RU2258711C2 - Supported ethylene (co) - Google Patents

Abstract

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[R² _bX_(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

Description

Technical field

The present invention relates to a highly active supported titanium-based catalyst suitable for the (co) polymerization of olefins, in particular, the (co) polymerization of ethylene using the gas-phase process, to its preparation and use.

BACKGROUND OF THE INVENTION

It is well known that in vanadium-based catalysts for the polymerization of olefins, halogenated hydrocarbons are used as promoters of activity, and there are several patents affecting their use. For example, vanadium-based catalysts developed by Union Carbide Corporation were successfully used for industrial production of polyethylene using a gas-phase method, the key point being the inclusion of halogenated hydrocarbons as promoters, which resulted in an improvement in the activity of vanadium-based catalysts in 4-10 time. In addition, US 4508842 and CN 87107589A describe the use of CFCl ₃ and the like as promoters; EP 286001 describes the use of CH ₂ Cl ₂ or CF ₂ ClCFCl ₂ as promoters; and US 4,892,853 describes the use of hexachloropropane or octachloropropane as promoters. In particular, Chinese Patent Application Publication No. CN 1056107A describes a vanadium-based catalyst obtained by depositing a promoter on a carrier and securing it by chemical bonding, where the promoter is chemically bonded to said catalyst by a halogenated alcohol reaction together with hydroxyl groups on surface of silicon dioxide, and organic compounds of aluminum, thus promoting the activity of the vanadium center.

As a result of studying the promoting effect of halogenated hydrocarbons on vanadium-based catalysts, Union Carbide Corporation researchers found that the activity of a titanium center can only promote CH ₂ Cl ₂ , and most halogen hydrocarbons, such as CFCl ₃ , CHCl ₃ , CCl ₄ , a titanium center in significantly inhibit and significantly reduce catalytic activity [Polymer Material Science and Engineering, pp. 106-107 (1991)]. The synthesis of polyethylene with bimodal or wide molecular weight distribution (MMP) using titanium / vanadium bimetallic catalysts is also based essentially on the inhibitory effect of CFCl ₃ , CHCl ₃ and the like on the titanium center [US 5442018].

However, this is not always the case, as demonstrated by the catalysts described for publication of Chinese patent application No. CN 1189505A. The said catalyst uses halocarbons described by the general formula R _a CX _(4-a) (where R is hydrogen, unsubstituted or halogen-substituted alkyl groups containing less than 6 carbon atoms, X is fluorine, chlorine or bromine, and a is a whole number less than 4). With a suitable molar ratio of halogenated hydrocarbons to titanium, the catalytic activity of commonly used Ziegler-Natta titanium center catalysts can be improved by 50-100% if ethylene is used in the gas phase polymerization. However, since halogenated hydrocarbons are added to the polymerization reactor separately, one obvious drawback will be the additional step necessary to add the halogenated hydrocarbons to the polymerization reactor with its attendant problems of inaccurate feeding, mixing problems, contacting with other catalyst components and the like. After extensive research by the present inventors, it has been found that in a titanium-based catalyst, using the silica support material, the halide promoter of the present invention becomes a component of the molecular structure of the catalyst composition as a result of the formation of a chemical bond with silicon dioxide due to passage chemical reaction between said promoter and hydroxyl groups on the surface of silicon dioxide, and, cr IU, the amount of promoter deposited on the carrier can be controlled by adjusting the temperature and time of thermal activation of the support material. Therefore, in order to obtain the promotion effect of the halide, there is no need to add halogenated hydrocarbons to the polymerization reactor from the outside, and thus, the disadvantages that distinguish the prior art can be overcome.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a highly active supported titanium-based catalyst suitable for (co) polymerizing ethylene, which overcomes the disadvantages associated with the prior titanium-based supported silicon dioxide catalyst, and which is obtained by applying a halide promoter to the support material. If the catalyst is used for the polymerization of ethylene, then not only the catalytic activity is significantly improved, but also the morphology of the particles of the resulting polymer is further improved, and the bulk density appreciably increases.

Another objective of the present invention is to provide a method for producing a catalyst of the present invention.

Another objective of the present invention is to propose the use of a catalyst of the present invention for the (co) polymerization of olefins.

In one aspect, the present invention provides a highly supported supported titanium-based catalyst suitable for (co) polymerizing ethylene, comprising:

A. supported on a carrier catalyst component, which is a titanium-containing active component deposited on an inert carrier material containing at least one titanium compound, at least one magnesium compound, at least one halide promoter, at least one electron donor compound and at least one porous inert carrier material; and

B. aluminum alkyl cocatalyst.

In a second aspect, the present invention provides a method for preparing a supported catalyst component of the present invention, comprising dissolving the aforementioned titanium compound and a magnesium compound in an electron donor compound, thereby obtaining a mother liquor, and then applying said compounds to an inert carrier material using impregnation.

In a third aspect, the present invention relates to the use of a catalyst according to the present invention for the (co) polymerization of olefins.

DETAILED DESCRIPTION OF THE INVENTION

In the aforementioned catalyst component A, a magnesium compound, an electron donor compound, a titanium compound and an inert support porous material are described in US 4302565, which is incorporated herein by reference for reference.

In the aforementioned catalyst component A, the halide promoter is a class of compounds described by the general formula FR ¹ [R ² _b X _(3-b) ], where:

F is an oxygen-containing functional group that is reactive with an organoaluminum compound, a titanium compound or hydroxyl groups such as aldehyde groups, acyl groups, hydroxyl groups and the like; R ¹ represents a divalent C ₁ -C ₆ aliphatic or aromatic group that is attached to an oxygen atom in the functional group F; R ² is hydrogen, unsubstituted or halogen-substituted C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl or C ₆ -C ₁₀ aromatic groups, b is 0, 1 or 2, and X is F, Cl or Br.

If F is a hydroxyl group, then the promoter is a halogenated alcohol, with specific compounds being 2,2,2-trichloroethanol, 2,2-dichloroethanol, 2-chloroethanol, 1,1-dimethyl-2,2,2 trichloroethanol, 4-chlorobutanol, para-chlorophenol, iso-chlorophenol, ortho-chlorophenol, 2-chlorocyclohexanol and the like, with 2,2,2-trichloroethanol, 2,2-dichloroethanol, 2-chloroethanol and 1,1- dimethyl-2,2,2-trichloroethanol is preferred.

If F is an acyl group, said promoter belongs to the class of halogenated atsilgalogenangidrida, and suitable examples of such compounds are trihloratsetilhlorangidrid, dihloratsetilhlorangidrid, hloratsetilhlorangidrid, o-hlorbenzoilhlorangidrid hlortsiklogeksilkarbonilhlorangidrid and 2, wherein trihloratsetilhlorangidrid, and dihloratsetilhlorangidrid hloratsetilhlorangidrid preferred.

In the above-mentioned catalyst component A, preferred titanium compounds are those described by the general formula Ti (OR) _4-n X _n , where R is a C ₁ -C ₁₄ aliphatic hydrocarbon group, X is a group selected from the group consisting of F, Cl, Br, and mixtures thereof, and n is 0, 1, or 2. Suitable examples are selected from the group consisting of titanium tetrachloride, titanium trichloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, triethoxy titanium chloride, diethoxy titanium dichloride, trichl methoxide titanium, ethoxy titanium trichloride and mixtures thereof, with titanium tetrachloride, ethoxy titanium trichloride and the like are preferred.

Magnesium compounds that can be used are preferably those described by the general formula MgX ₂ , wherein X is a group selected from Cl, Br, I, or mixtures thereof. Specific examples may be magnesium dichloride, magnesium dibromide, magnesium diiodide, with magnesium dichloride being preferred.

The electron donor (ED) compound that can be used is preferably selected from the group consisting of alkyl esters of aliphatic or aromatic carboxylic acids, aliphatic ethers, cyclic ethers, and aliphatic ketones. Among them, C ₁ -C ₄ saturated aliphatic carboxylic acid alkyl esters, C ₇ -C ₈ aromatic carboxylic acid alkyl esters, C ₂ -C ₆ aliphatic ethers, C ₃ -C ₄ cyclic ethers, C ₃ -C are preferred ₆ saturated aliphatic ketones. Most preferred are methyl formate, ethyl acetate, butyl acetate, diethyl ether, dihexyl ether, tetrahydrofuran (THF), acetone and methyl isobutyl ketone. These electron donor compounds can be used individually or as a mixture thereof, consisting of two or more components.

The support material is a particulate solid porous material that contains a certain amount of hydroxyl groups on its surface, with dehydrated silica being preferred. The preferred carrier material is silica particles characterized by an average particle diameter of 20-80 μm, a pore volume of 1.5-5 ml / g, a specific surface area of 230-350 m ² / g and an average pore diameter of 18-40 nm; the most preferred silica is characterized by an average particle diameter of 50 μm, a pore volume of 1.6 ml / g and a specific surface area of 300 m ² / g.

In the titanium-containing catalyst component A of the present invention, the magnesium compound, the electron donor compound and the halide promoter are used in amounts of from 0.5 to 50 moles, preferably from 1.5 to 5 moles; from 0.5 to 50 moles, preferably from 1 to 10 moles; and from 0.1 to 50 moles, preferably from 0.5 to 10 moles per mole of titanium compound, respectively.

Component B that can be used is alkylaluminum described by the formula AlR ₃ , where R may be the same or different, and they are C ₁ -C ₈ alkyl groups, and one or two of the alkyl groups may be substituted with chlorine. Preferred examples are selected from the group consisting of AlEt ₃ , Al (iso-Bu) ₃ , Al (n-C ₆ H ₁₃ ) ₃ , Al (n-C ₈ H ₁₇ ) ₃ and AlEt ₂ Cl. The above-mentioned alkylaluminum can be used individually or in combination.

The catalyst component of the present invention is preferably prepared using a process comprising the steps of:

(1) activating the carrier material in the usual manner, preferably by dehydration at 600 ° C. for 4 hours;

(2) adding a thermally activated carrier material to a lower alkane-based solvent, followed by adding an aluminum alkyl compound and then reacting the mixture for a certain period of time, after which the solvent is evaporated and dried, thereby obtaining a solid powder;

(3) dissolving the titanium compound and the magnesium compound in the electron donor compound to obtain a mother liquor, where the titanium compound is added to the electron donor compound before or after the magnesium compound is added, or both the titanium compound and the magnesium compound are added simultaneously;

(4) adding the carrier material activated in step (2) to the mother liquor from step (3) and carrying out the reaction between them for a certain period of time, followed by drying to remove excess solvent, i.e., an electron donor compound, to obtain, thus solid material;

(5) suspending the solid material from step (4) in a lower alkane-based solvent and then reducing it with one or more aluminum alkyl compounds, followed by drying, thereby obtaining the final catalyst component;

wherein said halide promoter is included in the catalyst component A as a result of i) adding during the processing of the support material in the aforementioned step (2), ii) adding during the application of the catalyst complex from the said step (3) to the support material and iii) adding during the reduction catalyst in the aforementioned step (5).

The lower alkane solvents used in step (2) and step (5) may be C ₃ -C ₉ alkanes, preferably C ₅ and C ₆ alkanes, such as isopentane, pentane, hexane and the like.

The aluminum alkyl compounds that can be used in step (2) and step (5) are preferably compounds described by the general formula AlR ′ _m X _3-m , where R ′ may be the same or different and they are C ₁ -C _{8 is an} alkyl group, X is halogen, m is an integer in the range of 1 to 3. Preferred aluminum alkyl compounds are AlEt ₃ , Al (n-C ₆ H ₁₃ ) ₃ , AlEt ₂ Cl and the like.

It should be especially noted that the halide promoter of the present invention can be incorporated into the catalytic component A by any effective method. For example, an excellent promoting effect can be achieved using one of the following methods: i) adding during the processing of the carrier material in the aforementioned stage (2), ii) adding during the application of the catalytic complex from the aforementioned stage (3) to the carrier material and iii) adding during catalyst reduction in the aforementioned step (5).

The catalyst according to the present invention is suitable for homopolymerization of ethylene and copolymerization of ethylene and α-olefins, the α-olefins being olefins containing 3-10 carbon atoms, such as propylene, butene-1, hexane-1, 4-methylpentene-1 , octane-1 and the like. The polymerization reaction can be carried out in an inert solvent using the suspension method or the gas phase method. The polymerization temperature may be in the range from 50 ° C to 100 ° C. Since the halide promoter is applied to the catalyst support in the catalyst of the present invention, the resulting catalyst is more suitable for the gas phase polymerization of ethylene, and it can exhibit excellent properties.

Compared to the prior art catalysts, the ethylene gas phase polymerization catalyst system of the present invention is obtained by chemically bonding a halide promoter and is suitable for all Ziegler-Natta catalysts with a titanium center. In addition, the promoter can be incorporated into the catalytic component A by any effective method. For example, an excellent promotion effect can be achieved using one of the following methods: i) adding a promoter during processing of the support material in the aforementioned step (2), ii) adding a promoter during the application of the catalytic complex from the above step (3) to the support material and iii ) adding a promoter during catalyst reduction in the aforementioned step (5). More specifically, if a 2,2,2-trichloroethanol or trichloroacetyl chloride is used as a promoter, an excellent promoter effect can be achieved with a very small amount, for example, with an amount ratio of 2,2,2-trichloroethanol (or trichloroacetyl chloride) / Ti equal to 0.1-3. Therefore, the catalyst system of the present invention is valuable to industry. Moreover, the catalytic system according to the present invention is particularly suitable for gas phase polymerization of ethylene, characterized by obtaining a smooth polymerization kinetics curve, the absence of clogging of the polymerization reactor or sticking to its wall. The polymers obtained by using the catalyst system of the present invention are characterized by density and melt index, which can be easily controlled. Finally, the catalytic system of the present invention is excellent in the inclusion of comonomer, and it is particularly suitable for the production of LLDPE (linear low density polyethylene).

Examples

The catalyst of the present invention is described in more detail using the following examples, but the catalyst system of the present invention is not limited to them.

Example 1

Obtaining a catalytic component (a):

(1) 11 g of spherical silica particles SYLOPOL 948 # (available from Grace Corporation, USA) were weighed out and after that activation was carried out at a temperature of 600 ° C for 4 hours.

(2) In a nitrogen atmosphere, a thermally activated silica from step (1) and 5 ml of a solution of AlEt ₃ in hexane (1 mmol / ml) were added to a flask equipped with a stirrer and containing hexane (100 ml) as a solvent. The reaction in the mixture was carried out at a temperature of 60 ° C. for half an hour, followed by a slow dropwise addition of 1.2 ml of trichloroacetyl chloride. After completion of the addition, the reaction in the mixture was carried out for half an hour, and then drying was carried out, passing a stream of high-purity nitrogen, thus obtaining flowing powders.

(3) To another flask equipped with a stirrer, 1.1 g of MgCl ₂ , 0.4 ml of TiCl ₄ and 100 ml of tetrahydrofuran were added. The mixture was heated with stirring to a boiling point at which it was kept for 3 hours, thereby obtaining a mother liquor of the catalyst.

(4) The silica treated in step (2) was mixed with the mother liquor of the catalyst from step (3). The mixture was stirred, keeping it at the boil under reflux for 1.5 hours, after which it was dried, passing a stream of high-purity nitrogen, thus obtaining a flowing, light yellow solid powder.

(5) The product from step (4) was previously reconstituted in 100 ml of hexane at a temperature of 60 ° C by first adding dropwise a 3.3 ml solution of AlEt ₂ Cl in hexane (2.2 mmol), and after completion of the addition, carrying out the reaction in the mixture for half an hour, and then by adding dropwise 14 ml of a solution of AlEt ₃ in hexane (1 mmol), where after the addition was complete, the reaction was carried out in the mixture for half an hour and then drying was carried out, passing a stream of high-purity nitrogen, thus obtaining powder catalytic to component. Ti, 0.74%.

Catalyst Evaluation:

Suspension homopolymerization of ethylene: suspension polymerization was carried out in a 2 liter stainless steel autoclave. The conditions were as follows: catalytic component, 1.2 mg (calculated on Ti); H ₂ / C ₂ H ₄ = 0.25 / 0.48 MPa; 1 ml of a solution of AlEt ₃ in hexane (1 mmol / ml); hexane, 1 liter; 80 ° C; 2 hours.

Results: catalytic activity to produce smooth kinetics; activity 1.61 x 10 ⁵ g PE / g Ti (1191.4 g PE / g catalyst); and bulk density of the powdered polymers 0.35 g / ml.

Example 2

Catalytic component (a) was obtained in the same manner as in example 1.

Catalyst Evaluation:

Gas-phase homopolymerization of ethylene: the polymerization was carried out in a φ 150 mm fluidized bed for gas-phase polymerization of ethylene, in the presence of 0.15 g of catalyst, 35 mmol of AlEt ₃ and 600 g of polyethylene powders as a dispersant, under the following polymerization conditions: total pressure 1.2 MPa ; H ₂ / C ⁼ ₂ = 0.20, temperature 88 ° C; 4 hours; productivity 4500 g PE / g catalyst; bulk density 0.36 g / cm ³ ; the density of the polymer is 0.960 g / cm ³ .

Example 3

Catalytic component (a) was obtained in the same manner as in example 1.

Gas-phase copolymerization of ethylene: the polymerization was carried out in a φ 150 mm fluidized bed for gas-phase polymerization of ethylene, in the presence of 0.15 g of the catalyst from Example 1, 35 mmol AlEt ₃ and 600 g of polyethylene powders as a dispersant, under the following polymerization conditions: total pressure 1 2 MPa; butene-1 as a comonomer, C ⁼ ₄ / C ⁼ ₂ = 0.063, H ₂ / C ⁼ ₂ = 0.20; temperature 88 ° C; 4 hours; productivity 8500g PE / g of catalyst; bulk density 0.36 g / cm ³ ; the density of the polymer is 0.926 g / cm ³ .

Comparative Example 1

Catalytic component (a) was obtained in the same manner as in Example 1, except that trichloroacetyl chloride was not added during the preparation.

Catalytic activity was evaluated in the same manner as in example 1.

Results: Ti, 0.69%; catalytic activity to obtain smooth kinetics; activity 1.12 x 10 ⁵ g PE / g Ti (772.8 g PE / g catalyst); and bulk density of powdered polymers 0.30 g / ml.

Reference Example 2

Catalytic component (a) was obtained in the same manner as in comparative example 1.

Catalytic activity was evaluated in the same manner as in example 2.

Results: activity 3,500 g PE / g catalyst; and bulk density 0.35 g / ml.

Reference Example 3

Catalytic component (a) was obtained in the same manner as in comparative example 1.

Catalytic activity was evaluated in the same manner as in example 3.

Results: activity 7000 g PE / g catalyst; and bulk density 0.35 g / ml.

Example 4

Catalytic component (a) was obtained in the same manner as in Example 1, except that 1.2 ml of trichloroacetyl chloride were added, followed by reaction in the resulting mixture for half an hour, after which 5 ml of a solution of AlEt ₃ in hexane was added. (1 mmol / ml).

Catalytic activity was evaluated in the same manner as in example 1.

Results: Ti, 0.93%; catalytic activity to obtain smooth kinetics; activity 1.61 x 10 ⁵ g PE / g Ti (1497.3 g PE / g catalyst); and bulk density of the powdered polymers 0.33 g / ml.

Example 5

Catalytic component (a) was obtained in the same manner as in example 1, except that 1.2 ml of trichloroacetyl chloride was added after the reduction reaction, followed by reaction in the resulting mixture for half an hour, after which drying was carried out by passing a stream high purity nitrogen.

Results: Ti, 0.87%; catalytic activity to obtain smooth kinetics; activity 1.40 x 10 ⁵ g PE / g Ti; and bulk density of the powdered polymers 0.31 g / ml.

Example 6

Catalytic component (a) was obtained in the same manner as in Example 1, except that 0.7 ml of 2,2,2-trichloroethanol was added instead of 1.2 ml of trichloroacetyl chloride.

Catalytic activity was evaluated in the same manner as in example 1.

Results: Ti, 0.80%; catalytic activity to obtain smooth kinetics; activity 1.38 x 10 ⁵ g PE / g Ti; and bulk density of the powdered polymers 0.32 g / ml.

Examples 7-9

Catalytic component (a) was obtained in the same manner as in example 1, except that instead of 1.2 ml of trichloroacetyl chloride, 0.7 ml of 2,2,2-trichloroethanol was added after the reduction reaction, followed by the reaction in the resulting as a result of the mixture for half an hour, after which drying was carried out, passing a stream of high-purity nitrogen. Ti, 0.93%.

Results: when polymerization is carried out at various partial pressures of hydrogen, catalytic activity can be achieved to produce smooth kinetics, and the results for polymerization are shown in Table A.

Example The amount of Ti added to the catalyst (mg) H ₂ (MPa) C ⁼ ₂ (MPa) C ⁼ ₆ Temperature (° C) Activity (10 ⁴ g PE / g Ti) Bulk Density (g / ml) Example 7 1,2 0.25 0.48 0 80 12.0 0.31 Example 8 1,2 0.25 0.48 12 ml 80 18.7 0.33 Example 9 0.6 0.25 0.75 0 80 41.0 0.33

Example 10

Catalytic component (a) was obtained in the same manner as in Example 1, except that instead of 1.2 ml of trichloroacetyl chloride, 0.7 ml of 2,2,2-trichloroethanol was added immediately after the activated silica was mixed with the mother liquor, followed by reaction in the resulting mixture for 1.5 hours, after which drying was carried out, passing a stream of high-purity nitrogen.

Results: Ti, 1.10%; catalytic activity to obtain smooth kinetics; activity 1.56 x 10 ⁵ g PE / g Ti; and bulk density of the powdered polymers 0.31 g / ml.

Example 11

The catalyst component (a) was obtained in the same manner as in Example 1, except that instead of 1.2 ml of trichloroacetyl chloride, 0.7 ml of 2,2,2-trichloroethanol was added during the preparation of the mother liquor.

Results: Ti, 1.05%; catalytic activity to obtain smooth kinetics; activity 1.45 x 10 ⁵ g PE / g Ti; and bulk density of the powdered polymers 0.31 g / ml.

Table 1
Catalyst Suspension Polymerization Evaluation Example Promoter Ti,% Activity (10 ⁴ g PE / g Ti) Bulk Density (g / ml) MI (melt index) FI (flow rate) MFR (melt flow rate) Example 1 A 0.74 16.1 0.35 0.95 29.6 31.1 Comparative Example 1 Is absent 0.69 11.2 0.30 Example 4 A 0.93 16.1 0.33 Example 5 A 0.87 14.0 0.31 0.86 26.6 30.9 Example 6 IN 0.80 13.8 0.32 0.52 15.93 30.6 Example 7 IN 0.93 12.0 0.31 0.28 6.96 24.9 Example 10 IN 1.10 15.6 0.31 0.88 26.2 29.8 Example 11 IN 1.05 14.5 0.31 1.12 34.7 31,0

Note: A, Cl ₃ CCOCl; B, Cl ₃ CCH ₂ OH.

table 2
Assessment for gas phase polymerization processes Example Promoter Activity
(g PE / g Ti) Bulk density
BD (g / ml) Example 2 IN 4500 0.36 Reference Example 2 Is absent 3500 0.35 Example 3 IN 8500 0.36 Reference Example 3 Is absent 7000 0.35

From table 1 it can be seen that the solid catalyst component (a) obtained using the promoter can obviously improve the activity of the catalyst system and / or bulk density of polyethylene. For example, the catalyst activity was significantly improved in Example 1, in which trichloroacetyl chloride was used as a promoter, the activity increasing from about 1.1 x 10 ⁵ g PE / g Ti to about 1.6 x 10 ⁵ g PE / g Ti, and volumetric the density increases from about 0.30 g / ml to about 0.35 g / ml.

Claims (15)

1. Highly supported supported titanium-based catalyst suitable for (co) polymerizing ethylene, comprising: A. supported on a carrier catalyst component, which is a titanium-containing active component supported on porous silicon dioxide as an inert carrier, containing at least one titanium compound, at least one magnesium compound, at least one aluminum alkyl compound at least one halide promoter, at least one electron-donor compound and porous silicon dioxide as an inert carrier; where said halide promoter is a class of compounds described by the general formula FR ¹ [R ² _b X _(3-b) ], where F is an oxygen-containing functional group that is reactive with an organoaluminum compound, a titanium compound or hydroxyl groups; R ¹ represents a divalent C ₁ -C ₆ aliphatic or aromatic group that is attached to the functional group F; R ² represents hydrogen, unsubstituted or halogen substituted C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl or C ₆ -C ₁₀ aromatic groups, b is 0, 1 or 2, and X represents fluorine, chlorine or bromine; and B. aluminum alkyl cocatalyst. 2. The highly supported supported titanium-based catalyst according to claim 1, wherein said functional group F is an aldehyde group, an acyl group or a hydroxyl group. 3. The highly supported supported titanium-based catalyst according to claim 1, characterized in that the said halide promoter is selected from the group consisting of 2,2,2-trichloroethanol, 2,2-dichloroethanol, 2-chloroethanol, 1,1- dimethyl-2,2,2-trichloroethanol, 4-chlorobutanol, para-chlorophenol, iso-chlorophenol, ortho-chlorophenol and 2-chlorocyclohexanol. 4. The highly supported supported titanium-based catalyst according to claim 1, wherein said halide promoter is selected from the group consisting of trichloroacetyl chloride, dichloroacetyl chloride, chloroacetyl chloride, o-chlorobenzoyl chloride and 2-chlorocyclohexylcarbonyl chloride. 5. The highly supported supported titanium-based catalyst according to claim 1, characterized in that said magnesium compound is selected from the group consisting of magnesium dichloride, magnesium dibromide, magnesium diiodide and mixtures thereof. 6. The highly supported supported titanium-based catalyst according to claim 1, wherein said titanium compound is selected from titanium tetrachloride, titanium trichloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, triethoxy titanium chloride, methane titanium dichloride, triethoxy titanium dichloride, tri-titanium dichloride , ethoxy titanium trichloride and mixtures thereof. 7. The highly supported supported titanium-based catalyst according to claim 1, characterized in that said electron-donating compound is selected from the group consisting of C ₁ -C ₄ alkyl esters of saturated aliphatic carboxylic acids, C ₇ -C ₈ aromatic alkyl esters carboxylic acids, C ₂ -C ₆ aliphatic ethers, C ₃ -C ₄ cyclic ethers, C ₃ -C ₆ saturated aliphatic ketones and mixtures thereof. 8. The highly supported supported titanium-based catalyst according to claim 1, characterized in that in the aforementioned catalyst component A, the magnesium compound, electron-donating compound and halide promoter are used in amounts of from 0.5 to 50 moles, from 0.5 to 50 moles and from 0.1 to 50 moles per mole of titanium compound, respectively. 9. The highly supported supported titanium-based catalyst according to claim 1, characterized in that said component B is selected from the group consisting of AlEt ₃ , Al (ISO-Bu) ₃ , Al (nC ₆ H ₁₃ ) ₃ , Al (nC ₈ H ₁₇ ) ₃ , AlEt ₂ Cl and mixtures thereof. 10. The highly supported supported titanium-based catalyst according to claim 1, characterized in that said porous silicon dioxide as an inert carrier has an average particle diameter of 20-80 μm and a pore volume of 1.5-5 ml / g. 11. The highly active supported titanium-based catalyst of claim 10, wherein said porous silicon dioxide as an inert carrier has a specific particle surface area of 230-350 m ² / g and an average particle pore diameter of 18-40 nm. 12. The highly supported supported titanium-based catalyst according to claim 1, characterized in that said porous silicon dioxide as an inert carrier has an average particle diameter of 50 μm and a pore volume of 1.6 ml / g. 13. A supported titanium-based catalyst according to claim 1, characterized in that said electron-donating compound is tetrahydrofuran. 14. A method of producing a catalyst component A in a catalyst according to any one of claims 1 to 13, comprising the steps of: (1) thermal activation of an inert carrier material - porous silicon dioxide; (2) adding a thermally activated inert carrier material, porous silicon dioxide, to a lower alkane-based solvent, followed by addition of an aluminum alkyl compound, and then carrying out the reaction in a mixture, followed by evaporation of the solvent and drying, thereby obtaining a solid powder; (3) dissolving the titanium compound and the magnesium compound in the electron donor compound to obtain a mother liquor, where the titanium compound is added to the electron donor compound before or after the magnesium compound is added, or both the titanium compound and the magnesium compound are added simultaneously; (4) adding an inert carrier material, a porous silica activated in step (2), to the mother liquor from step (3) and carrying out a reaction between them, followed by drying to remove excess electron-donating compound, thereby obtaining a solid material; (5) suspending the solid material from step (4) in a lower alkane-based solvent and then reducing it with one or more aluminum alkyl compounds, followed by drying, thereby obtaining the final catalyst component; wherein said halide promoter is included in catalyst component A in one of the following steps: i) adding during processing of the inert material the porous silica support in said step (2), ii) adding during the deposition of the catalyst complex from said step (3) to an inert the support material is porous silicon dioxide; and iii) additions during catalyst reduction in the aforementioned step (5). 15. The method of (co) polymerizing ethylene using a gas phase method or a suspension method in the presence of a catalyst according to any one of claims 1 to 13.