highly active supported vanadium-magnesium catalyst (VMC) has been studied in α-olefin (1-butene, 1-hexene)/ ethylene copolymerization in the presence of hydrogen. Data on the effect of α-olefin/ethylene ratio in copolymerization on the content of branchings in copolymers, kinetic profile, copolymer yield, molecular weight and molecular weight distribution of copolymers have been obtained. It was found that both α-olefins are effective chain transfer agents in the ethylene-α-olefins copolymerization. The copolymerization ability of VMC is much higher than that of the well known titanium-magnesium catalysts. It was found that the use of optimal conditions of ethylene/α-olefin polymerization on the VMC catalyst makes it possible to obtain copolymers with a high yield (10-16 kg gcat-1 cat for 2 h) the copolymers having broad and bimodal MWD. Data on the branchings distribution in copolymers prepared with VMC catalyst have been obtained via fractionation of copolymers on the fractions with narrow polydispersity (Mw/Mn ≈ 2). Quite a uniform distribution of branchings over fractions with different molecular weight was found in distinction to inhomogeneous distribution of branchings in copolymers produced over the well known supported titaniu-magnesium catalyst.
Catalysis
Valentina Nikolaevna Panchenko; Ludmila Viktorovna Vorontsova; Vladimir Aleksandrovich Zakharov
Abstract
The interaction of the external donor (propyltrimethoxysilane - PTMS) with titanium-magnesium catalysts (TMCs) containing dibutylphthalate (DBP) as internal donor, which were prepared in different ways, was studied by chemical analysis and infrared diffuse reflectance spectroscopy (DRIFTS). The chemical ...
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The interaction of the external donor (propyltrimethoxysilane - PTMS) with titanium-magnesium catalysts (TMCs) containing dibutylphthalate (DBP) as internal donor, which were prepared in different ways, was studied by chemical analysis and infrared diffuse reflectance spectroscopy (DRIFTS). The chemical composition of the catalysts after their interaction with heptane solutions of PTMS, PTMS/AlEt3 or AlEt3 during 1h at 70°C showed that this interaction led to removal of both TiCl4 and DBP from the catalysts. The fractions of DBP and Ti extracted, as well as the amounts of PTMS and AlEt3 bound, depended on the method of synthesizing the catalysts. DRIFT spectroscopy data concerning the state of DBP in the catalysts, before and after treatment with heptane solutions of PTMS or PTMS/AlEt3 during 1h at 70°C, showed that PTMS could substitute both TiCl4 and DBP, while adsorbing on coordinatively unsaturated Ti and Mg ions in the catalyst. The presence of AlEt3 played a key role in the interaction of PTMS with the catalyst. Activity data for propylene polymerization showed that treatment of TMC catalysts with PTMS before polymerization led to a sharp activity decrease due to deactivation of active sites, while the interaction of the catalyst with PTMS in the presence of AlEt3 led only to a slight decrease of activity, probably due to deactivation of non-stereospecific active centers.
Catalysis
Natalya N. Chumachenko; Vladimir A. Zakharov; Sergey A. Sergeev; Svetlana V. Cherepanova
Abstract
Supported catalysts synthesized via the interaction of Mg(OEt)2 with TiCl4 in the presence or absence of an internal stereoregulating donor (di-n-butyl phthalate), with different solvents (chlorobenzene, n-undecane, n-heptane) at different titanation temperatures have been studied by a set of physicochemical ...
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Supported catalysts synthesized via the interaction of Mg(OEt)2 with TiCl4 in the presence or absence of an internal stereoregulating donor (di-n-butyl phthalate), with different solvents (chlorobenzene, n-undecane, n-heptane) at different titanation temperatures have been studied by a set of physicochemical methods. Data on the chemical composition, X-ray structure and pore structure of these catalysts as well as data on their activity and stereospecificity in polymerization of propylene were obtained. Chemical composition, structure, activity and stereospecificity depend primarily on the presence of an electron donor stereoregulating component and on the solvent nature and titanation temperature. Activity of the catalysts is determined by totality of different characteristics: the chemical composition, in particular, the presence of inactive by-products like TiCl3(OEt), the MgCl2 X-ray structure and pore structure. More active catalyst which was synthesized under optimal conditions in the presence of di-n-butyl phthalate contains the minimal amount of TiCl3(OEt) by-product, and has a more ordered X-ray structure and a homogeneous mesoporous structure with a narrow mesopore size distribution.
Catalysis
Mikhail A. Matsko; Vladimir A. Zakharov; Marina I. Nikolaeva; Tatiana B. Mikenas
Abstract
The data on the effect of ethylene concentration on polymerization rate for several modifications of modern highly active titanium–magnesium catalysts TiCl4/MgCl2 are presented. These catalysts differ in titanium content and conditions of support preparation, activities, and the shape of kinetic ...
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The data on the effect of ethylene concentration on polymerization rate for several modifications of modern highly active titanium–magnesium catalysts TiCl4/MgCl2 are presented. These catalysts differ in titanium content and conditions of support preparation, activities, and the shape of kinetic curves. It is found that the observed order of polymerization rate with respect to ethylene in the range of ethylene pressures of 0.5–6 bar is 1.8-2.1 for all catalysts used (polymerization at 80°C, AlEt3 used as a cocatalyst). When AlEt3 was replaced with Al(i-Bu)3, the reaction order decreased to 1.3-1.4. In order to elucidate the possible reasons for the observed high order with respect to ethylene, we analyzed the data on the effect of monomer concentration on the molecular weight of polyethylene. The results gave grounds for suggesting that the observed order with respect to monomer is attributable to the effect of ethylene concentration on the number of active sites. The possible reaction scheme explaining the nonlinear dependence of the polymerization rate on monomer concentration was proposed based on these data.
