A solid component of catalyst for the polymerization of ethylene, the method of its production, the catalyst for polymerization of ethylene and a method of producing polyethylene

 

(57) Abstract:

Usage: obtain a solid component of catalyst and its use in the polymerization of ethylene and copolymerization of ethylene with an alpha olefin. The inventive solid component of catalyst for the polymerization of ethylene contains as alkoxysilane transition metal mixture tetrachlorogallate titanium with silicon tetrachloride and trichloride titanium or tetraalkylam zirconium content in the mixture of 0.92-1.01 silicon atoms 1 alkoxygroup. He is a product obtained by suspendirovanie in a solution of magnesium chloride in ethanol particles of silicon dioxide, activated dialkylamines, introduction to the suspension alkoxysilane transition metal with the atomic ratio of magnesium chloride magnesium transition metal from 2.5 to 5.0 evaporation of ethanol, suspendirovanie solid residue in an inert hydrocarbon, an introduction to the suspension solution alkylhalogenide in an inert hydrocarbon with respect to the number of chlorine atoms in alkylhalogenide and alkoxygroup in alkoxysilane transition metal from 1.73 up to 2.06, separation of the solid product with subsequent washing with an inert hydrocarbon and drying, when Soetoro 8,2:2,0: 36,2: 17,1, respectively, and the content of silicon dioxide 50-62 wt. on 100 wt. the solid component of catalyst. Also provided is a method of obtaining a solid component of catalyst polymerizatio ethylene, the catalyst for polymerization of ethylene, containing a solid component, and method for producing polyethylene using a catalyst containing a solid component. 4 S. p. f-crystals.

The invention relates to a solid component of catalyst, method of its production and use in the polymerization of ethylene and copolymerization of ethylene with alpha-olefins.

It is known that ethylene or even alpha-olefins can be polimerizuet at low pressure using catalysts of the type Ziegler-Natta. These catalysts usually consist of compounds of elements of subgroups IV to VI of the Periodic table (transition metal compounds), mixed with ORGANOMETALLIC compound or hydride of elements from groups I-III in the Periodic table.

Also known catalysts, in which the compound of the transition metal is fixed on a solid carrier, organic or inorganic, and sometimes physically and/or chemically treated. Examples of such solid carriers are oxidized compounds of divalent metals (e.g., oxides, oxidized inorganic salt and the catalyst is a halide compound of the divalent metal, processed electron-donor. In accordance with the description of U.S. patent N 4421674 a carrier for the catalyst is a solid smooth the product obtained by spray drying of a solution of magnesium chloride in ethanol. In particular, in U.S. patent N 4421674 indicated that microspheroidal solid particles, such as silicon dioxide, can be suspended in a solution of ethanol magnesium chloride to obtain a spherical carrier for catalysts having a core consisting of microspheroidal solid particles surrounded by a layer of activated magnesium chloride.

Now discovered that it is possible to get a solid connection catalysts Ziegler-Natta on media prepared with microspheroidal silicon dioxide and a solution of magnesium chloride in ethanol using a simple and well-known method, which not only eliminates the difficulties associated with spray drying, but also forms the solid components of catalysts with improved catalytic activity in the (co)polymerization of ethylene.

The present invention relates to a method of obtaining a solid catalyst component for polymerization of ethylene and copolymerization of ethylene with alpha-olefins, consisting Ethan, magnesium, chlorine and alkoxygroup. This method has the following stages:

a) prepare a solution of magnesium chloride in ethanol;

b) particles of activated silica is impregnated with a solution prepared at the stage through a suspension of particles of silicon dioxide in solution;

(C) in the suspension stage b: add at least one compound of titanium is selected from the alcoholate and galogensoderjasimi alcoholate of titanium and halide compounds of silicon with an atomic ratio between the magnesium in magnesium chloride and titanium in the range of 2.0/1-12,1/1 and the relationship between silicon atoms and alkoxygroup in the alcoholate or halide alcoholate of titanium in the range of from 0.1/1 to 4.0/1;

d) removing the ethanol from the suspension obtained in stage C by evaporation to extract solids;

e) the solid material obtained in stage d, reacts with alkylchloride aluminum in an atomic ratio between the chlorine atoms in alkylchloride aluminum and alkoxy groups in the anion or a halide alcoholate of titanium in the range of 0.5/1 to 7,0/1;

f) restore the solid catalyst component.

A solution of magnesium chloride in ethanol prigotovlyayut on stage and process. For this purpose p is raised to the water content, which is lower than about 5 wt.

Similarly, the ethanol is preferably anhydrous, or it may have a low water content, which, however, is less than about 5 wt. The dissolution of magnesium chloride can occur at room temperature (20-25aboutC) or at a higher temperature to reach the temperature of the irrigation ethanol at atmospheric pressure. The preferred operating temperature is approximately the 60aboutWith the preparation of solutions of ethanol with the concentration of magnesium chloride 1-15 wt.

At the stage b of the proposed method of silica particles impregnated with the solution prepared in stage a, through a suspension of particles of silicon dioxide in solution.

For this purpose the most suitable silicon dioxide is microspheroidal porous silicon dioxide having a particle size in the range of 10-100 μm, the content of silicon dioxide is more than 90 wt. the surface area in the range of 250-400 m2/g, pore volume in the range of 1.3 to 1.8 ml/g and an average pore diameter in the range of 1.3 to 1.8 ml/g To its impregnation of the silica must be activated by heating silicon dioxide in an inert atmosphere at a temperature of about 100-animateclick connection as alkilani and alkylamine, for example butylamine, octylamine butyl and aluminum-tributylamine, operating at room temperature or higher temperatures, for example about 60aboutC. the silicon Dioxide is preferably activated by processing octylaniline in an amount of about 10-20 wt. silicon dioxide.

The impregnation is carried out by suspension from 10 to 20 wt.h. particles of silicon dioxide for every 100 rpm.h. solution of ethanol, magnesium chloride, while in contact, if necessary, in the context of low mixing at a temperature which increases from room temperature (20-25about(C) up to about the boiling point of ethanol, preferably 50-65aboutWith in a period of time from 0.5 to 2.0 hours

According to the invention in a suspension from step b add on stage to process at least one compound of titanium is selected from the alcoholate and halide alcoholate of titanium and halide compounds of silicon with an atomic ratio between the magnesium in magnesium chloride and titanium in the range of 2.0/1-12,0/1, and the relationship between silicon atoms and alkoxygroup in the alcoholate or halide alcoholate of titanium in the range of 0.1/1 to 4,0/1.

Connected is from 1 to 4 carbon atoms in the fraction of the alcoholate. Special examples of these compounds are Tetra-n-propylate titanium, Tetra-n-butyl titanium, Tetra-ISO-propylate titanium, Tetra-ISO-butyl titanium and the corresponding mono - or di chloralose-titanium. These alkoxide can be mixed with titanium tetrachloride, however, it is preferable to use a mixture of titanium tetrachloride and tetrachlorogallate titanium selected from the above compounds in a molar ratio between about 1/3.

In accordance with the invention in a suspension from step b add halogenoalkane selected from chetyrehpolozyj compounds of silicon and galoisian. Special examples of these compounds are silicon tetrachloride, trichlorosilane and chlorathalonil. For this purpose, the preferred silicon tetrachloride.

At the stage of the process it is preferable to use the atomic ratio between magnesium and titanium 3.5/1 to 8.5/1 and the ratio between silicon atoms and alkoxygroup in the range of 0.5/1 to 4,0/1.

In accordance with the specific application of the invention the compound of zirconium or hafnium, selected from the halides, in particular tetrachloride, alcoholate and halide alcoholate, especially chloralose should be added to suspense,0/1. Thus obtained solid catalyst component, which can be used for polymerization of ethylene with the formation of polymers with a broad molecular weight distribution.

At the stage of the process procedure of the additive compounds of titanium, silicon and, if required, zirconium and hafnium, is not critical. However, this Supplement exercise and the resulting suspension support at a temperature in the range from room temperature (20-25about(C) up to about 100aboutWith over a period of time from 0.5 to 3 h, preferably at a temperature of about 60aboutC for about 1 h

At stage d process from the suspension obtained in stage C, remove the ethanol by evaporation. This evaporation should be carried out by distillation at atmospheric pressure or at reduced pressure, and finally, the solid product is dried for 0.5-2 hours at a temperature of approximately 120aboutWith the pressure of 5-10 mm RT.article.

At stage e of the process the solid product obtained in stage d, reacts with chlorine-alkylamines when the atomic ratio between the chlorine atoms in chlorine-alkylamine and alkoxygroup of alcoholate or halide alcoholate of titanium in the range of 0.5/1 to 7,0/1.

More precise, and placed in contact with chlorine-alkylamines, in total selected from a chlorine-diethylamine, polutorakratnogo connection ethylamine, chloride diisobutylaluminum and dichloride, isobutylamine, dissolved in a specified hydrocarbon solvent or other hydrocarbon solvent. The method is carried out at a temperature in the range from 10 to 100aboutWith over a period of time, which depending on the selected operating temperature may vary from 10 min to 24 h to obtain nuclear relations between chlorine and titanium in the solid product in the range of from 10/1 to 40/1. The preferred operating temperature is 20-90aboutWith over a period of time from 10 min to 1 h to obtain nuclear relations between chlorine and titanium in the solid product from 12/1 to 36/1. This processing has the effect of increasing the chlorine content of the solid component of catalyst with simultaneous restoration of partially or completely of titanium from the tetravalent state to the trivalent state and partial or total removal of the present alkoxygroup.

At the end of processing a solid component of catalyst is extracted at stage f, washed with a liquid aliphatic hydrocarbon solvent, NGOs dried.

A solid component of catalyst according to the invention consists of a carrier in the form of particles of silicon dioxide (50-90 wt.) and a catalytically active part (50-10 wt.), comprising titanium, magnesium and chlorine, and also alkoxygroup with the following atomic ratios: Mg/Ti 2,0/1-12,0/1; Cl/Ti 10/1-40/1; alkoxygroup Ti from 0/1 to 20/1. These alkoxygroup include ethoxypropan obtained from ethanol and alkoxygroup formed from a titanium alcoholate. The amount of titanium in the catalyst component typically varies from 0.5 to 5.0 wt. A solid component of catalyst preferably consists of a carrier in the form of particles of silicon dioxide (55-80 wt.) and a catalytically active part (45-20 wt.), containing titanium, magnesium, chlorine and alkoxygroup with the following atomic relations: Mg/Ti 3,5/1-8,5/1; Cl/Ti 12/1-36/1; alkoxygroup Ti 2,1/10/1. In this component of the catalysts, the amount of titanium is usually from 0.8 to 2.0 wt.

When zirconium or hafnium is present in the solid component of catalyst, the atomic ratio between titanium and zirconium or hafnium will be in the range of 0.5/1-2,0/1.

The invention also concerns a catalyst for the (co)polymerization of ethylene, comprising the proposed solid component kataliza haloalkyl derived aluminum (especially chlorides), containing from 1 to 5 carbon atoms in alkilani faction. Among them, preferred trialkylaluminium with 2-4 carbon atoms in alkilani fractions, such as triethylaluminium, tributylamine and triisobutylaluminum. The catalyst according to the invention has an atomic ratio between aluminum (socializaton) and titanium (solid component of catalyst, which is typically in the range from 20:1 to 250:1, preferably from 100:1 to 200:1.

This catalyst is very active in ways polymerization of ethylene and copolymerization of ethylene with alphaolefins. The use of silicon halide under the described conditions is essential to achieving such an activity, as can be seen from the experimental examples described below. In particular, it was proved that the halide of silicon makes the solid components of catalysts are highly active, even if the high content of alkoxygroup and if the solid components of catalysts containing zirconium or hafnium in addition to titanium.

The catalyst according to the invention can be used in the methods of polymerization, carried out by suspension in an inert diluent, or in gas phase in a fluidized or stirred bed. Alf is edocfile 4-6 carbon atoms, for example butene-1, hexene-1 and 4-methyl-penten-1. The usual polymerization conditions: temperature from 50 to 100aboutWith a total pressure of from 5 to 40 bar, and the relationship between the partial pressure of hydrogen and the partial pressure of ethylene, from 0 to 10. A high yield of the olefin polymer is achieved at any speed, and thus obtained polymer has an exceptional rheological properties, in particular it is present in the form of granules, which are not fragile and free fraction of very small particles.

In the experimental examples, use media from microspheroidal particles of silicon dioxide ranging in size from 20 to 60 μm, and the content of silicon dioxide is more than 99 wt. the surface area of 320 m2/g, pore volume of 1.65 mm/g and an average pore diameter of 25-26 nm.

P R I m e R 1 (comparative). 4.5 g (47,3 mmol) of anhydrous magnesium chloride and 100 ml of absolute ethanol, dehydrated aluminium, load 250 mm flask equipped with irrigation refrigerator, mechanical stirrer and thermometer. The mixture is heated to 60aboutC for 30 min for complete dissolution of the magnesium chloride.

15 g microspheroidal particles of silicon dioxide, pre-activated by contactgroup, suspended in the resulting solution. Suspension support at 60aboutC for 30 minutes

In the slurry, add 2.4 g (7.05 mol) of tetrabutyl titanium and 0,445 g (2,35 mmol) titanium tetrachloride and maintain contact at 60aboutC for 1 h

Then it is dried by evaporation of the solvent and the extracted solid material is heated under vacuum (5-10 mm RT.CT.) if 120aboutC for 1 h

12 g of the obtained solid particles suspended in 40 ml of anhydrous n-hexane and the suspension is added 9.6 ml of a 40% aqueous solution triethylaluminium of sexylolita (3,23 g, 13,03 mmol) in n-decane. Contact support for 15 min at 25aboutC. Then the solid is removed by filtration, washed with anhydrous n-hexane until then, until you have removed all the chloride in the washing liquid, and, finally, it is dried by evaporation of the solvent.

Get about 10 g of the solid component in the form of solid granules containing 58 wt. silicon dioxide and having a ratio of Mg:Ti:Cl alkoxygroup 7,2:1,0:16,6:9,4.

A solid component of catalyst prepared by the proposed method, used in the test for the polymerization of ethylene. More specifically, the polymerization is carried out in 5-lietoshanai between the hydrogen pressure and the pressure of ethylene of 0.47/1, temperature 90aboutC and for 2 h at this used 100 mg of solid component of catalyst and triethylamine as socializaton when the atomic ratio 190/1 between aluminum socializaton and titanium in the solid catalyst component.

Thus, the output, 2.4 kg of polyethylene per gram of solid component of catalyst, the polyethylene has the following characteristics:

Density (ASTM D-1505) 0,9595 g/ml

The index of the stream races

Plava ASTM D-1238, MFI (2,16 kg) of 1.38 g/10

The apparent raft - ness (ASTM D-1895) 0.35 g/ml

MFR (MFR ratio index, melt flow, defined as the ratio of MFI (to 21.6 mg)/MFI (2,16 kg).

The polyethylene was in pellet form with the following size distribution, microns: > 2000 01, 2000 < >1000 6,9 1000 < > 500 77,0 500 < > 250 14,0 < 250 2,0

P R I m m e R 2. (comparative). 4.5 g (47,3 mmol) of anhydrous magnesium chloride and 100 ml of absolute ethanol, dehydrated aluminium, load in a nitrogen atmosphere in a 250-millimeter flask, equipped with irrigation refrigerator, mechanical stirrer and thermometer. The mixture is heated to 60aboutC for 30 min to allow the magnesium chloride is completely dissolved.

15 g microspheroidal casteam 17 ml of 20 wt. butylaniline in heptane and 150 ml of n-hexane, suspended in the resulting solution. Suspension support at 60aboutC for 30 minutes

Then, the suspension is added 2.4 g (7.05 mmol) of tetrabutyl titanium and 0,445 g (2,35 mmol) titanium tetrachloride and maintain contact at 60aboutC for 1 h and Then it is dried by evaporation of the solvent and the solid product is extracted, heated under vacuum (5-10 mm RT.CT.) if 120aboutC for 1 h

12 g of the obtained solid particles suspended in 40 ml of anhydrous n-hexane and the suspension type of 19.2 ml of a 40% aqueous solution of triethyl-aluminum sesquichloride in n-decane (6,45 g; date 26,06 mmol). Contact is maintained for 1 h at 65aboutC. Then the solid is extracted by filtration, washed with anhydrous n-hexane until then, until you have removed all the chloride in the washing liquid, and finally dried by evaporation of the solvent.

So get about 10 g of the solid component of catalyst in solid granular form, containing 56 wt. silicon dioxide and having a ratio of Mg:Ti:Cl:alkoxygroup 6,3:1,0:18, 9:6,0.

A solid component of catalyst obtained by the proposed method, the IP is the future 2 liters of n-hexane. The method is carried out under a pressure of 15 bar in the presence of hydrogen, with a ratio between the hydrogen pressure and the pressure of ethylene of 0.47/1, temperature 90aboutC for 2 h with 100 mg of solid component of catalyst and triethylaluminum as socializaton when the atomic ratio 180/1 between aluminum socializaton and titanium in the solid catalyst component.

Achieved output equal to 4.2 kg of polyethylene per gram of solid component of catalyst, and it has the following characteristics: Density 0,9606 g/ml

Index (MFI)

melt flow (2,16 kg) 2.16 g/10 Apparent density of 0.30 g/ml

The ratio of the flow (MFR) of the melt 31

Polyethylene is present in granular form with the following size distribution, microns: > 2000 8,4 2000 < > 1000 19,9 1000 < > 500 63,7 500 < > 250 6,9 < 250 1,1

P R I m e R 3. 4.5 g (47,3 mmol) of anhydrous magnesium chloride and 100 ml of absolute ethanol, dehydrated aluminium, load in a nitrogen atmosphere in a 250-millimeter flask, equipped with irrigation refrigerator, mechanical stirrer and thermometer. The mixture is heated to 60aboutC for 30 min for complete dissolution of the magnesium chloride.

15 g microspheroidal particles dioxide credit is 20 wt. butyloctyl magnesium in heptane and 150 ml of n-hexane, suspended in the resulting solution. Suspension support at 60aboutC for 30 minutes

2.4 g (7.05 mmol) of tetrabutyl titanium, 0,445 g (2,35 mmol) titanium tetrachloride, and 3.3 ml (4,84 g, 26,52 mmol) of silicon tetrachloride is added to the suspension and support contact at 60aboutC for 1 h and Then it is dried by evaporation of the solvent and extract the solid substance is heated under vacuum (5-10 mm RT.CT.) 120aboutC for 1 h

13.5 g of the obtained solid product is suspended in 50 ml of anhydrous n-hexane and 12.7 ml of a 40% aqueous solution triethylaluminium of sesquichloride in n-decane (a 4.03 g; 16,29 mmol) is added to the resulting suspension. Contact support for 15 min at 25aboutC. and Then through a filter to extract the solid product is washed him anhydrous n-hexane until then, until you have removed all the chloride in the washing liquid, and, finally, it is dried by evaporation of the solvent.

So, get 12 g of solid component of catalyst in solid granular form, containing 62 wt. silicon dioxide and having a ratio of Mg:Ti:Cl:alkoxygroup 7,2:1, 0:18, 9:5,4.

A solid component of the AC is olymerization carried out in a 5-liter autoclave, containing 2 liters of n-hexane. The method is carried out under a pressure of 15 bar in the presence of hydrogen, with a ratio between the hydrogen pressure and the pressure of ethylene, equal to 0.47/1, at a temperature of 90aboutC for 2 h using 50 mg of solid component of catalyst and triethylamine as socializaton when the atomic ratio between the aluminium in socializaton and titanium in the solid component of catalyst equal to 200/1.

Achieved output, equal to 10.4 kg of polyethylene per gram of solid component of catalyst, the polyethylene has the following characteristics: Density 0,9589 g/ml

Index melt flow, MFI (2,16 kg) 2.2 g/10 Apparent density of 0.28 g/ml

The ratio of the melt flow, (MFR) of 29.9

Polyethylene in pellet form with the following size distribution in microns: > 2000 4,1 2000 < > 1000 31,2 1000 < > 500 52,2 500 < > 250 8,1 < 250 4,4

P R I m e R 4 (comparative). 4.5 g (47,3 mmol) of anhydrous magnesium chloride and 100 ml of absolute ethanol, dehydrated aluminium, load in a nitrogen atmosphere in a 250-millimeter flask, equipped with an irrigating refrigerator, mechanical stirrer and thermometer. The mixture is heated to 60aboutC for 30 min for complete dissolution of the magnesium chloride.

15 g micro isWith a solution containing 17 ml of 20 wt. butyloctyl magnesium in heptane and 150 ml of n-hexane, suspended in the resulting solution. Suspension support at 60aboutC for 30 minutes

3,20 g (9,40 mmol) of tetrabutyl titanium, of 3.60 g (9,38 mmol) of tetrabutyrate zirconium is added to the suspension and support contact at 60aboutC for 1 h

Then it is dried by evaporation of the solvent and extract the solid substance is heated under vacuum (50-10 mm RT.CT.) 120aboutC for 1 h

The thus obtained solid product is suspended in 100 ml of anhydrous n-hexane and 30 ml of 40.5%-aqueous solution dvuhgolosnogo connection isobutylamine in n-hexane (9,72 g; 62,7 mmol) is added to the resulting suspension. Contact is maintained for 1 h at 65aboutC. and Then through a filter to extract the solid product is washed him anhydrous n-hexane until then, until you have removed all the chlorides, and, finally, it is dried by evaporation of solvent.

So, get 10 g of the solid component of catalyst in pellet form, containing a 53.5 wt. silicon dioxide and having a ratio of Mg:Ti:Zr:Cl:alkoxygroup equal 6,5:1,0:1,0:24,8:4,1.

A solid component kata is Italy carried out in a 5-liter autoclave, containing 2 liters of n-hexane. The method is carried out under a pressure of 15 bar in the presence of hydrogen, with a ratio between the hydrogen pressure and the pressure of ethylene, equal to 0.47/1 at 90aboutC for 2 h with the use of solid component of catalyst and triethylaluminum as socializaton when the atomic ratio between the aluminium in socializaton and titanium in the solid component of catalyst equal to 140/1.

Achieved output, equal to 4.1 kg of polyethylene per gram of solid component of catalyst, the polyethylene has the following characteristics: Density 0,9636 g/ml

Index melt flow, MFI (2,16 kg) 2.9 g/10 Apparent density of 0.30 g/ml the ratio of the melt flow of 37.8

Polyethylene in pellet form with the following size distribution, microns: > 2000 0,1 2000 < > 1000 26,7 1000 < > 500 64,7 500 < > 250 7,4 < 250 1,1.

P R I m e R 5. 4.5 g (47,3 mmol) of anhydrous magnesium chloride and 100 ml of absolute ethanol, dehydrated aluminium, load in a nitrogen atmosphere in a 250-millimeter flask, equipped with an irrigating refrigerator, mechanical stirrer and thermometer. The mixture is heated to 60aboutC for 30 min for complete dissolution of the magnesium chloride.

15 g microspheroidal particles dioxide credit the relevant 17 ml of 20 wt. butyloctyl magnesium in heptane and 150 ml of n-hexane, suspended in the thus obtained solution. Suspension support at 60aboutwithin 30 minutes

3,20 g (9,40 mmol) of tetrabutyl titanium, of 3.60 g (9,38 mmol) of tetrabutyrate zirconium and 8.0 ml (11,74 g, 69,13 ml) silicon tetrachloride then add in suspension and maintain contact at 60aboutC for 1 h

Then carry out drying by evaporation of the solvent and extract the solid product is heated under vacuum (5-10 m RT.CT.) 120aboutC for 1 h

18.6 g of the obtained solid particles suspended in 100 ml of anhydrous n-hexane and 37 ml of 40.5% -aqueous solution of isobutylamine aluminum in n-hexane (11.9 g; 77,34 mmol) is added to the resulting suspension. Contact is maintained for 1 h at 65aboutC. and Then through a filter to extract the solid product is washed him anhydrous n-hexane until then, until you have removed all the chloride in the washing liquid, and finally dried by evaporation of the solvent.

So, get about 17 g of the solid component of catalyst in solid granular form, containing 50 wt. silicon dioxide and having a ratio of Mg:Ti:Zr:Cl:alkoxygroup, lsout in the test for the polymerization of ethylene. More precisely, conduct the polymerization in a 5-liter autoclave containing 2 liters of n-hexane. The method is carried out under a pressure of 15 bar in the presence of hydrogen, with a ratio between the hydrogen pressure and the pressure of ethylene of 0.47/1 at 90aboutC for 2 h using 50 mg of solid component of catalyst and triethylaluminum as socializaton, and the atomic ratio between the aluminium in socializaton and titanium in the solid component of catalyst is equal to 200/1.

Achieved output equal to 11 kg of polyethylene per gram of solid component of catalyst, the polyethylene has the following characteristics: Density 0,9591 g/ml Index melt flow, MFI (2,16 kg) 1.22 g/10 Apparent density of 0.23 g/ml

Polyethylene is present in granular form with the following size distribution, microns: > 2000 6,6 2000 < > 1000 40,0 1000 < > 500 42,7 500 < > 250 8,4 < 250 2,3

1. A solid component of catalyst for the polymerization of ethylene, comprising particles of activated dialkylamines silica treated with a solution of magnesium chloride in ethanol, and deposited them alkoxysilane transition metal and alkylhalogenide, characterized in that as alkoxysilane transition metal it contains compounds is the obsession in a mixture of 0.92 1.01 silicon atoms 1 alkoxygroup and represents a product received suspendirovanie in a solution of magnesium chloride in ethanol particles of silicon dioxide, activated dialkylamines, introduction to the suspension alkoxysilane transition metal with the atomic ratio of magnesium chloride magnesium transition metal from 2.5 to 5.0, evaporation of the ethanol, suspendirovanie solid residue in an inert hydrocarbon, an introduction to the suspension solution alkylhalogenide in an inert hydrocarbon with respect to the number of chlorine atoms in alkylhalogenide and alkoxygroup in alkoxysilane transition metal from 1.73 up to 2.06, separation of the solid product with subsequent washing with an inert hydrocarbon and drying, when the ratio of the number of atoms of magnesium, transition metal, chlorine and alkoxygroup in the dried product from 7,2 1,0 to 18.9 5.4 up 8,22,0 36,2 17,1, respectively, and the content of silicon dioxide 50 62 wt. on 100 wt. the solid component of catalyst.

2. A method of obtaining a solid component of Katalizator polymerization of ethylene by treatment with a solution of magnesium chloride in ethanol particles of silicon dioxide, activated dialkylamines, the interaction of product processing alkoxysilanes transition metal and alkylamidoamines, followed by the separation of torenia transition metal, a mixture of tetrachlorogallate titanium with silicon tetrachloride and titanium tetrachloride or etheralcohol zirconium content in the mixture 0,92 1,01 of silicon atoms to 1 alkoxygroup, and consistently implement the suspension of activated dialkylamines particles of silicon dioxide in a solution of magnesium chloride in ethanol at the rate of 100 ml solution of magnesium chloride in ethanol for every 15 g of silicon dioxide and the mass ratio of magnesium chloride: silicon dioxide 1 3, introduction to the suspension alkoxysilane transition metal with the atomic ratio of magnesium chloride magnesium transition metal from 2.5 to 5.0, the evaporation of ethanol, the suspension of the solid residue in an inert hydrocarbon, an introduction to the obtained suspension solution alkylhalogenide in an inert hydrocarbon with respect to the number of chlorine atoms in alkylhalogenide and alkoxygroup in alkoxysilane transition metal from 1.73 up to 2.06.

3. The catalyst for polymerization of ethylene, comprising triethylaluminum and a solid component comprising particles of activated dialkylamines silica treated with a solution of magnesium chloride in ethanol, and inflicted on them alkoxysilane transition metal and alkylhalogenide, characterized in that the solid component contains a product obtained by suspendirovanie in a solution of magnesium chloride in ethanol particles of silicon dioxide, Akti the fight mixture of tetrachlorogallate titanium with silicon tetrachloride and titanium tetrachloride or tetraalkylam zirconium content in the mixture 0,92 1,01 of silicon atoms to 1 alkoxygroup, when the atomic ratio of magnesium chloride magnesium transition metal from 2.5 to 5.0, evaporation of the ethanol, suspendirovanie solid residue in an inert hydrocarbon, an introduction to the suspension solution of alkylhalogenide in an inert hydrocarbon with respect to the number of chlorine atoms in alkylhalogenide and alkoxygroup in alkoxysilane transition metal from 1.73 up to 2.06, separation of the solid product with subsequent washing with an inert hydrocarbon and drying when the ratio of the number of atoms of magnesium, transition metal, chlorine and alkoxygroup in the dried product from 7,2 1,0 18,9 5,4 8,2 2,0 36,2 17,1, respectively, and the content of silicon dioxide 50 62 wt. on 100 wt. the solid component of catalyst, the atomic ratio of aluminum in triethylaluminium: transition metal in the solid component 200 1.

4. A method of producing polyethylene by polymerization of ethylene in an inert hydrocarbon solvent in the presence of hydrogen as molecular weight regulator and catalyst, including triethylaluminium and a solid component comprising particles of activated dialkylamines silica treated with a solution of magnesium chloride in ethanol, and inflicted on them alkoxysilane the transition component of the product, received suspendirovanie in a solution of magnesium chloride in ethanol particles of silicon dioxide, activated dialkylamines, introduction to the suspension alkoxysilane transition metal which is a mixture of tetrachlorogallate titanium with silicon tetrachloride and titanium tetrachloride or tetraalkylam zirconium content in the mixture 0,92 1,01 of silicon atoms to 1 alkoxygroup, when the atomic ratio of magnesium chloride magnesium transition metal from 2.5 to 5.0, evaporation of the ethanol, suspendirovanie solid residue in an inert hydrocarbon, an introduction to the suspension solution alkylhalogenide in an inert hydrocarbon with respect to the number of chlorine atoms in alkylhalogenide and alkoxygroup in alkoxysilane transition metal from 1.73 up to 2.06, the separation of the solid product with subsequent washing with an inert hydrocarbon and drying, when the ratio of the number of atoms of magnesium, transition metal, chlorine and alkoxygroup in the dried product from 7,2 1,0 18,9 5,4 8,2 2,0 36,2 17,1, respectively, and the content of silicon dioxide 50 62 wt. on 100 wt. the solid component of catalyst, the atomic ratio of aluminum in triethylaluminum: transition metal in the solid component 200 1.

 

Same patents:

The invention relates to components of catalysts for the polymerization of olefins, the catalysts obtained them, and their use in polymerization of olefins such as ethylene, propylene and mixtures thereof
The invention relates to the production of polyethylene of low and medium density, containing in the chain a small number of parts of butene-1

The invention relates to methods for CIS-butadiene rubber SKD and can be used in the synthetic rubber industry, and the product is used in tire, rubber, cable and other industries

FIELD: polymer materials.

SUBSTANCE: invention relates to polyethylene molding mass with multimodule molecular weight distribution intended to manufacture hollow articles such as gas tanks, canisters, barrels, and bottles using extrusion. Molding mass has density at least 0.940 g/cm3, contains low-molecular polyethylene with viscosity index 40-150 cm3/g in amount 30 to 60%, high-molecular copolymer of ethylene with another C4-C10-olefin with viscosity index 150-800 cm3/g in amount 30 to 65%, and ultrahigh-molecular polyethylene with viscosity index in the region 900-3000 cm3/g in amount 1 to 30%. Molding mass is prepared by cascade-based suspension polymerization.

EFFECT: increased degree of blowing and improved balance between hardness and fissuring resistance.

3 cl, 2 tbl, 5 ex

FIELD: organic chemistry, polymers, chemical technology.

SUBSTANCE: invention relates to technology for producing polyethylene by method of radical polymerization in mass under high pressure in the single-zone autoclave reactor. Invention describes a method for preparing polyethylene involving feeding ethylene in the single-zone reactor with stirring device and its polymerization in mass under pressure 140-230 MPa and temperature 210-265°C in the presence of chain-transferring agent - isopropyl alcohol, initiation of polymerization reaction with organic peroxides feeding as solutions in organic solvent at top and bottom parts of reactor and the following two-step separation of synthesized polyethylene from unreacted ethylene in systems of recycles of high and low pressures. Method involves using a mixture of isopropyl alcohol with glycols as the chain-transferring agent that comprise 2-5 carbon atoms in molecule, or with their derivatives - polyglycols with molecular mass 3 000 Da, not above, in the mass ratio isopropyl alcohol and glycol or polyglycol = 1:(0.05-0.25), respectively. Method provides improving strength and optical properties of synthesized polymer, reducing mass part (less 0.65%) extractable substances in it in realization the process of ethylene polymerization in the single-zone autoclave reactor, reducing intensity of gas evolving in processing the synthesized polyethylene and increase of elasticity of film made of polyethylene. Invention can be used in chemical and petroleum chemistry industry.

EFFECT: improved method for producing.

5 cl, 1 tbl, 21 ex

FIELD: polymer production and polymerization catalysts.

SUBSTANCE: invention provides and process of producing polyethylene or copolymers of ethylene with comonomers based on higher α-olefins via bringing ethylene into contact, under appropriate polymerization conditions, with catalytic system including chromium-containing catalyst, prepared in following steps: (1) interaction of inorganic oxide, namely silica-based carrier, with magnesium compound; (2) contacting resulting product with a base to form magnesium hydroxide on inorganic dioxide, namely silica; (3) drying product prepared in step (2); and (4) calcination of dry product in presence of oxygen, provided that such amount of magnesium compound being used as to provide larger surface area of the prepared catalyst than that of starting silica-containing inorganic oxide material. In thus prepared catalyst, chromium is available from following sources: (a) use, as silica-containing inorganic oxide, common silica- and chromium-containing gel from step (1); (b) adding chromium compound to dry combination of magnesium compound and silica-based carrier before calcination after step (3); (c) adding chromium compound to dried magnesium compound/silica combination before calcination; (d) adding chromium compound after calcination of silica-based carrier; or (e) adding chromium compound after drying step (3) by mixing additional magnesium compound with chromium compound solution.

EFFECT: expanded polymerization catalysts preparation possibilities.

15 cl, 8 tbl, 8 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing a photo- and thermostabilizer for preparing weatherproof polyethylene. Method for preparing photo- and thermostabilizer involves heating 2-tert.-butylphenol and methanol in autoclave in the presence of alkali and zinc oxide at temperature 220-250°C and prepared product represents a mixture comprising tert.-butylated hydroxy-exo-calyx[4]arenes and methylene-bis-phenols. For stabilizing high density polyethylene the use of a mixture of tert.-butylated hydroxy-exo-calyx[4]arenes and methylene-bis-phenols taken in the amounts 0.25-0.5% is the most effective. Photo- and thermostabilizer are prepared for a single stage by using available taw. Photo- and thermostabilizers of weatherproof polyethylene represents a mixture of tert.-butylated hydroxy-exo-calyx[4]arenes and methylene-bis-phenols and provides more effective photo- and thermostabilization as compared with using individual products as stabilizers.

EFFECT: improved preparing method.

2 tbl, 1 dwg

FIELD: chemical industry; petrochemical industry; other industries; methods and the devices for production of the oligomer of the linear alpha olefin.

SUBSTANCE: the invention is pertaining to the method of manufacture of the oligomer of the linear alpha olefin. The invention presents the method of production of the oligomer of the linear alpha olefin in the reactor containing the liquid and the gaseous phases including the phases of the catalytic oligomerization of ethylene in the presence of the complex of iron with the derivative of 2,6-bis(arylimino))pyridine up to oligomer of the alpha olefin with the average molecular-weight from 50 up to 350 with the heat release, and withdrawal of the heat by means of the heat exchanger, which is not in the direct contact with the liquid phase, with usage of at least, a part of the gaseous phase in the capacity of the coolant. The invention also presents the installation for realization of the above indicated method of production of the oligomer of the linear alpha olefin. The technical result of the invention is the effective cooling of the reaction mixture, prevention of the clogging of the cooling devices by the settlings of the paraffin and polyethylene.

EFFECT: the invention ensures the effective cooling of the reaction mixture, prevention of the clogging of the cooling devices by the settlings of the paraffin and polyethylene.

14 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: method of obtaining linear alfa-olefin oligomers in reactor, which contains liquid and gas phases, which are in equilibrium through surface of separation of gas/liquid phases, includes stages of catalytic oligomerisation of ethylene in presence of complex of nickel, palladium, cobalt, titanium, zirconium, hafnium, vanadium, chrome, molybdenum or tungsten into oligomer of alfa-olefin with average molecular weight from 50 to 350 with release of heat, and removal of heat in hear-exchanger, which is not in direct contact with liquid phase, using at least part of gas phase as cooling medium.

EFFECT: efficient prevention of heat-exchanger clogging-up.

8 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to polyethylene mixed compositions, intended for film manufacturing, which include two or more different ethylene polymers, each of which has different degree of complexity of long chain branching. Polyethylene composition is practically linear and has average index of branching constituting 0.85 or less. In addition, composition has density 0.935 g/cm3 or less, dullness - 10% or less and stability to falling load impact - 100g/mm or more, determined according to ASTM D-1709 methodology.

EFFECT: polyethylene compositions possess definite combination of required properties and characteristics, good optic properties and strengthening characteristics.

15 cl, 1 dwg, 5 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of chemical industry, in particular, to creation of highly active homogenous catalysts. Described is catalyst based on binary bridge bis(phenoximine) complex of titanium, in which as bridge between phenyl substituents of imine nitrogen it contains n - phenylene group, and corresponds to the following formula: . Described is method of preparing described above catalyst by interaction of tetradentate diimine ligand with compound of transitive metal, in which as components for ligand preparation used is 4,4"-diamino-l-terphenyl and 3,5-dicumylsalicilic aldehyde, and as compound of transitive metal used is titanium diisopropoxydichloride TiCl2(OPr)2. Described is process of ethylene polymerisation in medium of hydrocarbon solvent in presence of catalyst obtained by claimed method with co-catalyst.

EFFECT: increase of polymerisation process economy due to lower catalyst consumption; obtaining of linear polyethylene with high and extra-high molecular mass, with temperature of melting 140-142°C, improved morphology of polymer powder and absence of its adhering on reactors wall.

4 cl, 2 tbl, 17 ex

FIELD: construction.

SUBSTANCE: invention may be used to make protection elements in various equipment used for flaw detection, for medical purposes, for radioactive logging of oil and gas wells, in portable neutron generators, etc. Method includes polymerisation of ethylene on surface of elementary boron particles with average size of 3-8 mcm in presence of catalytic system immobilised on them, which consists of vanadium tetrachloride and aluminium-organic compound. First ethylene is pre-polymerised on surface of boron particles at 25-30° C and ethylene pressure of 1 at for 8-10 minutes, then temperature is increased up to 50-60°C, and ethylene polymerisation is continued at 50-60°C and pressure in the range from 1 to 10 at to produce layer of ultrahigh molecular polyethylene on them with molecular weight of at least 1·106 and thickness of 0.01-20 mcm. Radiation-protection composite material represents particles of elementary boron with polyolefin layer in the form of agglomerates of average size of 20-100 mcm.

EFFECT: produced composite material has even distribution of boron particles in polymer matrix, high strength, very high impact viscosity in wide range of temperatures, resistance to cracking and abrasion.

4 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: description is given of a catalyst system for polymerisation of ethylene, which contains: a solid component of titanium catalyst with diametre of approximately 5 to 60 microns (per 50% volume), wherein the solid component of titanium catalyst contains a titanium compound and a carrier, made from a compound of magnesium, alkylsilicate and monoester; and an organoaluminium compound with at least one aluminium-carbon bond. Also described is a solid component of titanium catalyst for producing polyethylene, which contains: a titanium compound; a carrier made from a compound of magnesium, alkylsilicate and monoester, a solid component of titanium catalyst with diametre of approximately 5 to 60 microns (per 50% volume). A method is also described for making a catalyst carrier for the said catalyst system, as well as a method of producing polyethylene, which involves polymerisation of ethylene in the presence of hydrogen and the catalyst system described above.

EFFECT: obtaining a catalyst carrier with considerable homogeneity and relatively large particles, with minimal fraction of fine particles, obtaining a solid component of titanium catalyst with high catalytic activity.

10 cl, 1 dwg, 1 tbl, 6 ex

FIELD: metalloorganic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to class of metallocene compounds of the general formula (I) wherein Y means fragment of the formula (II) wherein A means sulfur or selenium atom; B means carbon atom; D means carbon atom; R1, R2, R3, R4 and R5 mean hydrogen atom or hydrocarbon groups; Z is taken among fragment of the formula (II) and fragment of the formula (III) wherein R6, R7, R8 and R9 mean hydrogen atom or hydrocarbon groups; L means bivalent bridge group; M means zirconium atom; X means halogen atom; p = 2. Above described metallocenes are useful especially for polymerization of propylene.

EFFECT: improved preparing method, valuable properties of metallocenes.

15 cl, 5 tbl, 18 ex

FIELD: polymerization catalysts.

SUBSTANCE: catalyst is prepared by mixing hydrocarbon solutions of titanium tetrachloride, triisobutylaluminum-diphenyl oxide complex, and 1,3-pentadiene at Al/Ti molar ratio from 0.9:1 to 1.2:1 and at temperature form -70 to +20°C, after which mixture of paraffin, aromatic, and naphthene hydrocarbons is added, in particular industrial or transformer oil in amount 0.05 to 2% on the weight of catalyst suspension.

EFFECT: increased catalytic activity and reduced dosage of catalyst in polymerization process, which allows production of rubber with reduced titanium compound level without increasing intensity of washing away titanium compounds.

2 cl, 1 tbl, 11 ex

FIELD: polymer production.

SUBSTANCE: invention provides homogenous catalytic system for synthesis of copolymers and terpolymers of olefinic monomers, which system contains dialkyl bridge-type bis(indenyl)metallocene complexes with group IVB metals and trialkylaluminum at Al-to-metal ratio between 50 and 500. Catalytic system enables carrying out polymerization process at rates significantly exceeding ethylene or propylene homopolymerization rate.

EFFECT: significantly accelerated copolymerization process and achieved fractional and compositional homogeneity of ethylene/α-olefin and propylene/α-olefin copolymers.

1 tbl, 16 ex

Up!