Method of preparing catalyst and ethylene polymerization process utilizing this catalyst

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to a method for preparing supported titanium -manganese catalyst for synthesis of super-high molecular weight polyethylene via suspension ethylene polymerization process in hydrocarbon solvent. Titanium-containing catalyst supported by magnesium-containing carrier is prepared by reaction of organomagnesium compound Mg(C6H5)2•nMgCl2•mR2O, where n=0.37-0.7, m=2, R20 represents ether wherein R is i-amyl or n-butyl, with a silicon compound, namely product obtained by reaction of compound R'kSiCl4-k (R' is methyl or phenyl and k=0-1) with silicon tetraethoxide Si(OEt)4 at molar ratio R'kSiCl4-k/Si(OEt)4 = 6 to 40. Ethylene polymerization process in presence of above-defined catalyst in combination with co-catalyst is also described, wherein obtained super-high molecular weight polyethylene has loose density ≥ 0.39 g/cc.

EFFECT: increased molecular weight and loose density of polyethylene.

4 cl, 1 tbl, 8 ex

 

The invention relates to a method for producing a deposited catalyst containing a compound of titanium to magnesium-containing carrier, and intended for the synthesis of ultra-high molecular weight polyethylene with increased bulk density by the method of suspension polymerization of ethylene in a hydrocarbon solvent.

To obtain ultra-high molecular weight polyethylene (UHMWPE) by suspension polymerization can be used applied catalysts ziperovich type, containing in its composition chlorides titanium chlorides and magnesium obtained in various ways. In this case, the polymerization of ethylene is carried out in the absence of hydrogen at the temperature of polymerization ≤70°for polyethylene with a molecular mass of more than 1·106g/mol (characteristic viscosity, defined in decaline at 135°With more than 10 DL/g). The polymerization is carried out in the presence of socializaton - trialkyl aluminum. An important requirement of the catalyst for the synthesis of UHMWPE, it is possible to obtain the UHMWPE powder with an average particle size less than 200 microns, a narrow distribution of particle size and high bulk density (>0.4 g/cm3). This requires the use of applied catalysts having an average particle size less than 8 microns, a narrow distribution of particle size and n is skuu porosity.

UHMWPE can be synthesized in the presence of a catalyst obtained by the method [JP 59-53511, B01J 31/32, 1986]. This catalyst contains as a carrier of magnesium chloride obtained by the interaction of a solution of the compound MgCl2·3i-C8H17OH, the hydrocarbon diluent with TiCl4in the presence of electron-donor compounds (ethylbenzoic, ationist and others). The catalyst obtained in this way is characterized by a particle size of 5-10 microns, has a sufficiently high activity (up to 35 kg/g PE g Ti h ATM2H4) and allows to obtain a powder of polyethylene with a narrow grain size distribution and high bulk density. The disadvantage of this catalyst is the use of low temperatures (down to -20° (C) when cooking, use as reaction medium large quantities of liquid TiCl4the selection in the synthesis of catalyst a significant amount of hydrogen chloride.

Known inflicted catalyst for polymerization of ethylene, obtained by the interaction of magnesium-aluminum-alkyl compound composition RMgR'·nAlR3"·mD with chloropetalum and the subsequent interaction of the obtained solid product (carrier) with a halide of titanium [DE 3626060, B01J 31/32, 1987]. At the same time as magyarkanizsa connection RMgR' use (n-Bu)Mg(i-Bu) or (n-Bu)Mg(Oct), soluble in hydrocarbons is x, and as chloropetalum preferable to use tret-BuCl. The main disadvantage of the catalysts prepared in this way is sufficiently high activity during the suspension polymerization of ethylene and a large particle size (>10 μm).

A known method of preparation caused titanomagnievoe catalyst containing titanium tetrachloride by magnesium-containing carrier, which is produced by the interaction of the solution magyarkanizsa connection (MOS) structure MgPh2·nMgCl2·mR2O, where: Ph = phenyl, R2O = a simple ether with R = butyl or i-amyl, n=0.37-0.7, m=1-2) with carbon tetrachloride, followed by processing the obtained magnesium-containing carrier with titanium tetrachloride (RF 2064836, B01J 31/38, 10.08.96). This method allows to obtain a catalyst with controlled particle size in the range from 30 to 3 μm. However, to obtain a catalyst with a particle size in the area 7-3 μm required for the production of UHMWPE, the interaction MOS with CCl4be carried out at low temperatures (from -5°-15°C); the process of interaction MOS with CCl4becomes trudnoperevarivaemym, especially when increasing amounts of equipment and quantity of catalyst.

A known method of preparation caused titanomagnievoe catalyst containing tetrachloride ti is Ana on the magnesium-containing carrier, which is produced by the interaction of the solution magyarkanizsa connection (MOS) structure MgPh2·nMgCl2·mR2O, where: Ph = phenyl, R2O = a simple ether with R = butyl or i-amyl, n=0.37-0.7, m=1-2) with Si(OEt)4(RF 2152404, C08F 4/64, 10.07.2000) with subsequent processing of the carrier electron-donor compound and titanium tetrachloride. However, this method allows to obtain catalysts with a particle size of only more than 10 μm.

The closest is the cooking method applied titanomagnievoe catalyst described in the patent of the Russian Federation 2257263, B01J 31/38, 27.07.05, in which the magnesium-containing carrier is produced by interaction of the solution magyarkanizsa connection (MOS) structure MgPh2·nMgCl2·mR2O, where: Ph = phenyl, R2O = a simple ether with R = butyl or i-amyl, n=0.37-0.7, m=1-2, with alkalarian RxSiCl4-xwhere: R = alkyl, phenyl, x=1-2.

The main disadvantage of the catalysts obtained in a known manner, is relatively low bulk density of UHMWPE obtained at polymerization temperatures of 40-70°C.

The invention solves the problem of developing a method of obtaining applied titanomagnievoe catalyst for synthesis by the method of suspension polymerization of ultra-high molecular weight polyethylene UHMWPE with high yield and high bulk density.

The task is solved in that the nose of the tel for applied titanium-magnesium catalyst is produced by interaction of the solution magyarkanizsa compounds consisting of: Mg(C 6H5)2·nMgCl2·mR2O, where n=0.37-0.7, m=2, R2O - simple ether with R=i-Am, n-Bu, with compounds of silicon, as silicon compounds are used, the product obtained by the interaction of the compounds of structure R1kSiCl4-kwith tetraethoxide silicon Si(OEt)4where R1= methyl or phenyl; k=0-1, when the molar ratio R1xSiCl4-x/Si(COt)4=6-40, when the ratio of Si(OEt)4/Mg=0.05-0.3, and R1xSiCl4-xMg=1.6-2.0, at a temperature of 10-30°With the Proposed method for the preparation of the catalyst ensures polyethylene with high yield and with high bulk density in the area of 0.39-0.45 g/cm3.

The polymerization is carried out in the mode of the suspension at a temperature of 40-70°in the medium of a hydrocarbon solvent (e.g. hexane, heptane) pressure ethylene ≥1 bar, in the presence of socializaton - trialkyl aluminum (triisobutylaluminum or triethylaluminum).

The invention is illustrated by the following examples.

Example 1.

(A). Preparation of the solution magyarkanizsa connection.

In a glass reactor of 1 liter equipped with a stirrer and a thermostatic device, download 29.2 g of powdered magnesium (1.2 mol) in 450 ml of chlorobenzene (4.4 mol), 203 ml dibutylamino ether (1.2 mol) and an activating agent, representing the races of the thief 0.05 g of iodine in 3 ml of butyl chloride. The reaction is carried out in an atmosphere of inert gas (nitrogen, argon) at a temperature of from 80 to 100°C for 10 hours By the end of the reaction the reaction mixture defend and separate the liquid phase from the precipitate. The liquid phase is a solution in chlorobenzene magyarkanizsa connection structure MgPh2·0.49MgCl2·2(Bu)2O with a concentration of 1.0 mol Mg/l

(B). Synthesis media.

200 ml of the obtained solution (0.2 mol Mg) is loaded into the reactor with a stirrer and a temperature of 15°C for 2.3 hours metered into the reactor solution mixture PhSiCl3(64 ml) with Si(OEt)4(2.2 ml) at a molar ratio of 40:1, (Si(OEt)4/Mg=0.05, PhSiCl3/Mg=2.0). Then the reaction mixture is heated to 60°C for 30 min and kept at this temperature for 1 h to Remove the mother liquor and the precipitate is washed with heptane 4 times 250 ml at a temperature of 20°C. Obtain 33 g of powdered magnesium-containing carrier in the form of a suspension in heptane.

To the resulting suspension of magnesium-containing medium in 150 ml of heptane add 22 ml of TiCl4(TiCl4/Mg=1), the reaction mixture is heated to 60°C and maintained under stirring for 2 h, then the solid precipitate defend and washed with heptane at a temperature of 60-70°5 times in 200 ml. Receive the applied catalyst with titanium content 1.2 wt.%.

Polymerization of ethylene wire is t in a steel reactor with a volume of 0.8 l, equipped with stirrer and heating jacket. As a solvent for polymerization using heptane (250 ml) and socializaton - triethylaluminium (AlEt3) with a concentration of 1.4 mmol/liter Polymerization is carried out at a temperature of 60°C, pressure of 4 ATM ethylene. within 3 hours the Results of polymerization are shown in table.

Example 2.

The catalyst was prepared in the conditions of example 1, except that a mixture of PhSiCl3with Si(OEt)4when the molar ratio of 18:1, (Si(OEt)4/Mg=0.1, PhSiCl3/Mg=1.8. The catalyst contains 1.2 wt.% titanium. The polymerization of ethylene is carried out in the conditions of example, except that the polymerization temperature of 70°and curing time 3.5 hours the Results of polymerization are shown in table.

Example 3.

The catalyst was prepared in the conditions of example 2, except that the temperature of the mixture interaction PhSiCl3with Si(OEt)4with magnetogenesis connection 10°C. the Catalyst contains 1.6 wt.% titanium. The polymerization of ethylene is carried out in the conditions of example 2, except that the first is used for polymerization for 5 minutes a mixture of ethylene with 5% vol. propylene at a pressure of 1 ATM., and then polymerization is carried out at a pressure of 3 ATM ethylene. 3 including the Results of polymerization are shown in table.

Example 4.

The catalyst was prepared in the conditions of example 1, excluded the eat they use a mixture of PhSiCl3with Si(OEt)4when the molar ratio 6:1, (Si(OEt)4/Mg=0.3, PhSiCl3/Mg=1.8. The catalyst contains 2.1 wt.% titanium. The polymerization of ethylene is carried out in the conditions of example 3 for 4 o'clock the Results of polymerization are shown in table.

Example 5.

The synthesis of the catalyst is carried out analogously to example 2, except that use magyarkanizsa connection structure MgPh2·0.49MgCl2·2(i-Am)2O with a concentration of 0.9 mol Mg/L. Catalyst contains 1.8 wt.% titanium. The polymerization of ethylene is carried out in the conditions of example 3, except that the polymerization temperature 60°C. the Results of polymerization are shown in table.

Example 6.

The synthesis of the catalyst is carried out analogously to example 5, except that instead of PhSiCl3use MeSiCl3and interaction magyarkanizsa connection with a mixture MeSiCl3/Si(OEt)4is carried out at a temperature of 20°C. the Catalyst contains 2.4 wt.% titanium. The polymerization of ethylene is carried out in the conditions of example 3 for 1.2 hours the Results of polymerization are shown in table.

Example 7.

The synthesis of the catalyst is carried out analogously to example 2, except that the interaction magyarkanizsa connection with a mixture PhSiCl3/Si(OEt)4is carried out at a temperature of 30°and use PhSiCl 3with Si(OEt)4when the molar ratio of 16:1, (Si(OEt)4/Mg=0.1, PhSiCl3/Mg=1.6. The catalyst containing 2.0 wt.% titanium. The polymerization of ethylene is carried out in the conditions of example 3 for 3.3 hours the Results of polymerization are shown in table.

Example 8 (comparative).

The catalyst was prepared in accordance with the patent of the Russian Federation No. 2257263 in the conditions of example 5, except that to interact with magnetogenesis connection when receiving media use PhSiCl3when the ratio Si/Mg=1.8. The catalyst contains 1.0 wt.% titanium. The polymerization of ethylene is carried out in the conditions of example 5 for 2 hours the Results of polymerization are shown in table.

From the presented examples and the table shows that the catalyst prepared according to the method proposed in the invention, allows to obtain UHMWPE with high bulk density PE≥0.39 g/cm3compared with the catalyst prepared according to the prototype (PhSiCl3as glorieuses agent without addition of tetraethoxysilane; comparative example 8). In the latter case, obtain a polymer with a lower bulk density (compare experiments 5 and 8, carried out under the same conditions of polymerization).

1. The method of obtaining the deposited catalyst for the synthesis of ultra-high molecular weight polyethylene in the mode of suspension of hydrocarbons in the environment is one solvent, containing compound of titanium to magnesium-containing carrier, which is produced by the interaction of the solution magyarkanizsa compounds consisting of: Mg(C6H5)2·nMgCl2·mR2O, where n=from 0.37 to 0.7, m=2, R2O - simple ether with R=i-Am, n-Bu, with a compound of silicon, characterized in that the silicon compound is used a product obtained by the interaction of the compounds of structure R1kSiCl4-kwith tetraethoxide silicon Si(OEt)4where R1= methyl or phenyl; k=0-1, when the molar ratio R1kSiCl4-x/Si(OEt)4=6-40.

2. The method according to claim 1, characterized in that the interaction magyarkanizsa connection with the silicon compound of the above composition is carried out at a temperature of 10-30°C.

3. The method according to claim 1, characterized in that the ratio of Si(OEt)4/Mg=0.05 to 0.3, and R1xSiCl4-x/Mg=1,6-2,0.

4. The polymerization of ethylene in the mode of suspension in the medium of hydrocarbon solvent in the presence of a catalyst containing a compound of titanium to magnesium-containing carrier, characterized in that the use of the catalyst prepared according to any one of claims 1 to 3 in combination with socialization - trialkyl aluminum.



 

Same patents:

FIELD: polymer production.

SUBSTANCE: invention relates to 1-butene copolymers containing up to 40 mol % ethylene or propylene derivatives. Copolymer of 1-butene with ethylene or propylene is described, which copolymer contains up to 40 mol % of ethylene and/or propylene units derivatives and manifests following properties: (a) product of copolymerization constants r1·r2 ≤ 2; (b) content of 1-butene units in the form of stereoregular pentads (mmmm) > 98%; and (c) lack of 4,1-inclusions of 1-butene units. Described are also: polymer compositions for manufacturing films, which contains above-indicated polymer; industrial product obtained from this copolymer; and a method for preparing such copolymer comprising 1-butene/ethylene (and/or propylene) copolymerization in presence of stereoregular catalyst containing (A) solid catalytic component including Ti compound and electron-donor compound selected from MgCl2-supported phthalates; (B) alkylaluminum compound; and (C) outer electron-donor compound of formula Ra5Rb6Si(OR7)c, wherein a and b are integers from 0 to 2, c is integer from 1 to 3, and sum (a+b+c)= 4, R5, R6, and R7 represent alkyl, cycloalkyl, or aryl radicals with 1-18 carbon atoms, optionally containing heteroatoms.

EFFECT: achieved specific balance between stereoregularity and distribution of comonomer, lack of 4,1-inclusions, and increased stretching strength.

26 cl, 8 tbl, 14 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to butene-1 (co)polymers and a method of their synthesis. Except for, invention relates to articles made of butene-1 (co)polymers. Homopolymers of butene-1 are characterized by the following properties: (i) value of molecular-mass partition expressed as the ratio Mw/Mn based on measurement with using analysis carried out by gel-permeation chromatography method is less 6, and (ii) strength value of melt is above 2.8 g. These homopolymers are used for making tubes. Method for synthesis of butene-1 homopolymers is carried out in the presence of a stereospecific catalyst comprising (A) a solid component containing Ti compound and internal electron-donor compounds chosen from phthalates and applied on a carrier MgCl2; (B) alkylaluminum compound, and (C) tert.-hexyltrimethoxysilane as an external electron-donor compound. Butene-1 homopolymers possess a set of mechanical properties providing the presence both barostability after prolonged period time and their easy processing for making tubes.

EFFECT: valuable properties of (co)polymers, improved method of synthesis.

12 cl, 1 tbl, 3 ex

FIELD: polymerization catalyst and polymer production.

SUBSTANCE: invention relates to preparation of high-activity catalyst deposited on solid support and designed for suspension polymerization of ethylene and copolymerization of ethylene with α-olefins, in particular, for production of ultrahigh-molecular weight polyethylene. Catalyst according to invention comprises organoaluminum compound (40-200 wt parts) and solid component (1 wt part) containing 12-15% catalytically active titanium compounds and 85-88% magnesium dichloride support prepared by interaction of magnesium metal, ethanol, aluminum, silicon, and titanium compounds, said solid component being represented by particles containing titanium, magnesium, chlorine, aluminum, and silicon at atomic ratio between 1.0:6:16:0.07:0,02 and 1:7:18:0.06:0.01, respectively. Described are also preparation of solid catalyst component, and (co)polymerization of ethylene at temperature between 0 and 100°C and pressure between 0.1 and 5.0 MPa. Catalyst according to invention allows obtaining polyethylene with elevated molecular weight under high polymer yield conditions, which minimizes time required for preparation of homogenous spinning solutions in the gel formation process and minimizes degree of degradation of dissolved polymer properties.

EFFECT: increased molecular weight and yield of polyethylene .

8 cl, 1 dwg, 3 tbl, 26 ex

FIELD: polymerization processes and catalysts.

SUBSTANCE: invention relates to preparing supported titanium-magnesium catalyst for production of polyethylene and superhigh-molecular weight polyethylene via suspension polymerization of ethylene in hydrocarbon solvent. Invention provides a method for preparing supported ethylene polymerization catalyst containing titanium compound on magnesium-containing support, which is prepared by interaction of dissolved organomagnesium compound having following composition: MgPh2·nMgCl2·mR2O, wherein R represents butyl or isoamyl, n=0.37-0.7, and m=1-2, with compounds inducing conversion of organomagnesium compound into solid magnesium-containing support. As such compounds, there is used a composition including product of reaction of alkylsilane R'kSi4-k, wherein R is alkyl or phenyl and k=1, 2, with silicon tetraalkoxide Si(OEt)4 at molar ratio 2-4, respectively, and a dialkylaromatic ether. Catalyst is characterized by high activity at temperatures ≤60°C and particle size within a range 5.5 to 3.0 μm. Catalyst allows a polymer powder with average particle size ≤150 μm, narrow particle size distribution, and high loose density (≥250 g/L) to be obtained.

EFFECT: enhanced low-temperature catalyst activity and selectivity.

3 cl, 1 tbl, 15 ex

FIELD: polymer production.

SUBSTANCE: superhigh-molecular weight polyethylene is obtained in suspension conditions at temperature between 40 and less than 70°C in hydrocarbon solvent medium using supported catalyst. The latter is prepared through interaction of compound Mg(C6H5)2n*MgCl2*mR2O (R2O is ether, R = i-Am, n-Bu) with silicon compound, which is a product prepared by reaction of compound R1kSiCl4-k with silicon tetraethoxide Si(OR)4 (R1 represents methyl or phenyl and k=0.1) at molar ratio R1kSiCl4-k/Si(OR)4 = 2-4 at 15-45°C and Si/Mg = 1-2.5. Loose weight of obtained polymer is higher than 0.35 g/cc.

EFFECT: increased yield of superhigh-molecular weight polyethylene with improved morphology.

1 tbl, 13 ex

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to catalytic systems used in polymerization of alpha-olefins, methods for preparing catalytic systems for polymerization of alpha-olefins and methods for polymerization (and copolymerization) of alpha-olefins. Invention describes the catalytic system for polymerization of olefins comprising solid titanium component of catalyst, organoaluminum compound comprising at least one bond aluminum-carbon and organosilicon compound comprising at least one (cycloalkyl)-methyl group used as an external donor of electrons. Also, invention describes the catalytic system for polymerization of olefins comprising solid titanium component of the catalyst prepared by contacting titanium compound with magnesium compound and comprising from about 0.01 to about 500 moles of titanium compound per one mole of magnesium compound, organoaluminum compound comprising at least one bond aluminum-carbon wherein the mole ratio of aluminum to titanium in the catalytic system is in the range from about 5 to about 1000, and organosilicon compound comprising at least one (cycloalkyl)-methyl group and used a external donor of electrons wherein the mole ratio of organoaluminum compound and organosilicon compound in the catalytic system is in the range from about 2 to about 90. Also, invention describes methods for preparing catalyst used in polymerization of olefins and comprising interaction of Grignard reactive comprising (cycloalkyl)-methyl group with ortho-silicate to form organosilicon compound comprising a (cycloalkyl)-methyl link, mixing organosilicon compound with organoaluminum compound comprising at least one bond aluminum-carbon and solid titanium component of the catalyst to form the catalyst, and a method for polymerization of olefins. Invention provides preparing propylene block-copolymer showing good fluidity in the melt, capacity for molding, hardness, impact viscosity and impact strength in combination with high effectiveness of the catalyst and good technological effectiveness of the preparing process.

EFFECT: improved and valuable properties of catalysts.

17 cl, 10 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention, in particular, relates to preparation of Ziegler-type catalyst comprising transition metal (titanium or vanadium) compound on magnesium-containing carrier. Carrier is prepared via interaction of organomagnesium compound-containing solution depicted by formula Mg(C6H5)2·nMgCl2·mR2O, wherein n=0.37-0.7, m=2, and R2O is ether with R = i-Am or n-Bu, with chlorination agent, namely XkSiCl4-k, wherein X is OR' or R', in which R can be C1-C4-alkyl or phenyl, and k=1-2. Above named polymerization and copolymerization process are carried out with catalyst of invention in combination with cocatalyst.

EFFECT: reduced size distribution range of polymers and enabled average particle size control.

3 cl, 1 tbl, 13 ex

The invention relates to methods for macromolecular higher poly-alpha-olefins and catalysts for carrying out the method

The invention relates to a method for producing a catalyst for polymerization of olefins and method of polymerization of olefin monomers with its use

FIELD: polymerization catalyst and polymer production.

SUBSTANCE: invention relates to preparation of high-activity catalyst deposited on solid support and designed for suspension polymerization of ethylene and copolymerization of ethylene with α-olefins, in particular, for production of ultrahigh-molecular weight polyethylene. Catalyst according to invention comprises organoaluminum compound (40-200 wt parts) and solid component (1 wt part) containing 12-15% catalytically active titanium compounds and 85-88% magnesium dichloride support prepared by interaction of magnesium metal, ethanol, aluminum, silicon, and titanium compounds, said solid component being represented by particles containing titanium, magnesium, chlorine, aluminum, and silicon at atomic ratio between 1.0:6:16:0.07:0,02 and 1:7:18:0.06:0.01, respectively. Described are also preparation of solid catalyst component, and (co)polymerization of ethylene at temperature between 0 and 100°C and pressure between 0.1 and 5.0 MPa. Catalyst according to invention allows obtaining polyethylene with elevated molecular weight under high polymer yield conditions, which minimizes time required for preparation of homogenous spinning solutions in the gel formation process and minimizes degree of degradation of dissolved polymer properties.

EFFECT: increased molecular weight and yield of polyethylene .

8 cl, 1 dwg, 3 tbl, 26 ex

FIELD: organic chemistry, polymers, in particular method for olefin polymerization.

SUBSTANCE: invention relates to method for CH2=CHR olefin polymerization wherein R represents hydrogen or C1-C12-hydrocarbon group to produce polymer with increased bulk density; catalytic component and catalyst useful in said method. Catalytic component contains at least two fraction (A) and (B), wherein both contain Mg, Ti and halogen as essential elements. Said catalytic component contains 1-60 mass % of (B) fraction whish has less mean diameter than (A) component by 75 % or less. Catalyst of olefin polymerization is obtained by interaction of abovementioned catalytic component organometal compounds of metals from 1-3 groups of Periodical system, optionally in presence of electron-attractive compound. Method for olefin polymerization is carried out in presence of catalytic component (A), containing Mg, Ti and halogen as essential elements and catalytic component (B), also containing Mg, Ti and halogen as essential elements which makes it possible to produce polymer with less mean particle size than mean particle size of polymer obtained with catalytic component (A) at the same polymerization conditions.

EFFECT: method of high productivity; polymer of high bulk density.

25 cl, 6 ex, 1 tbl

FIELD: polymerization processes and catalysts.

SUBSTANCE: invention relates to preparing supported titanium-magnesium catalyst for production of polyethylene and superhigh-molecular weight polyethylene via suspension polymerization of ethylene in hydrocarbon solvent. Invention provides a method for preparing supported ethylene polymerization catalyst containing titanium compound on magnesium-containing support, which is prepared by interaction of dissolved organomagnesium compound having following composition: MgPh2·nMgCl2·mR2O, wherein R represents butyl or isoamyl, n=0.37-0.7, and m=1-2, with compounds inducing conversion of organomagnesium compound into solid magnesium-containing support. As such compounds, there is used a composition including product of reaction of alkylsilane R'kSi4-k, wherein R is alkyl or phenyl and k=1, 2, with silicon tetraalkoxide Si(OEt)4 at molar ratio 2-4, respectively, and a dialkylaromatic ether. Catalyst is characterized by high activity at temperatures ≤60°C and particle size within a range 5.5 to 3.0 μm. Catalyst allows a polymer powder with average particle size ≤150 μm, narrow particle size distribution, and high loose density (≥250 g/L) to be obtained.

EFFECT: enhanced low-temperature catalyst activity and selectivity.

3 cl, 1 tbl, 15 ex

FIELD: polymer production.

SUBSTANCE: superhigh-molecular weight polyethylene is obtained in suspension conditions at temperature between 40 and less than 70°C in hydrocarbon solvent medium using supported catalyst. The latter is prepared through interaction of compound Mg(C6H5)2n*MgCl2*mR2O (R2O is ether, R = i-Am, n-Bu) with silicon compound, which is a product prepared by reaction of compound R1kSiCl4-k with silicon tetraethoxide Si(OR)4 (R1 represents methyl or phenyl and k=0.1) at molar ratio R1kSiCl4-k/Si(OR)4 = 2-4 at 15-45°C and Si/Mg = 1-2.5. Loose weight of obtained polymer is higher than 0.35 g/cc.

EFFECT: increased yield of superhigh-molecular weight polyethylene with improved morphology.

1 tbl, 13 ex

FIELD: polymerization catalysts.

SUBSTANCE: catalytic component according to invention contains magnesium, titanium, halogen, and electron donor, wherein the latter contains at least one compound, notably polyol ester I having general formula R1CO-O-CR3R4-A-CR5R6-O-CO-R2 (I), wherein groups R1 and R2, the same or different, represent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; groups R3-R5, the same or different, are selected from group consisting of hydrogen, halogen, and above-defined hydrocarbon residue, said groups R3-R6 optionally containing one or several heteroatoms substituting carbon and/or hydrogen atom, wherein said heteroatoms are selected from group consisting of oxygen and halogen atoms, or two or more groups R3-R6 being connected with each other to form saturated or unsaturated monocyclic ring; and A represents bivalent linking group between two hydrocarbon radicals having from 1 to 10 atoms, said linking group being selected from group consisting of aliphatic, alicyclic, and aromatic bivalent radicals and can bear linear or branched C1-C20-substituents, provided that two or more substituents of said linking group and above-defined R3-R6 groups can be interconnected to form saturated or unsaturated monocyclic ring. Invention further discloses catalyst containing above-defined solid catalytic component and its employment in polymerization of CH2=CHR hydrocarbons, wherein R represents hydrogen or C1-C6-alkyl group.

EFFECT: enabled preparation of polymers characterized by high stereoregularity and increased polymerization yield.

34 cl, 6 tbl, 110 ex

FIELD: polymer production.

SUBSTANCE: invention relates to magnesium halide-based compositions, processes for preparation thereof and catalysts as well as to polymerization processes. Invention provides a component of magnesium halide-based olefin polymerization catalyst prepared from magnesium halide, solvent appropriate as electron donor, and electron-donor compound represented by linear or branched, substituted or unsubstituted aliphatic or aromatic alcohol having 1 to 25 carbon atoms, wherein magnesium halide is characterized by solubility in the solvent exceeds 0.7 mole/L and does fall under effect of increase in temperature up to boiling temperature. Catalyst precursor includes reaction product of the above-defined catalyst component and a second component including transition metal selected from group consisting of titanium, zirconium, hafnium, vanadium, and a combination thereof. Olefin polymerization catalyst disclosed includes reaction product of catalyst precursor with co-catalyst, namely alkylaluminum compound.

EFFECT: increased contend of magnesium in catalyst, increased solubility of catalyst, and reduced expenses on catalyst preparation in case of small amount of charge.

14 cl, 4 dg, 1 tbl

FIELD: polymer production.

SUBSTANCE: invention relates to supported catalytic compositions, methods for preparing such compositions, and polymer preparation processes using these compositions. In particular, invention provides supported catalytic composition including interaction product of: (i) catalyst precursor composition comprising product of reaction of magnesium halide, an ether, electronodonor compound, in particular linear or branched aliphatic C1-C25-alcohol, and transition metal compound, in particular compound of group IV element; (ii) porous inert carrier; and (iii) cocatalytic composition; wherein supported catalytic composition contains less than 1% electronodonor compounds other than those including linear or branched aliphatic or aromatic alcohol having from 1 to 25 carbon atoms and wherein molar ratio of electronodonor compound to magnesium is less than or equal to 1.9. Described are also method of preparing supported catalytic composition, method of preparing polymer comprising reaction of at least one olefin monomer in presence of above-mentioned supported catalytic composition. Described are also supported catalyst precursor composition, supported catalytic composition, method of preparing supported catalytic composition, and method of preparing polymer comprising reaction of at least one olefin monomer in presence of supported catalytic composition, and supported catalyst precursor composition.

EFFECT: increased catalytic activity and enabled preparation of polymer for films at lower partial pressure of ethylene.

15 cl, 5 dwg, 3 tbl, 7 ex

FIELD: chemical industry; petrochemical industry; methods of production of the composition of the solid procatalytic agent for utilization in the catalytic compositions for polymerization.

SUBSTANCE: the invention is pertaining to the method of production of: the composition of the solid procatalytic agent for usage in the Ziegler-Natta type catalytic composition for polymerization; to the procatalytic agents for usage in the formation of the similar catalytic compositions; to the methods of their production and to the methods of their application for production of the olefinic polymer. The invention presents the method of production of the composition of the solid procatalytic agent for usage in the composition of the Ziegler-Natta procatalytic agent for polymerization of the olefins providing for: contacting the predecessor composition containing the magnesium compound with the compound being the titanium halogenide and the internal donor of electrons; separation of the solid procatalytic agent from the reactionary medium; the extraction of the composition of the solid procatalytic agent by its contacting one or several times with the liquid dilutant. The invention also presents the method (a version)providing for the phase of the solid procatalytic agent drying before the extraction of the composition. The invention also presents the description of the composition of the solid procatalytic agent for the usage in the Ziegler-Natta type catalytic composition for polymerization of olefins. The technical result of the invention is production of the catalytic compositions used in the production of the polymeric compounds of α-olefins, having the reduced contents of the xylene-soluble fractions and the heightened rigidity. The catalytic agents have the higher productivity and produce the polymers of α-olefins having the higher volumetric possibility to use the reduced levels of hydrogen for achievement of the equivalent molecular mass of the polymer, need the reduced quantities of the agents of regulation of selectivity and produce the polymers having the reduced contents of oligomers.

EFFECT: the invention ensures production of the catalytic compositions for production of the polymeric compounds of α-olefins with the reduced share of the xylene-soluble fractions, heightened rigidity, higher productivity, producing the polymers of α-olefins with the reduced share of oligomers.

9 cl, 11 tbl, 90 ex

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to catalytic systems used in polymerization of alpha-olefins, methods for preparing catalytic systems for polymerization of alpha-olefins and methods for polymerization (and copolymerization) of alpha-olefins. Invention describes the catalytic system for polymerization of olefins comprising solid titanium component of catalyst, organoaluminum compound comprising at least one bond aluminum-carbon and organosilicon compound comprising at least one (cycloalkyl)-methyl group used as an external donor of electrons. Also, invention describes the catalytic system for polymerization of olefins comprising solid titanium component of the catalyst prepared by contacting titanium compound with magnesium compound and comprising from about 0.01 to about 500 moles of titanium compound per one mole of magnesium compound, organoaluminum compound comprising at least one bond aluminum-carbon wherein the mole ratio of aluminum to titanium in the catalytic system is in the range from about 5 to about 1000, and organosilicon compound comprising at least one (cycloalkyl)-methyl group and used a external donor of electrons wherein the mole ratio of organoaluminum compound and organosilicon compound in the catalytic system is in the range from about 2 to about 90. Also, invention describes methods for preparing catalyst used in polymerization of olefins and comprising interaction of Grignard reactive comprising (cycloalkyl)-methyl group with ortho-silicate to form organosilicon compound comprising a (cycloalkyl)-methyl link, mixing organosilicon compound with organoaluminum compound comprising at least one bond aluminum-carbon and solid titanium component of the catalyst to form the catalyst, and a method for polymerization of olefins. Invention provides preparing propylene block-copolymer showing good fluidity in the melt, capacity for molding, hardness, impact viscosity and impact strength in combination with high effectiveness of the catalyst and good technological effectiveness of the preparing process.

EFFECT: improved and valuable properties of catalysts.

17 cl, 10 ex

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to the catalyst component used in polymerization of olefins comprising Mg, Ti, halogen and at least two electron-donor compounds wherein indicated catalyst component and at least one of electron-donor compounds repenting in the amount in the range from 20 to 50 mole% with respect to the complete amount of donors are chosen from succinic acid esters that are not extractable by above 25 mole% and at least one additional electron-donor compound that is extractable by above 35 mole%. Indicated components of catalyst provides preparing polymers possessing good insolubility level in xylene, high content level of stereoblocks and broad MWD value that is suitable for preparing polymers used in the region using bi-oriented polypropylene films. Also, invention relates to catalyst used in polymerization of olefins, methods for preparing propylene polymers and propylene polymer.

EFFECT: improved preparing method, valuable properties of catalyst.

24 cl, 3 tbl, 17 ex

FIELD: polymer production.

SUBSTANCE: invention relates to 1-butene copolymers containing up to 40 mol % ethylene or propylene derivatives. Copolymer of 1-butene with ethylene or propylene is described, which copolymer contains up to 40 mol % of ethylene and/or propylene units derivatives and manifests following properties: (a) product of copolymerization constants r1·r2 ≤ 2; (b) content of 1-butene units in the form of stereoregular pentads (mmmm) > 98%; and (c) lack of 4,1-inclusions of 1-butene units. Described are also: polymer compositions for manufacturing films, which contains above-indicated polymer; industrial product obtained from this copolymer; and a method for preparing such copolymer comprising 1-butene/ethylene (and/or propylene) copolymerization in presence of stereoregular catalyst containing (A) solid catalytic component including Ti compound and electron-donor compound selected from MgCl2-supported phthalates; (B) alkylaluminum compound; and (C) outer electron-donor compound of formula Ra5Rb6Si(OR7)c, wherein a and b are integers from 0 to 2, c is integer from 1 to 3, and sum (a+b+c)= 4, R5, R6, and R7 represent alkyl, cycloalkyl, or aryl radicals with 1-18 carbon atoms, optionally containing heteroatoms.

EFFECT: achieved specific balance between stereoregularity and distribution of comonomer, lack of 4,1-inclusions, and increased stretching strength.

26 cl, 8 tbl, 14 ex

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