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


C08F4/652 -

 

(57) Abstract:

A solid component of catalyst for polymerization and copolymerization of ethylene, containing magnesium, halogen and titanium, obtained by (i) dissolving in an inert organic solvent dialkylamide or alkylpolyglucoside, tin halide (IV) and possibly also alkylhalogenide and their contact up until a granular solid substance will not precipitate from solution; (ii) contact the specified granular solids and their interaction with halide, alcoholate or halogen-alcoholate of titanium with the formation of a solid component of catalyst. 3 S. and 6 C.p. f-crystals, 1 Il.

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

It is well known that the polymerization of ethylene or alpha-olefins can be carried out using the process of low pressure with catalysts of the Ziegler-Natta. These catalysts consist mainly of elements of groups IV-VI of the Periodic system of elements (transition metal compounds), mixed with the ORGANOMETALLIC compound or hydride of elements of groups I to III of the Periodic System.

1R2or MgR3X with R4(4-n)SiCln, where R1, R2, R3and R4represent alkyl groups, and X is halogen. Eaborn C. E. in "Organo Silicon Compounds", Butterworths Scientific Pubblications", London, 1960; Rochow, E. G. in "Chemistry of Silicon"what mangalavanam and silicon tetrachloride, which gives a noncrystalline solid connection. Similarly, T. Am.Chem.Soc. Vol.67, page 540, 1945; T. Am.Chem.Soc. Vol. 76, page 1169, 1954; and T. Organometallic Chem. Vol.6, page 522, 1966, describe the alkylation reaction between alkalinisation and tin tetrachloride is used.

According to the invention it was found that the solid product of the interaction between dialkylamines or alkalinisation and chloride of tin or alkylolamides capable of interacting with the compound of titanium with the formation of a solid component of catalyst that is highly active in the polymerization and copolymerization of ethylene, and the ratio of tetravalent titanium in the titanium in the trivalent state is defined as the ratio between tin and magnesium in the solid substance and the concentration of titanium in the above interactions.

In accordance with this aspect of the invention relates to a solid catalyst component for polymerization and copolymerization of ethylene, containing magnesium, halogen and titanium, obtained by:

(i) dissolving in an inert organic solvent dialkylamide or alkilani of halide, tin halide (IV) and possibly also alkylhalogenide when the atomic ratio m is 15:1, and when the molar ratio between alkylhalogenide and tin halide, 0: 1 to 10:1, and their contact up until a granular solid substance will not precipitate from solution;

(ii) contacting the specified granular solids and its interaction with the titanium halide, alcoholate or halogen-alcoholate in the atomic ratio between the magnesium in granular solid substance and the titanium compound is titanium, varying from 0.01:1 to 60:1, with formation of a solid catalyst component.

In accordance with one of the preferred embodiments in the solution phase (i) optionally introducing a measured quantity of at least one compound of metal M selected from vanadium, zirconium and hafnium, receiving the solid components of catalysts suitable for the production of polymers and copolymers of ethylene with a wide molecular weight distribution.

In accordance with another preferred embodiment of the deposition stage (i) is carried out in the presence of solid substances in the form of particles, preferably of silicon oxide, getting dealt a solid component of catalyst.

At stage (i) of the invention granular solid Villalonga in an inert organic solvent.

Dialkyl magnesium, suitable for the purpose of the invention, are compounds that can be determined by the formula MgR'R", where R' and R" are the same or different, each independently of the other, represent an alkyl group, linear or branched, containing from 1 to 10 carbon atoms. Specific examples diallylamine are determine, ethylbutylamine, directimage, butylaniline and dioctylamine. You can also use the corresponding halides, especially chlorides, alkaline.

The halides of tin, suitable for purposes of the invention are the chlorides and bromides of tin, and preferably use the tin tetrachloride is used.

Alkylhalogenide suitable for purposes of the invention are primary, secondary and tertiary alkylchloride and were synthesized, in which the alkyl group contains from 1 to 20 carbon atoms. Specific examples of alkylhalogenide are ethylbromide, butyl chloride, vexilloid, artilharia and cyclohexylurea.

Suitable solvents for dissolving the above compounds are liquid under the operating conditions of organic solvents which are inert (not active) in relation to other components. Examples polhodes, heptane and octane.

Stage (i) may be accomplished through the preparation of a solution dialkylamide or alkylpolyglucoside and possibly alkylhalogenide in the selected organic solvent, adding to this solution of tin halide and maintain contact at a temperature equal to -30oC to +30oC in order to cause precipitation of granular solids. In practice, working in the above conditions, almost complete precipitation receive for a period of time equal to 0.5 5 o'clock

Granular solid matter deposited in the sediment at the stage (i), conveniently separated from the liquid phase and washed thoroughly with inert liquid solvent, particularly a hydrocarbon solvent such as hexane and heptane.

At stage (ii) obtained as described above, the solid is brought into contact, and it interacts with the connection of titanium selected from the halides of titanium, alcoholate or halogen-alcoholate. Specific examples of these compounds are titanium tetrachloride, tetrabromide titanium, Tetra-n-propylate titanium, Tetra-n-butyl titanium, Tetra-isopropyl titanium, Tetra-ISO-butyl titanium and the corresponding mono - or di - chloro -, and mono or di-bromo-alcedinidae titanium is titanium tetrachloride.

At stage (ii) granular solid is suspended in an inert organic solvent such as a hydrocarbon solvent, aliphatic type, such as hexane, heptane, octane, etc., and to the suspension is added a compound of titanium, possibly dissolved in the same or a similar solvent. Thus obtained suspension is maintained at a temperature of 50 to 100oC, and preferably 60 to 90oC over a period of time equal to 0.5 -5 hours, preferably 1-2 hours Thereby obtaining a solid component of catalyst, which can be distinguished from the specified suspension, for example, viparita organic solvent at atmospheric or reduced pressure.

When it is desirable to obtain polyethylene having a broader molecular weight distribution, to a solution of stage (i) add at least one compound of the metal M, selected from vanadium, zirconium and hafnium. The compound of the metal M can be added in the form of a solution in a suitable organic solvent, such as complex alkilany ether, such as ethyl acetate. Suitable compounds for this purpose are the halides, halogenated, alcoholate or halogen-alcoholate with a preference halides, such to apnea. In this way the atomic ratio between the magnesium introduced with dialkylamines or alkalinisation, and the amount of titanium and the metal or metals M varies from 1:1 to 30:1 and the atomic ratio of titanium and the metal or metals M varies from 0.1:1 to 2:1.

When the desired deposited solid component of catalyst in the solution phase (i) suspended granular solid carrier, preferably microspherical silica, so that the deposition stage (ii) is carried out in the presence of the media itself.

Using studies of x-ray radiation observed that, when in accordance with the invention in the deposition reaction stage (i) use the tetrachloride of tin and dialkylamino formed solid product (media), consisting of MgCl2(in its alpha and Delta forms), along with the connection with unknown structure and having a range of x-ray radiation corresponding to presented on the attached drawing. The relative amount of both forms of media, both known and unknown, depend on the ratios between the reagents dialkylamines and tin tetrachloride is used, which interact on stage (i) ways and affect the reaction is capable of is Ethan and quite unexpectedly, the ratio between the amount of titanium in the trivalent and tetravalent state. The amount of titanium, which is associated with the medium on the stage (ii), also depends on the concentration of the compound of titanium on the specified stage (ii). On the other hand, the ratio of tetravalent and trivalent form in the docked Titan, apparently, to a large extent dependent on the concentration of titanium in stage (ii). Finally, it was found that the activity shown by the solid component of catalyst obtained at the end of stage (ii), during polymerization increases when decreasing the amount of titanium, fixed on the carrier.

This leads to the conclusion that both known and unknown forms of media to give a solid component of catalyst required properties and mainly high catalytic activity in the polymerization and copolymerization of ethylene.

The invention also relates to catalysts for the polymerization and copolymerization of ethylene, comprising the above solid catalyst component in combination with an ORGANOMETALLIC compound of aluminium (co-catalyst), which can be selected from trialkyl aluminum halides (preferably chlorides) alkylamine containing from 1 to 6 carbon atoms in the alkyl part. Among these trialbuy tridecylamine. In the catalyst the atomic ratio between aluminum (co-catalyst) and titanium (solid catalyst component) typically varies from 0.5:1 to 1000:1 and preferably from 50:1 to 200:1.

These catalysts are highly active in the polymerization of ethylene and copolymerization of ethylene with alpha-olefins and can be used in a fluidized bed or mixed layer in polymerization carried out by or through suspension technology in an inert diluent, or in gas phase.

Alpha-Olefins that can be copolymerizate, are usually compounds containing 3 to 15 carbon atoms, such as butene-1, hexene-1, 4-methylpentene-1, octene-1, undecene-1, 1,4-hexadiene and ethylidene norbornene. The usual polymerization conditions are a temperature of 50 100oC, the total pressure of 5 to 40 bar with a ratio between the partial pressures of hydrogen and ethylene, 0 to 10.

In all cases there is a high performance polyolefin and the polymer thus obtained has excellent rheology and, in addition, is in the form of non-fragile granules with a narrow size distribution of particles.

Example 1. 240 ml of 20% weight butylacrylamide loaded into the flask with a capacity of 500 ml, equipped with reflux condenser, mechanical stirrer and thermometer. The tetrachloride of tin added for a period of time equal to 15 minutes at -20oC. the Mixture over 1 hour left to interact with -20oC, and then slowly (1.5 h) bring to the 20oC. the Precipitated solid is separated by filtration, washed thoroughly with n-hexane and dried by evaporation of the solvent. Obtain 28.6 g of a carrier containing 16.4 wt. magnesium and 49.7 wt. chlorine.

10 g of the thus obtained carrier at the 90oC for 1 h, treated with 100 ml of titanium tetrachloride (172 g, 907 mmol). The solid is separated by filtration, washed thoroughly with n-hexane, and then dried by evaporation of solvent.

Gain of 5.3 g of solid catalyst component containing 17.6 wt. magnesium, 66,7 wt. chlorine and 6.5 wt. titanium, 48% of which is in the form of trivalent titanium.

A solid component of catalyst obtained as described above, is used in the test for the polymerization of ethylene. More specifically, the polymerization is carried out in an autoclave having a volume of 5 l, containing 2 liters of n-hexane, using 500 mg of solid component of catalyst and 7 mmol of triethylaluminum in Yeni, equal to 1.5 h, in the presence of hydrogen with a ratio between the pressures of hydrogen and ethylene, equal 0,86.

Get the output, equal to 8.4 kg of polyethylene per 1 g of solid catalyst component and the polyethylene thus obtained has the following properties:

Density (ASTM D-1505) 0,9631 g/ml

MFI (2,16 kg) 3.7 g/10'

(Melt flow index ASTM D-1238)

MFR 27,8

(MFR ratio of melt flow, defined as the ratio of MFI (21,6 kg) and MFI (2,16 kg)

Apparent density (ASTM D-1895) of 0.38 g/ml

In addition, polyethylene is in the form of granules having the following distribution of particle size, microns:

>2000 to 1.2 wt.

2000< >1000 6.6 wt.

1000< >500 7.4 wt.

500< >250 of 17.7 wt.

250< >125 38.5 wt.

125< >63 24.6 wt.

<63 6.0 wt.

Example 2. 18 g of the carrier obtained as described in example 1, are suspended in 100 ml of n-heptane, and to the suspension is added 0.55 g of titanium tetrachloride (2.9 mmol). Contact is maintained for 1 h at 90oC, and then the slurry is dried, viparita solvent.

Obtain 9.5 g of a solid catalyst component containing, by weight. magnesium 16,6; chlorine 52,0; titanium 1,4, 40% of which is of usator used in the test for the polymerization of ethylene. More specifically, the polymerization is carried out, working in an autoclave having a volume of 5 l, containing 2 liters of n-hexane, using 25 mg of solid component of catalyst and 7 mmol of triethylaluminum as a co-catalyst. Operating temperature is 90oC, the total pressure of 15 bar, for a period of time equal to 1.5 h, in the presence of hydrogen, with a ratio between the pressures of hydrogen and ethylene, equal 0,86.

Get the output, equal to 12.6 g of polyethylene per 1 g of solid component of catalyst, and the resulting polyethylene has the following properties:

Density 0,9590 g/ml

MFI (2,16 kg) 1.68 g/10'

MFR 68,8

The apparent density of 0.35 g/ml

In addition, polyethylene is in the form of granules, with the following distribution of particle size, microns:

>2000 1.4 wt.

2000< >1000 5.1 wt.

1000< >500 to 10.1 wt.

500< >125 35.5 wt.

125< >63 16.5 wt.

<63 3.2 wt.

Example 3. 480 ml of a solution of 20 wt. butylaniline (Mg1But1,5Oct0,5; 7060 g, 420 mmol) in n-heptane and 4.9 ml of tin tetrachloride (1069 g, 42 mmol) under nitrogen atmosphere loaded into the flask with a capacity of 1000 ml equipped with a reflux condenser, mechanical stirrer and thermometer. The tetrachloride is>C for 1 h, and then slowly (1.5 h) bring to the 20oC. the Solid precipitate was separated by filtration, washed thoroughly with n-hexane and dried by evaporation of the solvent. Gain of 8.2 g of a carrier containing 21.8 wt. magnesium and 49.5 wt. chlorine.

7.0 g thus obtained carrier is suspended in 130 ml of n-heptane, and suspension add value (0.475) g of titanium tetrachloride (2.5 mmol). Contact support at the 90oC for 1 h, and then the slurry is dried, viparita solvent.

Thus obtain 6.6 g of a solid catalyst component containing 22,7 wt. magnesium, 5.7 wt. chlorine and 1.5 wt. titanium is completely in the tetravalent form.

Obtained in accordance with the above-described solid catalyst component used in the test for the polymerization of ethylene. More specifically, the polymerization is carried out in an autoclave having a volume of 5 l, containing 2 liters of n-hexane, using 50 mg of solid component of catalyst and 1.5 mmol of triethylaluminum as a co-catalyst. Operating temperature 90oC, the total pressure of 15 bar, for a period of time equal to 1.5 h, in the presence of hydrogen, with a ratio between the pressures of hydrogen and ethylene, equal 0,86.

Get wihout the following properties:

Density 0,9601 g/ml

MFI (2,16 kg) 2.25 g/10'

MFR 30,0

The apparent density of 0.20 g/ml

In addition, polyethylene is in the form of granules, with the following distribution of particle size, microns:

>2000 to 14.8 wt.

2000< >1000 32,0 wt.

1000< >500 to 26.2 wt.

500< >250 17,2 wt.

250< >125 8.2 wt.

125< >63 1.2 wt.

<63 0.4 wt.

Example 4. 250 ml of a solution of 20 wt. butylaniline (Mg1But1,5Oct0,5; 25,0 g, 210 mmol) in n-heptane and 100 ml of tin tetrachloride (222 G6 852 mmol) under nitrogen atmosphere loaded into the flask with a capacity of 1000 ml equipped with a reflux condenser, mechanical stirrer and thermometer. The tetrachloride of tin added for a period of time equal to 25 min at -20oC. the Temperature is brought to 70oC, and the mixture is left to interact for 1 h Solid precipitate was separated by filtration and thoroughly washed with n-heptane.

Thus obtained carrier is suspended in 200 ml of n-heptane, and suspension add 1,72 g of titanium tetrachloride (9.1 mmol). Contact support at the 90oC for 2 h, and then the slurry is dried, viparita solvent.

Thus obtain 28.6 g of solid component of catalyst, the soda is consistent with the above solid catalyst component used in the test for the polymerization of ethylene. More specifically, the polymerization is carried out in an autoclave having a volume of 5 l, containing 2 liters of n-hexane, using 50 mg of solid component of catalyst and 1.0 mmol of triethylaluminum as a co-catalyst. A solid component of catalyst loaded into the reactor together with 4.5 bar of hydrogen at 30oC. the Reactor for 30 min cook until stationary conditions, feeding ethylene up to a total pressure of 15 bar, and elevating the temperature to 90oC. under these conditions the polymerization continued for 60 minutes

Get the output, equal to 2.1 kg of polyethylene per 1 g of solid component of catalyst, and the resulting polyethylene has the following properties:

Density 0,9515 g/ml

MFI (2,16 kg) 0,61 g/10'

MFR 24,7

Example 5.90 ml 20 wt. butylaniline (Mg1But1,5Oct0,5; 13,1 g of 78.8 mmol) in n-heptane, 80 ml of n-heptane and of 6.31 g of hafnium tetrachloride (19.7 mmole) under nitrogen atmosphere loaded into the flask with a capacity of 500 ml, equipped with a reflux condenser, mechanical stirrer and thermometer. The contents of the flask for 14 min, heated to 40oC, then brought to -20oC and for a period of time equal to 30 minutes, add 18.8 ml of tin tetrachloride (41,4 g, 158 mmol). Temperature for a period of time, p is the filtered and thoroughly washed with n-heptane.

The washed solid is suspended in 200 ml of n-heptane, and the suspension type of 3.78 g of titanium tetrachloride (to 19.9 mmol). Contact leave for 1 h at 90oC, and then the slurry is dried, viparita solvent.

Get 17,5 g of solid catalyst component containing 9.6 wt. magnesium, 46,9 wt. chlorine, of 0.12 wt. titanium, 48% of which is in the form of trivalent titanium, and 20 wt. hafnium.

Prepared in accordance with the above-described solid catalyst component used in the test for the polymerization of ethylene.

More specifically, the polymerization is carried out, working in an autoclave having a volume of 5 l, containing 2 liters of n-hexane, using 150 mg of solid component of catalyst and 3.0 mmole of triethylaluminum as a co-catalyst. Working conditions are a temperature of 90oC, with a total pressure of 15 bar, for a period of time equal to 3 h in the presence of hydrogen, with a ratio between the pressures of hydrogen and ethylene, equal to 1.4.

Get the output, equal to 1.7 g of polyethylene per 1 g of solid catalyst component, and the thus obtained polyethylene has the following properties:

Density 0,9482 g/ml

MFI (2,16 kg): 0,46 g/10'

Apparent density of 0.29

2000< >1000 of 14.0 wt.

1000< >500 to 22.0 wt.

500< >250 of 25.2 wt.

250< >125 of 23.1 wt.

125< >63 5.6 wt.

<63 0.4 wt.

Example 6. 4.4 g of hafnium tetrachloride (13.7 mmol) and 220 ml of ethyl acetate under nitrogen atmosphere loaded into the flask with a capacity of 1000 ml equipped with a reflux condenser, mechanical stirrer and thermometer. Temperature for 1 h, brought to 77oC as long as the hafnium salt is dissolved, then add 17 g microspherical silica, and the mixture is left to interact with 77oC for 1 h and Then it is dried, viparita solvent. To the thus obtained solid substance add 165 ml of n-heptane and 63 ml of a solution of 20 wt. butylaniline (Mg1But1,5Oct0,5; 9,18 g, with 55.1 mmol) in n-heptane. The reaction mixture is kept at 60oC for 30 min, then the solid is separated by filtration and thoroughly washed with n-heptane.

The washed solid is suspended in 160 ml of n-heptane and suspension for a period of time equal to 30 minutes, at 25oC add 55 ml of tin tetrachloride (122 g, 469 mmol). Suspension support in contact with 80oC for 1 h, the solid is then separated from Phi the keys 160 ml 7-heptane and 2.75 g of titanium tetrachloride (14.5 mmol). Contact is maintained with the 90oC for 2 h, and then the mixture is dried, viparita solvent.

So get 24,8 solid catalyst component containing 3.3 wt. magnesium, 14.9 wt. chlorine, 2.5 wt. titanium, fully in tetravalent form, and 10 wt. hafnium.

Prepared in accordance with the above-described solid catalyst component used in the test for the polymerization of ethylene. More specifically, the polymerization is carried out, working in an autoclave having a volume of 5 l, containing 2 liters of n-hexane, using 100 mg of solid component of catalyst and 1.5 mmol of triethylaluminum as a co-catalyst. operating temperature 80oC with a total pressure of 15 bar, for a period of time equal to 4 h in the presence of hydrogen with a ratio between the pressures of hydrogen and ethylene, equal to 0.2.

Get the output, equal to 7.8 kg of polyethylene per 1 g of solid component of catalyst, and the resulting polyethylene has the following properties:

Density 0,9515 g/ml

MFI (2,16 kg) 0.05 g/10'

MFR 74,6

Apparent density of 0.38 g/ml

In addition, polyethylene is in the form of granules, with the following distribution of particle size, microns:

>2000 0.1 wt.

2000< >1000 23 0.3 wt.

<63 0.0 wt.

Example 7. A solid component of catalyst was prepared by working as described in example 6, but using 6.5 ml of tin tetrachloride (14.4 g, a 55.4 mmol).

Get to 31.8 g of solid catalyst component containing 3.1 wt. magnesium is 14.5 wt. chlorine, 2.8 wt. titanium, fully in tetravalent form and 11 wt. hafnium.

Obtained in accordance with the above-described solid catalyst component used in the test for the polymerization of ethylene. More specifically, the polymerization is carried out, working in an autoclave having a volume of 5 l, containing 2 liters of n-hexane, using 150 mg of solid component of catalyst and 5.0 mmol of triethylaluminum as a co-catalyst. Operating temperature 80oC with a total pressure of 15 bar, for a period of time equal to 4 h in the presence of hydrogen with a ratio between the pressures of hydrogen and ethylene, is 0.45.

Get the output, equal to 2.9 kg of polyethylene per 1 g of solid component of catalyst, and the resulting polyethylene has the following properties:

Density 0,9591 g/ml

MFI (2,16 kg) 0.14 g/10'

MFR 67,9

The apparent density of 0.40 g/ml

In addition, polyethylene is in the form of granules, with the following distribution razmara is,0 wt.

250< >125 2.2 wt.

125< >63 0.3 wt.

<63 0.0 wt.

1. A solid component of catalyst for the (co)polymerization of ethylene, providing a product of the interaction of compounds of magnesium, tin and titanium, characterized in that it is obtained by the sequential dissolution diallylamine and tetrachloride tin in an inert organic solvent at a molar ratio of 1 0,1 8,5 respectively before the formation of granular sludge with subsequent introduction into a slurry of the granular precipitate of titanium tetrachloride in a molar ratio of magnesium and titanium 0,07 25 1 emitting solid product.

2. Component under item 1, characterized in that it is obtained with a preliminary interaction dialkylamide with tetrachloride hafnium at a molar ratio of 1 4 4 1 respectively.

3. Component under item 2, characterized in that it is obtained when using hafnium tetrachloride supported on a carrier microspherical silica.

4. The catalyst for the (co)polymerization of ethylene, comprising a solid component, which is a product of the interaction of compounds of magnesium, tin and titanium, and alyuminiiorganicheskikh connection, characterized in that the solid component Alchymist fact, what it contains as a solid component, the solid component of catalyst for the (co)polymerization of ethylene under item 2.

6. The catalyst p. 5, characterized in that it contains as a solid component, the solid component of catalyst for the (co)polymerization of ethylene under item 3.

7. The method of obtaining the (co)polymers of ethylene by polymerization of ethylene or copolymerization of ethylene with alpha-olefins in the presence of a catalyst comprising a solid component, which is a product of the interaction of compounds of magnesium, tin and titanium, and alyuminiiorganicheskikh connection, characterized in that as the catalyst use of catalyst for the (co)polymerization of ethylene under item 4.

8. The method according to p. 7, wherein the process is carried out in the presence of a catalyst (co)polymerization of ethylene under item 5.

9. The method according to p. 8, wherein the process is carried out in the presence of a catalyst (co)polymerization of ethylene under item 6.

 

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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

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