A method of obtaining a solid component of catalyst for the (co) polymerization of ethylene, a solid component of catalyst for the (co) polymerization of ethylene, the catalyst for the (co)polymerization of ethylene and method for producing (co)polymers of ethylene

C08F4/652 -

 

(57) Abstract:

Use: in the production of polyethylene and copolymers of ethylene. Essence: (co)polymers of ethylene produced by polymerization of ethylene or copolymerization with alpha-olefins in suspension in the presence of a catalyst comprising 60-128 mol. including trialkylamine 1, mol.h. trialkylamine and 1 mol.h. the solid component. A solid component obtained by spraying an ethanol solution of magnesium chloride, the interaction of magnesium chloride Tetra - C1-C8-alcoholate of ti and C1-C20-alkylamidoamines, followed by separation of the solid product. Magnesium chloride has a 22 wt.% hydroxyl groups in the calculation of the ethanol, the particle size of 3 to 100 microns with an average size of 15 μm, an apparent density of 0.3 g/mm, a specific surface area of 17 m2/g and a total porosity of about 75. %. It is suspended in a liquid hydrocarbon solvent and injected into a suspension of C1-C5-aliphatic alcohol and Tetra-C1-C8the titanium alcoholate at a molar ratio alcohol : magnesium chloride and 1.5 : 1, the chloride of magnesium alcoholate is 1 : 1. Then heat the suspension to 80-120oC, the resulting homogeneous solution is cooled, and receive the particles in suspension, enter C1-C20oxolinic groups to 0.75 : 1. The resulting suspension is heated. 4 S. p. f-crystals.

The invention relates to the field of polymers and relates to a method of obtaining a solid component of catalyst for the (co)polymerization of ethylene, the solid component of catalyst, catalyst for (co)polymerization of ethylene and method of (co)polymerization of ethylene.

A method of obtaining a solid component of catalyst for the (co)polymerization of ethylene by the interaction of magnesium chloride obtained by spraying an ethanol solution of magnesium chloride with tetraalkylam titanium and alkylamidoamines, followed by separation of the solid product.

Also known solid component obtained in this way, the catalyst containing, and (co)polymerization of ethylene (U.S. patent N 4843049, class C 08 F 4/64, publ. 1989).

In accordance with this invention it has been found that a catalyst having a composition similar to the catalyst described in U.S. patent N 4843049, and received with use of special techniques that can provide unexpectedly superior value, performance and output in the polymerization of ethylene.

In accordance with this object of the invention is a method of obtaining a solid component of catalysis the creators of magnesium chloride, with Tetra-(C1-C8)-alcoholate of titanium, and (C1-C20-alkylamidoamines, followed by separation of the solid product, characterized in that the use of magnesium chloride with a content of hydroxyl groups 22 wt. in the calculation of the ethanol, and particles of magnesium chloride with a size of 3 to 100 microns with an average size of 15 μm have an apparent density of 0.3 g/ml, specific surface area of 17 m2and the total porosity of about 75. the specified magnesium chloride are suspended in a liquid hydrocarbon solvent and injected into a suspension (C1-C5)- aliphatic alcohol and Tetra-(C1-C8-titanium alcoholate at a molar ratio (C1-C5)-aliphatic alcohol

magnesium chloride, which is about 1.5 to 1, and a molar ratio of magnesium chloride, Tetra-(C1-C8-titanium alcoholate of 1 1, the suspension is then heated to 80-120oC with the formation of a homogeneous solution, which is cooled to obtain granulated particles in suspension, and then is introduced into this suspension (C1-C20-alkylalkoxysilane when the ratio of the number of chlorine atoms in (C1-C20)-alkylhalogenide: the total number of CNS groups 0,75 1, and finally the resulting suspension heated to 60oC.

would be a product of the interaction of magnesium chloride, obtained by spraying an ethanol solution of magnesium chloride, Tetra-(C1-C8)-alcoholate of titanium, and (C1-C20-alkylamidoamines, followed by separation of the solid product. According to the invention it differs in that it is a product obtained by the sequential implementation of the suspension of magnesium chloride in a liquid hydrocarbon solvent, is introduced into the suspension (C1-C5)-aliphatic alcohol and Tetra-(C1-C8)-titanium alcoholate at a molar ratio (C1-C5)-aliphatic alcohol, magnesium chloride, which is about 1.5 to 1, and a molar ratio of magnesium chloride, Tetra-(C1-C8-titanium alcoholate of 1 1, heating the suspension up to 80-120oC with the formation of a homogeneous solution, cooling the solution to obtain granulated particles in suspension in the slurry (C1-C20)-alkylhalogenide when the ratio of the number of chlorine atoms in (C1-C20-alkylamidoamines the total number of CNS groups, equal to 0.7: 1, and heating the resulting suspension to 60oC, when using magnesium chloride content of hydroxyl groups of 22 wt. in the calculation of the ethanol in the form of particles with a size of 3-100, mccu about 75.

In addition, the object of the invention is a catalyst for the (co)polymerization of ethylene, comprising trialkylaluminium and a solid component, which is a product of the interaction of magnesium chloride obtained by spraying an ethanol solution of magnesium chloride, Tetra-(C1-C8)-alcoholate of titanium, and (C1-C20-alkylamidoamines, followed by separation of the solid product, wherein the solid component contains a product obtained by the sequential implementation of the above operations using the above substances, the following ratio of the catalyst components (mol. part):

Trialkylaluminium 60-128

A solid component in terms of titanium 1

And, finally, the object of the invention is a method for (co)polymers of ethylene by polymerization of ethylene or copolymerization with alpha-olefins in suspension in the presence of the above catalyst.

In the preparation of the solid component of catalyst according to the invention, the source media from the magnesium chloride can be obtained by known methods by dissolving anhydrous or substantially anhydrous magnesium chloride in ethanol and drying to spray drying, the solution is sprayed through nozzles or similar devices, and liquid particles formed thereby is brought into contact with a flow of inert gas fed countercurrent or cocurrent flows into the evaporation chamber. Typically, the temperature of the gas stream at the inlet is 250-400oC, the temperature of the gas stream at the outlet 140-250oC, and the difference between the temperatures of the incoming and outgoing flow is at least 40oC. Conducting the process under these conditions, can be removed from the dryer, the solid is in the form of particles, described above, and the content of the alcoholic-OH groups in the solid substance is from 18 to 25 wt. (refer to the weight percent of ethanol).

In accordance with the method of the present invention the carrier is suspended in a liquid hydrocarbon solvent, such as liquid aliphatic hydrocarbon such as hexane, pentane, decane and dodecane, and in this way the resulting suspension add tetralogy titanium, which can be selected from Tetra-n-propylate titanium, Tetra-n-butyl titanium, Tetra-isopropylate titanium and tetracene, and Tetra-isobutylene titanium. The preferred compound is Tetra-n-butyl titanium. To this suspension also adds an aliphatic alcohol, such as methanol, ethanol, propanol, isoprop is nnow thus, the suspension is heated at temperatures of 80-100oC as long, until it forms a homogeneous solution, then this solution is cooled, preferably gradually, to room temperature (20-25oC) or to a temperature close to the room, in order to cause formation of a solid precipitate. This sediment in the normal state is in the form of granules, the size of which varies from 10 to 100 μm (average size of 30 to 45 μm), the apparent density of these granules is from 0.45 to 0.5 g/ml, specific surface area of 7-10 m2/g, a porosity of about 55-70. the content of the alcoholic-OH groups 60-65 wt.

It was found that in the liquid phase of the suspension alcohol is practically absent, the concentration is of the order of several parts per million.

Aluminium chloride, usually selected from monochloride diethylaluminum add to the suspension, and incubated the mixture at temperature for 30-120 minutes.

In a preferred embodiment, the aluminum chloride may dilute the hydrocarbon solvent is added to the suspension, maintaining it at a temperature of 30-35oC, after which the resulting suspension is heated at 60oC for 1 hour.

In conclusion, a solid component of catalyst separated from the reaction products, for example, filtration catalyst, obtained by the method of the present invention is a spherical solid granules, the size of which is usually from 1 to 30 μm (average size of 7-15 μm) having a specific surface area of 10-20 m2/g, a porosity of about 65-85. apparent density of 0.4-0.4 g/ml and the following composition, expressed in atomic ratios:

Ti1Mg0,3-3,1Al0,4-0,65Cl3,2-8,2/Et+OEt+OR1/1,9-3,

where R1represents a linear or branched alkyl containing 1-5 carbon atoms, preferably n-butyl.

In addition, the titanium present in the solid component of catalyst is partially in the trivalent form and partially in tetravalent form when the ratio of trivalent titanium full titanium from 0.6:1 to 1:1.

This solid catalyst component has a chemical composition similar to the composition of the component is described in U.S. patent N 4843049 above, while it differs values of particle size and specific surface area, which is usually lower. When it is used for polymerization of ethylene under conditions similar to the conditions of U.S. patent N 4843049, a component of the catalyst of this invention exhibits markedly improved activity, with proizvoditelite for polymerization of ethylene and copolymerization of ethylene with a-olefins, containing from 3 to 8 carbon atoms, such as propylene and butene-1. The polymerization is usually carried out in suspension at a temperature of from 75 to 95oC in the presence of hydrogen, is used as a regulator, with a total pressure of from 5 to 15 ATM and the ratio between the pressure of the ethylene and the hydrogen pressure from 1 to 6. The catalyst of this invention is particularly useful in the polymerization of ethylene in the ethylene polymers having a narrow molecular weight distribution suitable for the process of injection molding. In particular, can be obtained polyethylene having the required values of melt index and sensitivity to shear, as well as the necessary relationship between srednevekovym molecular weight and srednekislovsky molecular weight.

Example 1. Preparation of solid catalyst component

(1) Ethanol solution of magnesium chloride spray dried to obtain a solid carrier for the catalyst in the form of spherical particles having a size of from 3 to 100 μm (average size of 15 μm), an apparent density of 0.30 g/ml, specific surface area of 17 m2/g, a porosity of about 75. and content of the alcoholic-OH groups 22 wt. refers to ethanol, of 2.45 g of this carrier is suspended in 50 ml of anhydrous n-decanta.

Calculation of the ratio of reagents

of 2.45 g of magnesium chloride with ethanol content of 22 wt. react with 2.8 g of n-butanol and 7 g of tetrabutyl titanium.

of 2.45 g of magnesium chloride with a content of 22% ethanol 1,911 g of pure magnesium chloride 20 mmol.

of 2.8 ml of n-butanol (density 0,80978) of 2.267 g 30 mmol.

7 g of tetrabutyl titanium 20 mmol.

Therefore: the molar ratio of n-butanol/magnesium chloride 1,5; the molar ratio of magnesium chloride/tetrabutyl titanium 1.

(2) the Suspension is heated in vacuum at 100oC for 60 minutes. Get a clear solution which is cooled to room temperature (20-25oC) with the deposition swollen solids in the form of spherical particles having a size from 10 to 100 μm (average size of 35 μm), the apparent density of 0.5 g/ml, specific surface area of 8 m2/g, a porosity of about 65. and content of the alcoholic-OH groups 60 wt. (expressed in butanol).

(3) To the mixed solution, which support the 35oC, is added dropwise 11 g diethylacetanilide dissolved in 50 ml of n-decane (the ratio between the chlorine atoms in diethylacetanilide and the total number of CNS groups (OEt + OBu) is 0.75.1). At the end gobaille of porous glass. Thus obtained 8 g of the solid component of catalyst, washed three times in 100 ml of n-decane.

Thus obtained catalyst component has the following characteristics: the content of the titanium 11 Mac. the ratio between the titanium in the trivalent state and all titanium /trivalent + tetravalent titanium/ is 0,80 1; magnesium content of 7.9 wt. the aluminium content of 2.1 wt. the chlorine content of 36.3 wt. the content of the organic fraction of 42.7 wt. the organic fraction consists mainly of ethyl groups (Et), taksigrup (OEt) and n-butoxypropyl (OBu).

In accordance with the atomic content of components, component of the catalyst can be expressed by the following formula:

Ti1Mg1,4Alfor 0.3Cl4,4(Et+OEt+OBu)2,30,

where OEt is 3.7 wt. and OBu 30,8 wt. the total weight.

Polymerization of ethylene

In a reactor with a stirrer capacity of 5 l load consistently 1820 ml of anhydrous n-heptane, 0.35 g of triethylamine and 16 mg of solid component of catalyst obtained by the method described above.

16 mg of solid catalyst component (a titanium content of 11 wt.) 1,76 mg titanium 0,0367 mmol.

0.35 g triethylaluminum 3,070 mmol.


output: 400 kg of polyethylene per gram of titanium in the solid catalyst component.

The polyethylene obtained in this way is a free-flowing granules with a mean diameter of 250 microns, the content of fine particles (<74 μm) of 2.3% and an apparent density of 0.41 g/ml, and has the following characteristics: melt index (ASTM d 1238) of 7 g/10 min; sensitivity to shear (ASTM d 1238) - 27; Mw/Mn(the ratio between srednevekovym molecular weight and srednekislovsky molecular weight) -3,85; density (ASTM d 2839) 0,9615 g/ml.

Example 2. Preparation of solid catalyst component

In the reactor with stirrer capacity of 250 ml of suspended of 2.45 g of the carrier described in paragraph (1) of example 1, in 50 ml of anhydrous n-decane. To this suspension is added to 2.8 ml of n-butanol and 7 g of Tetra-n-butyl who eat cooled to room temperature (20-25oC) with the deposition swollen solids in the form of spherical particles having a size of from 20 to 100 μm (average size of 45 μm), an apparent density of 0.45 g/ml, specific surface area of 7 m2/g, a porosity of about 63. and content of the alcoholic hydroxyl groups of 55 wt. (applies to butanol).

To mix the solution, the temperature of which is supported by the 35oC, is added dropwise 6.8 g of ethylaminoethanol, rastvorennogo in 50 ml of n-decane (the ratio between the chlorine atoms in ethylaminoethanol and the total number of CNS groups (OEt + OBu) 0.75 1). Upon completion of the addition, the suspension is heated at 60oC for 1 hour.

The solid is filtered off on a sintered glass filter. Thus obtain 7.5 g of the solid component of catalyst, which is three times washed with 100 ml of n-decane.

Thus obtained solid catalyst component has the following characteristics: the titanium content of 12.8 wt. the ratio between the titanium in the trivalent state and all-titanium (trivalent + tetravalent titanium) is 0.70 1; magnesium content of 8.0 wt. the aluminium content of 2.1 wt. the chlorine content of 36.7 wt. the content t of the catalyst can be expressed by the following formula:

Ti1Mg1,28Al0,28Cl3,9(Et+ONt+OBu)2,50,

where OEt represents 4.7 wt. and OBu to 28.3 wt. the total weight.

Polymerization of ethylene

Polymerization of ethylene was conducted by the same method as in example 1, using triethylamine and 14 mg of solid catalyst component, the receipt of which is given above.

14 mg of solid catalyst component (a titanium content of 8.2 wt.) 1,148 mg titanium 0,0239 mmol.

0.35 g of triethylaluminum 3,070 mmol.

The molar ratio of Al/Ti 128.

Get 770 g of polyethylene, the performance range is 55, and the output 428 (the definition of these values indicated in example 1).

The polyethylene obtained in this way is a free-flowing granules with a mean diameter of 240 μm, the content of fine particles (<74 μm) of 3.3% with an apparent density of 0.40 g/ml, and has the following characteristics: melt index (A STM D 1238) of 5.2 g/10 min; sensitivity to shear (ASTM d 1238) 27,4; Mw/Mn(the ratio between srednevekovym molecular weight and srednekislovsky molecular weight) of 3.95; density (ASTM D-2839) - 0,9625 g/ml.

Example 3. Preparation of solid catalyst component

In a reactor with a stirrer with a capacity of 500 l load of th is Ana. To a stirred suspension supported at room temperature, add 19,2 kg of anhydrous n-butanol and the suspension is heated at 120oC for 2 hours and then cooled to room temperature. This precipitates the swollen solid substance in the form of spherical particles having a size from 10 to 100 μm (average size of 30 μm), an apparent density of 0.48 g/ml, specific surface area of 10 m2/g, a porosity of about 68. and content of the alcoholic-OH groups 60,4 wt. 58% of them are butanol, and 2.4% for ethanol.

To a suspension supported when the temperature of the 35oC add 66,2 kg ethylaminoethanol, the ratio between the chlorine atoms in ethylaminoethanol and the total number of CNS group is 0.75 to 1. Upon completion of the addition, the suspension is heated at 60oC for 1 hour.

After cooling the suspension, the substance is filtered off and washed with 300 l of anhydrous n-decane.

Get 64,2 kg of a solid component of catalyst having the following characteristics: the titanium content of 13.1 wt. the ratio between the trivalent titanium and the entire amount of titanium (trivalent + tetravalent titanium) is 0.70 1; magnesium content 6,28 wt. containing the components in proportion to their atomic content, component of the catalyst can be expressed by the following formula:

Ti1Mg0,96Al0,12Cl4/Et+OEt+OBu/1,28,

where OEt represents 1.2 percent and OBu 29.0% of the total weight.

Polymerization of ethylene

Polymerization of ethylene was conducted by the same method described in example 1, using 0.35 g of triethylamine and 16 mg of solid catalyst component, the receipt of which is described above.

16 mg of solid catalyst component (a titanium content of 13.1 wt.) 2,096 mg titanium 0,0437 mmol.

0.35 g of triethylaluminum 3,070 mmol.

The molar ratio of Al/Ti 65.

Receive 592 g of polyethylene, however, the performance is 37, and the output 282 (definitions are given in example 1).

The polyethylene obtained in this way is a free-flowing granules with a mean diameter of 225 μm, the content of fine particles (<74 μm) of 2.8% with an apparent density of 0.44 g/ml, and has the following characteristics: melt index /A STM D1238/ 6.7 g/10 min; sensitivity to shear (ASTM D1238) 28; Mw/Mn(the ratio between srednevekovym molecular weight and srednekislovsky molecular weight) of 3.75; density /ASTM D2839/ 0,9620 g/ml.

Example 4. Polymerization of ethylene

A solid component ASS="ptx2">

80 g/HR of the solid catalyst component (a titanium content of 13.1 wt.) 10,48 g titanium per hour 0,218 mol/hour.

053 kg/h of triethylaluminum 4,649 mol/hour.

The molar ratio of Al/Ti 21.

Use a reactor with a capacity of 40 m3the temperature inside the reactor is 90oC, total pressure of 10 ATM at a ratio of ethylene/hydrogen is 1:1, the feed rate of heptane is 6000 kg/h, the solid component of catalyst of 80 g/hour, triethylaluminum 0.53 kg/hour. The concentration of the pulp is 390 g/l, the residence time of 3.5 hours.

Example 4 is an example implementation of the invention on an industrial scale, in which the solvent for the reaction mixture containing the unreacted triethylamine returned to the reactor-polymerization. Thus, the amount of recycled triethylaluminum was two times more than fresh triethylaluminum, and the total molar ratio of Al/Ti in the reactor-polymerizate can be calculated as roughly 60-65.

In these conditions have the capacity of 40, and the output 305, determine the values indicated in example 1.

The polyethylene obtained in this way is a free-flowing granules with a mean diameter of 270 μm, the content of fine particles (<74 Obsticales to shift (ASTMD1238) 27-28; density (ASTMD2839) -0,9620-0,9630 g/m; impact strength Izod (ASTMD256) 125 j/m

1. A method of obtaining a solid component of catalyst for the (co)polymerization of ethylene by the interaction of magnesium chloride obtained by spraying an ethanol solution of magnesium chloride, Tetra-(C1WITH8)-alcoholate of titanium, and (C1WITH20-alkylamidoamines, followed by separation of the solid product, characterized in that the use of magnesium chloride with a content of hydroxyl groups 22 wt. in the calculation of the ethanol, a particle size of 3 to 100 microns with an average size of 15 μm, an apparent density of 0.3 g/ml, a specific surface area of 17 m2/g and a total porosity of about 75. and magnesium chloride are suspended in a liquid hydrocarbon solvent and injected into a suspension (C1WITH5)-aliphatic alcohol and Tetra-(C1- C8-titanium alcoholate at a molar ratio (C1- C5)-aliphatic alcohol, magnesium chloride 1.5 to 1 and a molar ratio of magnesium chloride, Tetra-(C1WITH8-titanium alcoholate 1 1, the suspension is then heated up to 80 120oWith the formation of a homogeneous solution, which is cooled to obtain granulated particles in suspension, and then introduced into the suspension (C1WITH20)-alkylaminocarbonyl groups 0,75 1, and the resulting suspension heated to 60oC.

2. A solid component of catalyst for the (co)polymerization of ethylene, representing a product of the interaction of magnesium chloride obtained by spraying an ethanol solution of magnesium chloride, Tetra-(C1- C8)-alcoholate of titanium, and (C1WITH20-alkylamidoamines, followed by separation of the solid product, characterized in that it is a product obtained by the sequential implementation of the suspension of magnesium chloride in a liquid hydrocarbon solvent, introducing into the suspension (C1WITH5)-aliphatic alcohol and Tetra-(C1< / BR>
WITH8)-titanium alcoholate at a molar ratio (C1- C5)-aliphatic alcohol, magnesium chloride 1.5 to 1 and a molar ratio of magnesium chloride, Tetra-(C1WITH8-titanium alcoholate 1 1, heating the suspension to 80 to 120°C with the formation of a homogeneous solution, cooling the solution to obtain granulated particles in suspension in the slurry (C1WITH20)-alkylhalogenide when the ratio of the number of chlorine atoms in (C1WITH20)-alkylhalogenide the total number of CNS groups 0,75 1 and heating the resulting suspension to 60oSince, when using chloride is equal to 15 μm with an apparent density of 0.3 g/ml, a specific surface area of 17 m2/g and a total porosity of about 75.

3. The catalyst for the (co)polymerization of ethylene, comprising trialkylaluminium and a solid component, which is a product of the interaction of magnesium chloride obtained by spraying an ethanol solution of magnesium chloride, Tetra-(C1WITH8)-alcoholate of titanium, and (C1WITH20- alkylamidoamines, followed by separation of the solid product, wherein the solid component contains a product obtained by the sequential implementation of the suspension of magnesium chloride in a liquid hydrocarbon solvent, introducing into the suspension (C1- C5)-aliphatic alcohol and Tetra-(C1WITH8)-titanium alcoholate at a molar ratio (C1WITH5)-aliphatic alcohol, magnesium chloride 1.5 to 1 and a molar ratio of magnesium chloride, Tetra-(C1- C8-titanium alcoholate 1 1, heating the suspension to 80 120oWith the formation of a homogeneous solution, cooling the solution to obtain granulated particles in suspension in the slurry (C1WITH20)-alkylhalogenide when the ratio of the number of the chlorine atom in (C1WITH20)-alkylhalogenide the total amount with the content of hydroxyl groups of 22 wt. in the calculation of the ethanol in the form of particles with a size of 3 to 100 microns with an average size of 15 μm with an apparent density of 0.3 g/ml, a specific surface area of 17 m2/g and a total porosity of about 75. in the following ratio of catalyst components, mol.h.

Trialkylaluminium 60 128

A solid component in terms of titanium 1

4. The method of obtaining the (co)polymers of ethylene by polymerization of ethylene or copolymerization with alpha-olefins in suspension in the presence of a catalyst comprising trialkylaluminium and a solid component, which is a product of the interaction of magnesium chloride obtained by spraying an ethanol solution of magnesium chloride, Tetra-(C1WITH8)-alcoholate of titanium, and (C1WITH20-alkylamidoamines, followed by separation of the solid product, wherein the process is carried out in the presence of a catalyst comprising, as the solid component of the product obtained by the sequential implementation of the suspension of magnesium chloride in a liquid hydrocarbon solvent, introducing into the suspension (C1- C5)-aliphatic alcohol and Tetra-(C1WITH8)-titanium alcoholate at a molar ratio (C1WITH5)-aliphatic alcohol chloride mA who evania suspension up to 80 120oWith the formation of a homogeneous solution, cooling the solution to obtain granulated particles in suspension in the slurry (C1WITH20)-alkylhalogenide when the ratio of the number of chlorine atoms in (C1WITH20)-alkylhalogenide and the total number of CNS groups 0,75 1 and heating the resulting suspension to 60oWith the use of magnesium chloride with a content of hydroxyl groups 22 wt. in the calculation of the ethanol in the form of particles with a size of 3 to 100 microns with an average size of 15 μm with an apparent density of 0.3 g/ml, a specific surface area of 17 m2/g and a total porosity of about 75. in the following ratio of catalyst components, mol.h.

Trialkylaluminium 60 128

A solid component in terms of titanium 1Z

 

Same patents:

The invention relates to the field of polymer chemistry and relates to a catalyst for polymerization of alpha-olefins and the way in which it is used
The invention relates to a solid component of catalyst, the method of its production and its use in the polymerization of ethylene and copolymerization of ethylene with alpha-olefins

The invention relates to the chemistry of high molecular compounds, and to methods of producing polymers of higher-olefins, effectively reducing hydrodynamic resistance (SDS) of hydrocarbon liquids
The invention relates to a solid component of catalyst, the method of its production and its use in the polymerization of ethylene and copolymerization of ethylene with alpha-olefins

The invention relates to methods of producing ultra-high molecular weight polyethylene (UHMWPE), i.e. polyethylene with srednevozrastnoe molecular weight of 1-6 million (characteristic viscosity in decaline at 135oWith 10-30 DL/g), high output, adjustable particle size and improved properties for processing

FIELD: chemical industry, in particular two-component heterogeneous immobilized catalyst for ethylene polymerization.

SUBSTANCE: claimed catalyst includes alumina, mixture of transition metal complexes with nitrogen skeleton ligands (e.g., iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex). According the first embodiment catalyst is prepared by application of homogeneous mixture of transition metal complexes onto substrate. iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex (or vise versa) are alternately applied onto substrate. According the third embodiment catalyst is obtained by mixing of complexes individually applied onto substrate. Method for polyethylene producing by using catalyst of present invention also is disclosed.

EFFECT: catalyst for producing polyethylene with various molecular weights, including short chain branches, from single ethylene as starting material.

7 cl, 5 tbl, 27 ex

FIELD: olefin polymerization.

SUBSTANCE: invention relates to method for introducing of several catalysts in gas-phase or suspension reactor. Claimed method includes integration before introducing into single reactor of (a) solution, suspension or emulsion containing the first catalytic substance; and (b) solution, suspension or emulsion containing the second catalytic substance and optionally activator; followed by (c) introducing of (a) and (b) composition into single reactor in presence of hydrogen and one or more olefins wherein one polyolefin composition is formed.

EFFECT: polymers with wide bimodal molecular mass distribution.

14 cl, 3 ex

FIELD: polymerization catalysts and polymerization processes.

SUBSTANCE: high-activity ethylene (co)polymerization-appropriate supported titanium-based catalyst is composed of (A) supported catalytic component, notably titanium-containing active component on porous silica, containing at least one titanium compound, at least one magnesium compound, at least one alkylaluminum compound, at least one halide promoter, at least one electron-donor compound, and inert porous silica carrier, wherein halide promoter belongs to the class of compounds described by general formula F-R1[R2bX(3-b)], in which F represents oxygen-containing functional group reactive to organoaluminum compound, titanium compound, and hydroxyl groups; R1 bivalent C1-C6-aliphatic or aromatic grouplinked to functional group F; R2 hydrogen atom, unsubstituted or halogen-substituted C1-C6-alkyl, halogen-substituted C3-C6-cycloalkyl, or halogen-substituted C6-C10-aryl; b=0,1 or 2; and X represents fluorine, chlorine, or bromine atom; and (B) alkylaluminum cocatalyst. Invention also discloses catalyst preparation method and ethylene (co)polymerization process in presence of above-defined catalyst.

EFFECT: enabled preparation of catalyst with good morphology and flowability of particles, high catalytic activity, good sensitivity to addition of hydrogen, and ability to include comonomer; improved particle morphology of polymers.

15 cl, 2 tbl, 11 ex

FIELD: chemical industry; methods of production of polyethylene in the tubular reactors with curing chambers or without them.

SUBSTANCE: the invention is pertaining to the method of production of polyethylene in the tubular reactors with the curing chambers or without them. The method provides, that the chain-radical initiator with cold ethylene or without it is fed into the flowing liquid medium containing ethylene with a comonomer. Conduct swirling of two being mixed streams at an angle or by means of the provided swirling component - in the cross section of the stream. In the zone of the area of introduction of the chain-radical initiator there is a narrowing of the cross-section, in which through a eccentrically located optimized outlet hole of the finger-shaped feeding component in the swirled stream introduce the chain-radical initiator.

EFFECT: the invention ensures a reliable introduction of the initiator in the tubular reactors with curing chambers or without them.

20 cl, 9 dwg

FIELD: polymerization processes.

SUBSTANCE: invention provides ethylene polymerization process at pressure between 1000 and 4000 bar and temperature from 140 to 320°C, which is characterized by that water is continuously or stepwise is fed into reactor so that reaction proceeds at such pressure and temperature, at which water is in supercritical state.

EFFECT: improved heat extraction and thereby increased degree of ethylene conversion.

9 cl, 2 tbl, 7 ex

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to a nickel-containing catalyst and to a method for the oligomerization reaction of ethylene to a mixture of olefin products with high degree of linearity. Invention describes a composition of catalyst comprising product prepared by interaction of the following components in a polar organic solvent in the presence of ethylene: (a) bivalent nickel simple salt with solubility at least 0.001 mole per liter in indicated polar organic solvent; (b) boron hydride-base reducing agent; (c) water-soluble base; (d) ligand chosen from o-dihydrocarbylphosphinobenzoic acids and their alkaline metal salts; (e) trivalent phosphite wherein the molar ratio of ligand to phosphite is in limits from about 50:1 to about 1000:1. Also, invention describes a method for preparing the catalyst composition and a method for synthesis of a mixture of olefin products showing the high degree of linearity. Invention provides preparing the economically effective catalyst useful in synthesis of olefin substances showing the high degree of linearity.

EFFECT: improved and valuable properties of catalyst.

10 cl, 2 tbl, 3 ex

FIELD: polymer production.

SUBSTANCE: invention relates to polyolefin production technology, notably to synthesis of ethylene copolymers on modified chromium oxide catalyst under low pressure conditions is gas-phase fluidized-bed reactor. More particularly, low-pressure polyethylene production via continuous gas-phase ethylene/α-olefin copolymerization process is disclosed, said process being carried out in a reactor with fluidizing grate using catalyst containing chromium oxide, modifying oxide, fluorine, and silica as carrier. Reaction mixture composed of ethylene, α-olefin, hydrogen, and nitrogen and compositionally adjusted when being circulated by adding appropriate amounts of indicated constituents, provided that nitrogen content lies allays within a range of 30-50% based on the total volume of reaction mixture, is fed into reactor below fluidizing grate. Additional amounts of nitrogen are continuously introduced into reactor as a separate stream above fluidizing grate at the catalyst supply level. Chromium oxide contained in catalyst is chromium reduction product with chromium in the form of Cr2+ and modifying oxide is aluminum oxide prepared from alkoxyalumoxane. Silica carrier is modified with fluorine in the preliminary drying step.

EFFECT: increased yield of polyethylene based on unit mass of catalyst and reduced consumption of catalyst without loss in product quality.

1 dg, 3 tbl, 10 ex

FIELD: polymer production.

SUBSTANCE: invention relates to a gas-phase process for producing polyethylene from ethylene in fluidized-bed reactor, which process comprises: (i) hydrogenation stage, wherein supplied ethylene including impurities or secondary components such as acetylene and ethane reacts with hydrogen to remove acetylene via catalytic hydrogenation and to form ethylene, while a part of ethylene is converted into ethane; and (ii) polymerization stage, hen ethylene leaving stage (i) reacts in gas phase in fluidized-bed reactor to form polyethylene, wherein fluidizing gas contains, at the entry of reactor, ethylene and ethane in amount 20 to 70% based on the total volume of fluidizing gas, optionally with other components.

EFFECT: reduced investment and energetic expenses and increased yield of product for one pass in unit time.

5 cl, 2 dwg, 1 tbl, 3 ex

Up!