RU2575167C2 - Catalytic composition, intended for olefin polymerisation and method for obtaining thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to component of catalyst, intended for polymerisation of olefins, and to catalyst, containing said catalyst component. Described is catalyst component, containing product of reaction of at least one titanium-containing compound, at least one hydroxygroup-containing compound, at least one chlorine-containing compound and at least one polybutadiene block-copolymer. Chlorine-containing compound is selected from the group, which includes chlorine-containing organic compound, boron trichloride, trichlorophenylsilane, silicon tetrachloride, phosphorus trichloride, phosphorus pentachloride, methyldichlorophosphate and phosphorus oxychloride. Method for obtaining said catalyst component and its application for homopolymerisation or copolymerisation of olefins is also described.

EFFECT: obtaining catalyst, possessing excellent granule shape, high catalytic activity and good sensitivity with respect to hydrogen.

27 cl, 4 dwg, 13 tbl, 37 ex

Description

FIELD OF THE INVENTION

The present invention relates to a catalyst component for the polymerization of olefins, and to a catalyst containing said catalyst component. The present invention also relates to a method for producing said catalyst and to its use.

BACKGROUND

Successful development in the 1970s. highly effective catalysts for the polymerization of olefins has led to a significant development of the industrial production of polyolefins. Over the past 20 years, a significant development has occurred in the production of catalysts, which is comparable to the development of the polymerization of olefins. Highly effective polymerization catalysts and highly developed application technologies still play an important role in the field of olefin polymerization. After many years of research on the basis of the co-grinding technique, a procedure was developed for the preparation of Mg-Ti-containing catalysts with high efficiency, and a chemical reaction technique was developed on the basis of the suspension introduction technique. The specified modified chemical reaction methodology has been used in various patents related to the use of chemical raw materials, such as organomagnesium compounds, chlorinating agents and transition metal compounds, titanium, to obtain various types of catalysts, such as disclosed in CN 1158136, CN 1299375, CN 1795213, US 3787384, US 4148754, US 4173547, US 4301029, US 4508843, US 4921920 and US5124296. One irreparable disadvantage of the preparation of Mg-Ti containing catalysts in this way is the fact that it is difficult to control the preparation steps and therefore the shape of the catalyst granules.

In recent developments, some materials, such as emulsifiers, are added to the dispersed catalyst precursor system containing Mg / Ti compounds to form an emulsion, and catalyst particles precipitate after the reaction, so that the shape of the catalyst granules can be improved. For example, perfluoropolyether is used in EP 0258089 A and perfluorooctane is used in CN 1537118 A. However, the techniques described above include complex preparation steps and their regulation is complex. It is also difficult to control the shape of the granules of the obtained catalyst and the substances used are expensive and inaccessible.

In addition, recent studies have shown that the addition of electron donors in the preparation of a catalyst component can help regulate the activity of the catalyst during polymerization and its sensitivity to hydrogen, reduce the content of oligomers in polymerization products, etc. In CN 1129709 A, the preparation of the catalyst uses electron donor compounds to improve the activity of the catalyst and its sensitivity to hydrogen and bulk density of polymerization products. The electron donor compounds used in this patent include organic compounds containing one or a large number of lone electron pairs, mainly esters of organic acids.

In conclusion, it should be noted that, despite a large number of studies in the field of preparation of Ziegler-Natta catalysts, catalysts obtained by a simple method and possessing excellent granule shape, high catalytic activity, and good sensitivity to hydrogen are still needed in this area.

SUMMARY OF THE INVENTION

The present invention relates to the production of solid particles of a Ziegler-Natta catalyst in a controlled manner in order to obtain a catalyst component having a good particle shape (such as a spherical particle shape), a narrow particle size distribution, high catalytic activity and good sensitivity to hydrogen, which can be useful when using a catalyst for polymerization, such as gas phase or slurry polymerization, and the catalyst preparation procedure is Simple and easy to use.

The present invention relates to a catalyst component for the polymerization of olefins, which contains the reaction product of at least one organomagnesium compound, at least one titanium-containing compound, at least one hydroxy-containing compound, at least one chlorine-containing organic compound and at least one polybutadiene block copolymer,

, в которой R¹ обозначает C₂-C₂₀-гидрокарбильную группу, и может обладать насыщенной или ненасыщенной линейной цепью, разветвленной цепью или циклической цепью, и 0<n≤2; предпочтительно, если R¹ обозначает C₂-C₂₀-алкильную группу и конкретным соединением может являться по меньшей мере одно соединение, выбранное из группы, включающей дибутилмагний, диизобутилмагний, диоктилмагний, бутилоктилмагний, этилхлорид магния и бутилхлорид магния;where the specified organomagnesium compound is described by formula (I), $$Mg{R}_n^{\mathrm{one}}C{l}_{2-n}$$

in which R ¹ is a C ₂ -C ₂₀ hydrocarbyl group, and may have a saturated or unsaturated linear chain, branched chain or cyclic chain, and 0 <n≤2; preferably, if R ¹ is a C ₂ -C ₂₀ -alkyl group and the particular compound may be at least one compound selected from the group consisting of dibutyl magnesium, diisobutyl magnesium, dioctyl magnesium, butyl octyl magnesium, ethyl ethyl chloride and magnesium butyl chloride;

where the specified titanium-containing compound is described by the formula (II), Ti (OR ² ) _m Cl _4-m , in which R ² denotes a C ₂ -C ₂₀ -hydrocarbyl group, and may have a saturated or unsaturated linear chain, branched chain or cyclic chain, and 0≤m≤4; preferably, m is 4 or 0, since the tetravalent titanium compounds at room temperature are usually liquid and their compatibility with some solvents is also good; a particular compound may be at least one compound selected from the group consisting of titanium tetrachloride, tetraethyl titanate and tetrabutyl titanate, preferably titanium tetrachloride; wherein said hydroxy-containing compound is described by formula (III), HOR ³ , in which R ³ is a C ₂ -C ₂₀ hydrocarbyl group, and may have a saturated or unsaturated linear chain, branched chain or cyclic chain; said hydroxy-containing compound is preferably a fatty alcohol or aromatic alcohol, more preferably if it is at least one compound selected from the group consisting of n-butanol, n-hexanol, isooctanol, benzyl alcohol and phenylethanol.

Preferably, if said co-precipitating precipitating agent, a polybutadiene block copolymer, is a polystyrene-block polybutadiene (SB) copolymer containing a diblock copolymer, triblock copolymer (SBS, BSB) and their derivatives. The block may optionally have a linear structure, a structure containing branched chains, or a star-shaped structure; the polybutadiene content in said polybutadiene block copolymer is from 3 to 97% (wt.%), preferably from 10 to 90% (wt.%).

Preferably, if said co-precipitating precipitating agent, a polybutadiene block copolymer, is a polybutadiene-block-polyethylene oxide (PB-block-PEO) copolymer containing a diblock copolymer, a triblock copolymer (PB-block-PEO-block-PB, PEO -block-PB-block-PEO) and their derivatives. The block may optionally have a linear structure, a structure containing branched chains, or a star-shaped structure and the like; the polybutadiene content in said polybutadiene block copolymers is from 3 to 97% (wt.%), preferably from 10 to 90% (wt.%).

, в которой R⁴ обозначает C₂-C₂₀-алкильную группу или алкоксигруппу и 0≤р<3; конкретным хлорсодержащим борорганическим соединением является по меньшей мере одно соединение, выбранное из группы, включающей дихлорметилбор, дихлорэтилбор, дихлорбутилбор, дихлорметоксибор, дихлорэтоксибор, трихлорид бора и дихлорбутоксибор, предпочтительно по меньшей мере одно соединение, выбранное из группы, включающей дихлорбутилбор, дихлорметоксибор, дихлорэтоксибор, трихлорид бора и дихлорбутоксибор.Preferably, if the specified chlorine-containing organic compound is a chlorine-containing organoboron compound described by formula (IV), $$B{R}_p^{\mathrm{four}}C{l}_{3-p}$$

in which R ⁴ denotes a C ₂ -C ₂₀ alkyl group or alkoxy group and 0≤p <3; a particular chlorine-containing organoboron compound is at least one compound selected from the group consisting of dichloromethylboron, dichloroethylboron, dichlorobutylboron, dichloromethoxyboron, dichloroethoxyboron, boron trichloride and dichlorobutoxyboron, at least one compound selected from the group of chloroethylboron, chloroethylboron boron and dichlorobutoxyboron.

, в которой R⁵ обозначает C₂-C₂₀-алкильную группу или алкоксигруппу, 0≤q<3 и d равно 0 или 1; конкретным хлорсодержащим фосфорорганическим соединением является по меньшей мере одно соединение, выбранное из группы, включающей дихлорметилфосфор, дихлорэтилфосфор, дихлорбутилфосфор, трихлорид фосфора, пентахлорид фосфора, оксихлорид фосфора, метилдихлорфосфат, этилдихлорфосфат и бутилдихлорфосфат, предпочтительно по меньшей мере одно соединение, выбранное из группы, включающей трихлорид фосфора, пентахлорид фосфора и оксихлорид фосфора.Preferably, if the specified chlorine-containing organic compound is a chlorine-containing organophosphorus compound of the formula (V), $$O_{d}P{R}_q^{5}C{l}_{3-q}$$

in which R ⁵ denotes a C ₂ -C ₂₀ alkyl group or alkoxy group, 0≤q <3 and d is 0 or 1; a particular chlorine-containing organophosphorus compound is at least one compound selected from the group consisting of dichloromethylphosphorus, dichloroethylphosphorus, dichlorobutylphosphorus, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, methylene dichlorophosphate, butyl trichloride, preferably trichloride phosphorus, phosphorus pentachloride and phosphorus oxychloride.

, в которой R⁶ обозначает C₂-C₂₀-алкильную группу или алкоксигруппу и 0≤е<4; конкретным хлорсодержащим кремнийорганическим соединением является по меньшей мере одно соединение, выбранное из группы, включающей трихлорфенилсилан, трихлорметилсилан, трихлорэтилсилан, трихлороктилсилан, трихлорметоксисилан, трихлорэтоксисилан, трихлорбутоксисилан, дихлордиметоксисилан, дихлордиэтоксисилан и тетрахлорид кремния, предпочтительно по меньшей мере одно соединение, выбранное из группы, включающей трихлорметилсилан, трихлорэтилсилан, трихлорметоксисилан, трихлорэтоксисилан и тетрахлорид кремния.Preferably, if the specified chlorine-containing organic compound is a chlorine-containing organosilicon compound described by formula (VI), $$Si{R}_e^{6}C{l}_{\mathrm{four}-e}$$

wherein R ⁶ is a C ₂ -C ₂₀ alkyl group or alkoxy group and 0 ≤ e <4; a particular chlorine-containing organosilicon compound is at least one compound selected from the group consisting of trichlorophenylsilane, trichloromethylsilane, trichloroethylsilane, trichloroctylsilane, trichloromethoxysilane, trichloroethoxysilane, trichlorobutoxylmethanediol, tri-chloroethylsilane tetraethyl, tetraethyl, tetraethyl, tetraethyl, tetraethyl, tetraethyl, tetraethyl, ethylene, tetra , trichloroethylsilane, trichloromethoxysilane, trichloroethoxysilane and silicon tetrachloride.

, в которой R⁷ обозначает C₂-C₂₀-гидрокарбильную группу и 0,5≤f≤2,5; предпочтительно, если R⁷ обозначает обладающую линейной цепью или разветвленной цепью C₂-С₆-гидрокарбильную группу; конкретным хлорсодержащим алюминийорганическим соединением является по меньшей мере одно соединение, выбранное из группы, включающей дихлорэтилалюминий, этилсесквихлорид алюминия, диэтилхлорид алюминия и дихлоризобутилалюминий.Preferably, if the specified chlorine-containing organic compound is a chlorine-containing organoaluminum compound described by formula (VII) $$Al{R}_f^{7}C{l}_{3-f}$$

in which R ⁷ denotes a C ₂ -C ₂₀ -carbonyl group and 0.5 f f 2 2.5; preferably, if R ⁷ denotes a straight chain or branched chain C ₂ -C ₆ -hydrocarbyl group; a particular chlorine-containing organoaluminum compound is at least one compound selected from the group consisting of dichloroethyl aluminum, ethyl sesquichloride aluminum, diethyl aluminum chloride and dichloroisobutyl aluminum.

Preferably, an acyl chloride is used in the reaction to obtain a catalyst component. Said acyl chloride is described by formula (VIII), R ⁸ COCl, in which R ⁸ is a C ₂ -C ₂₀ hydrocarbyl group, and may have a saturated or unsaturated linear chain, branched chain or cyclic chain; said acyl chloride is at least one compound selected from the group consisting of formyl chloride, acetyl chloride, propionyl chloride, butyryl chloride, benzoyl chloride, phenylacetyl chloride, phenylpropionyl chloride and phenylbutyryl chloride, preferably at least one compound selected from benzyl chloride;

Alternatively, preferably, silane is used in the reaction to produce the catalyst component. Said silane is described by formula (IX), Si (OR ⁹ ) _g Cl _4-g , in which R ⁹ is a C ₂ -C ₂₀ hydrocarbyl group, and may have a saturated or unsaturated linear chain, branched chain or cyclic chain and 0 <g≤4; said silane is at least one compound selected from the group consisting of chlorotrimethoxysilane, chlorotriethoxysilane, chlorotributoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, dichlorodibutoxysilane, tetraethylorthosilicate, tetraethyl orthoethylate tetraethyl group, preferably

The present invention also relates to a method for producing the above catalyst component.

The method of obtaining the specified component of the catalyst proposed in the present invention, carried out without the use of acyl chloride or silane, includes the following steps:

step a) the organomagnesium compound is reacted with a hydroxy-containing compound to give a clear solution;

step b) the polybutadiene block copolymer is dispersed in a C ₄ -C ₂₀ alkane or aromatic solvent to give a solution, which is then reacted with the clear solution obtained in step a), and a mixture is obtained; and

step c) to the mixture obtained in step b), a chlorine-containing organic compound and a titanium-containing compound are successively added to obtain said catalyst component.

The method of obtaining the specified component of the catalyst proposed in the present invention, carried out using acyl chloride or silane includes the following steps,

step a) the organomagnesium compound is reacted with a hydroxy-containing compound to give a clear solution;

step b) the polybutadiene block copolymer is dispersed in a C ₄ -C ₂₀ alkane or aromatic solvent and a solution is obtained which is then reacted with the indicated acyl chloride or said silane and the clear solution obtained in step a), and a mixture is obtained; and

step c) to the mixture obtained in step b), a chlorine-containing organic compound and a titanium-containing compound are successively added to obtain said catalyst component.

Preferably, if said titanium-containing compound is used in an amount of 0.01 to 10 moles in said preparation method, said hydroxy-group-containing compound is used in amounts of 0.1 to 20 moles, said chlorine-containing organic compound is used in an amount of 0.1 to 50 moles, said acyl chloride or said silane is used in an amount of 0.001 to 20 moles, based on 1 mol of an organomagnesium compound, and the content of polybutadiene block the polymer in the reaction system is regulated in the range from 0.001 to 100 g / L. Preferably, if the amount of said titanium-containing compound is from 0.05 to 5 moles, the amount of said hydroxy-containing compound is from 0.2 to 10 moles, the amount of said chlorine-containing organic compound is from 0.5 to 20 moles, the amount of said acyl chloride or said silane ranges from 0.01 to 10 moles, and the content of the polybutadiene block copolymer in the reaction system is controlled in the range from 0.01 to 50 g / l.

In step a), the organomagnesium compound and the hydroxy-containing compound are reacted with each other, preferably at a relatively high temperature, preferably at a temperature below the boiling point of the reactants and usually not above 90 or 70 ° C. Depending on the nature of the reagents and the reaction conditions, the required reaction time is usually from 5 minutes to 2 hours, preferably from 10 minutes to 1 hour. After the completion of the reaction, the organomagnesium compound and the hydroxy-group-containing compound are mixed with an inert diluent, which is usually selected from aliphatic hydrocarbons such as isobutane, pentane, hexane, heptane, cyclohexane and mixtures thereof. A suitable inert solvent is usually hexane or heptane.

In step b), a co-precipitating precipitating agent, a polybutadiene block copolymer, is dispersed in a C ₄ -C ₂₀ alkane or aromatic solvent, preferably in a solvent such as hexane, heptane, toluene or a mixture thereof, and a solution is obtained which is then thoroughly mixed with (the specified acyl chloride or the specified silane and) a clear solution obtained in stage a). Depending on the type and nature of the precipitating reagent forming the joint precipitate, the concentration of the solution obtained in the C ₄ -C ₂₀ alkane or aromatic solvent is adjusted to be in the range from 0.1 to 100 g / l, preferably from 1 to 50 g / l. The precipitating reagent forming the joint precipitate should be added to the reaction system in such an amount that its content in the system is in the range from 0.001 to 100 g / l, preferably from 0.01 to 50 g / l. The temperature of the mixture is usually below the boiling point of the system. For convenience, it is usually in the range of 0 to 90 ° C, preferably in the range of 10 to 50 ° C. The mixing time is usually in the range from 0.5 minutes to 5 hours, preferably from 10 minutes to 1 hour.

In step c), the mixing of all materials to produce a uniform mixture is completed at a certain temperature. First, the temperature of the solution of the system obtained in the two previous stages is lowered to a temperature in the range from -90 to 30 ° C, preferably from -70 to 0 ° C, while the solution remains clean and transparent and no clouding or precipitation occurs. Then, a chlorine-containing organic compound and a titanium-containing compound are slowly added successively with thorough mixing to facilitate complete mixing of the substances at such a rate of addition that there is no obvious reaction and heating of the system. After complete mixing of the substances, any known suitable technique can be used to increase the temperature of the system, while the system turns from transparent to cloudy and precipitates. During the deposition step, the reaction time should be long enough to obtain the entire precipitate, it can be from 1 minute to 10 hours, preferably from 3 minutes to 5 hours.

It has been experimentally found that after the deposition step is carried out to ensure a good shape of the catalyst particles, it is preferable to conduct the reaction at a certain temperature for a certain period of time necessary for aging, which can increase the strength of the catalyst particles, thereby reducing the likelihood of destruction of the catalyst particles during polymerization. The aging temperature, the duration of which can be adjusted from 0.5 to 10 hours, preferably from 1 to 5 hours, is usually equal to or higher than the final temperature of the precipitation reaction.

After aging, the precipitate is usually washed to remove excess reagents and by-products from the reaction. Any inert solvent such as isobutane, pentane, hexane, heptane, cyclohexane, toluene, various aromatic solvents and a mixture thereof can be used to carry out the washing step. In experiments, toluene is usually used to wash the precipitate twice, and then an excess of hexane is used for thorough washing, then the suspension of the catalyst is dried under a nitrogen atmosphere and a powdery catalyst is obtained.

In addition, the present invention also relates to a catalyst for the homopolymerization or copolymerization of olefins, which contains the reaction products of the aforementioned catalyst component of the present invention and an aluminum alkyl compound, wherein the aluminum alkyl compound used is described by the formula AlR ″ ₃ , in which R ''_'3 may denote one or more C ₁ -C ₈ -alkyl groups, which may be identical or different from each other, and one or two alkyl groups may be s are substituted by chlorine atoms; for use, one or more two aluminum alkyl compounds can be selected and mixed, preferably if they are 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 the like.

The specified catalyst proposed in the present invention, can be used according to the method of application of the Ziegler-Natta catalyst for the polymerization of olefins, known in the art. For example, it can be used with another catalyst or electron donor, or with one or more types of Ziegler-Natta catalysts or non-Ziegler-Natta catalysts.

When using said catalyst for homopolymerization or copolymerization of olefins, said olefin is ethylene, propylene, butylene, hexene or octene. The specified catalyst proposed in the present invention is applicable to various olefins, it can regulate the polymerization, including the homogeneous polymerization of one olefin or the copolymerization of various olefins. The olefin is preferably an α-olefin, such as ethylene, propylene and butylene, or a mixture of ethylene, propylene, butylene with one or more types of α-olefins. The best comonomer is a C ₂ -C ₁₂ olefin, preferably a C ₄ -C ₁₂ olefin such as 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1- decene and 4-methylpentene, a diene such as butadiene, 1,4-hexadiene and 1,7-octadiene, and a cycloolefin such as norbornene, or any mixture thereof.

The specified catalyst proposed in the present invention can be used in one or more polymerization reactors designed for carrying out the polymerization reaction in accordance with conventional polymerization technologies. This can be a polymerization reaction in the gas phase, in suspension or in a block, and the polymerization reaction can be carried out in a batch or continuous mode.

When using a slurry or block polymerization reactor, the temperature during the reaction is usually in the range of 40 to 130 ° C, preferably in the range of 60 to 110 ° C; the pressure during the reaction is usually in the range from 0.1 to 8 MPa, preferably in the range from 0.3 to 6 MPa; the residence time in the reactor is usually in the range of 0.2 to 6 hours, preferably in the range of 0.5 to 3 hours. Typically, an aliphatic hydrocarbon having a boiling point of 0 to 100 ° C. and, if necessary, a polymerization reaction are used as a diluent. can be carried out under supercritical conditions.

When using a gas phase polymerisation reactor, the temperature during the reaction is usually in the range of 60 to 130 ° C, preferably in the range of 70 to 110 ° C; the pressure during the reaction is usually in the range from 0.5 to 4 MPa, preferably in the range from 1 to 3 MPa; the residence time in the reactor is usually in the range from 0.5 to 10 hours, preferably in the range from 1 to 8. If necessary, a suitable aliphatic hydrocarbon can be used as a diluent and the polymerization reaction can be carried out in a condensed state.

The amount of catalyst usually depends on the nature of the catalyst, the type of reactor, the reaction conditions, and the requirements for the properties of the polymerization product. A commonly used amount of catalyst may be used.

Using the specified catalyst in the present invention, it is possible to provide high catalytic activity and good sensitivity to hydrogen, the shape of the particles of the polymerization product can completely repeat the shape of the catalyst particles, i.e. the so-called "copy effect" is provided. Therefore, the catalyst of the present invention has good overall performance.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows the obtained by scanning electron microscopy (SEM) photograph of a component of the catalyst corresponding to example 10;

Figure 2 shows a diagram of the distribution of particle sizes corresponding to example 13;

Figure 3 shows the obtained by scanning electron microscopy (SEM) photograph of a component of the catalyst corresponding to comparative example 4; and

Figure 4 shows a diagram of the distribution of particle sizes corresponding to comparative example 4.

OPTIONS FOR CARRYING OUT

The present invention will be explained in more detail using the following examples. Obviously, these examples in no way limit the scope of the present invention. The scope of rights protected by the present invention is determined by the content of the claims.

The research methods used in the examples given in the present invention are as follows.

1. Particle size distribution of the carrier and catalyst: using a device for determining the particle size distribution, n-hexane is used as a dispersing agent and the research range is from 0.02 to 2000 microns;

2. The mass ratio of metals (mainly magnesium and titanium) in the catalytic system: using plasma emission spectroscopy (ICP (induction-coupled plasma));

3. Determination of the melt index: ASTM-D1238;

4. Determination of bulk density: DIN-53194.

Example 1

30 ml of hexane, 3.15 ml of a hexane solution of dibutylmagnesium (1M) and 1.0 ml of isooctanol are successively measured and mixed, then the temperature is raised to 50 ° C and the reaction mixture is kept under stirring for 0.5 h and a clear solution is obtained. 3 ml of a hexane solution (10 g / l) of a polystyrene-polybutadiene triblock copolymer (Kraton, FG1901X, in which the polybutadiene content is 70%) is added. Then, the temperature of the system was lowered to −50 ° C. and 3.15 ml of a hexane solution of boron trichloride (1 M) and 0.35 ml of titanium tetrachloride were successively added. After the addition is complete, the temperature is rapidly increased to 50 ° C over 10 minutes and the reaction mixture is maintained for 2 hours. The temperature of the catalyst suspension is reduced to room temperature, the suspension is allowed to stand and it is allowed to precipitate, and then it is washed 3 times with 50 ml of hexane. After washing is completed by drying, a brown solid free-flowing powdery substance is obtained having an average particle size of 17.4 μm.

Elemental analysis (ICP): 10.62 wt.% Ti, 14.73 wt.% Mg.

The ethylene polymerization procedure A: 1 l of hexane, 1 mmol of triethylaluminium and a certain amount of catalyst components are added to a 2 l stirring steel tank, then the temperature is increased to 85 ° C, hydrogen is added in one portion to ensure a pressure of 0.5 MPa, and the total system pressure is maintained at 1.03 MPa with ethylene for polymerization. After carrying out the reaction for 2 hours, the addition of ethylene is stopped, the temperature is lowered and the pressure is released. Powdered polyethylene is weighed, the activity of the catalyst is calculated, and the bulk density of the powdered polyethylene and the melt index of the powdered polyethylene are determined at a charge of 2.16 kg. The results are shown in table 1.

Ethylene B polymerization procedure: 1 l of hexane, 1 mmol of triethyl aluminum and a certain amount of catalyst components are added to a 2 l stirred steel tank, then the temperature is increased to 85 ° C, hydrogen is added in one portion to ensure a pressure of 0.18 MPa, and the total system pressure is maintained at 1.03 MPa with ethylene for polymerization. After carrying out the reaction for 2 hours, the addition of ethylene is stopped, the temperature is lowered and the pressure is released. Powdered polyethylene is weighed, the activity of the catalyst is calculated, and the bulk density of the powdered polyethylene and the melt index of the powdered polyethylene are determined at a charge of 2.16 kg. The results are shown in table 1.

Example 2

When preparing the catalyst, instead of 0.35 ml, 1 ml of titanium tetrachloride is used; other conditions are the same as in Example 1. The average particle size is 13.6 μm.

Elemental analysis (ICP): 11.52 wt.% Ti, 12.43 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 1.

Example 3

When preparing the catalyst, 0.6 ml of n-octanol is used instead of 1.0 ml of isooctanol and "the temperature is rapidly increased to 50 ° C over 10 minutes" is replaced by "the temperature is slowly raised to room temperature and then heated to 50 ° C." Other conditions are the same as in example 1, and the average particle size is 21.2 microns.

Elemental analysis (ICP): 11.25 wt.% Ti, 16.57 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 1.

Comparative Example 1

The conditions are the same as in Example 1, except that the polystyrene-polybutadiene triblock copolymer hexane solution is not added. The resulting catalyst has an average particle size of 68.53 μm, and the particle size distribution is a wider multimodal distribution.

Elemental analysis (ICP): 10.26 wt.% Ti, 14.18 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 1.

Table 1 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 ∗ (g / 10 min) Bulk density OD (g / ml) Example 1 Polymerization of Ethylene A 6.8 98.72 0.30 Polymerization of Ethylene B 23,4 2.13 0.31 Example 2 Polymerization of Ethylene A 9.8 86.38 0.29 Polymerization of Ethylene B 28.9 1.55 0.31 Example 3 Polymerization of Ethylene A 9.1 36.73 0.30 Polymerization of Ethylene B 31,4 0.83 0.31 Comparative Example 1 Polymerization of Ethylene A 5.7 72.59 0.28 Polymerization of Ethylene B 18.5 1.72 0.28 ∗ IR _2.16 = melt index calculated at a load of 2.16 kg

From the data for examples and comparative example presented in Table 1, it can be seen that, if SBS is used as a joint precipitate during the preparation of the catalyst, SBS is used, then the particle shape of the obtained catalyst and polymers is good, the particle size distribution is narrow, bulk density ( OP) polymer resin is high and overall catalyst performance is good.

Example 4

30 ml of hexane, 3.15 ml of a hexane solution of dibutylmagnesium (1M) and 1.0 ml of isooctanol are successively measured and mixed, then the temperature is raised to 50 ° C and the reaction mixture is kept under stirring for 0.5 h and a clear solution is obtained. Then add 3 ml of a hexane solution (10 g / l) of a polystyrene-polybutadiene triblock copolymer (Kraton, FG1901X, in which the polybutadiene content is 70%), the temperature is lowered to -50 ° C and 0.6 ml of phosphorus trichloride hexane solution is added sequentially (1M) and 0.35 ml of titanium tetrachloride. After the addition is complete, the temperature is rapidly increased to 50 ° C for 10 minutes and the reaction mixture is kept for 2 hours.

The temperature of the catalyst suspension was lowered to room temperature, the suspension was maintained and allowed to precipitate, and then it was washed 3 times with 50 ml of hexane. After washing is completed by drying, a brown solid free-flowing powdery substance is obtained having an average particle size of 17.6 μm.

Elemental analysis (ICP): 9.86 wt.% Ti, 12.69 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 2.

Example 5

Instead of 3 ml, 6 ml of a hexane solution (10 g / l) of a polystyrene-polybutadiene triblock copolymer are used, and instead of 0.6 ml of phosphorus trichloride, 0.6 ml of phosphorus oxychloride is used. Other conditions are the same as in example 4, and the average particle size is 9.83 microns.

Elemental analysis (ICP): 10.67 wt.% Ti, 13.58 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 2.

Example 6

In the preparation of the catalyst, 3.0 ml of isooctanol is used instead of 1.0 ml and "the temperature is rapidly increased to 50 ° C over 10 minutes" is replaced by "the temperature is slowly raised to room temperature and then heated to 50 ° C." Other conditions are the same as in example 4, and the average particle size is 19.7 microns.

Elemental analysis (ICP): 10.36 wt.% Ti, 14.62 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 2.

Reference Example 2

The conditions are the same as in Example 4, except that the polystyrene-polybutadiene triblock copolymer hexane solution is not added. The resulting catalyst has an average particle size of 64.76 μm, and the particle size distribution is a wider multimodal distribution.

Elemental analysis (ICP): 10.07 wt.% Ti, 13.16 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 2.

table 2 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 (g / 10 min) Bulk Density (g / ml) Example 4 Polymerization of Ethylene A 7.3 71.28 0.29 Polymerization of Ethylene B 16.9 1.88 0.31 Example 5 Polymerization of Ethylene A 11.7 82.59 0.30 Polymerization of Ethylene B 26.7 1.34 0.31 Example 6 Polymerization of Ethylene A 9.3 38.96 0.28 Polymerization of Ethylene B 19.5 1.91 0.30 Reference Example 2 Polymerization of Ethylene A 5.9 68.32 0.26 Polymerization of Ethylene B 14.6 1,67 0.27

From the data presented in Table 2 for examples and a comparative example, it can be seen that if SBS is used as the precipitating reagents forming a joint precipitate, the particle shape of the obtained catalyst and polymers is good, the particle size distribution is narrow, bulk density (OD a) polymer resin is high and overall catalyst performance is good.

Example 7

30 ml of hexane, 3.15 ml of a hexane solution of dibutylmagnesium (1M) and 1.0 ml of isooctanol are successively measured and mixed, the temperature is raised to 50 ° C and the reaction mixture is kept under stirring for 0.5 h and a clear solution is obtained. Then add 1 ml of a hexane solution (10 g / l) of a polystyrene-polybutadiene triblock copolymer (Kraton, FG1901X, in which the polybutadiene content is 70%), the temperature is lowered to -10 ° C and 0.36 g of silicon tetrachloride and 0 , 35 ml of titanium tetrachloride. After the addition is complete, the temperature is rapidly increased to 50 ° C over 10 minutes and the reaction mixture is maintained for 2 hours. The temperature of the catalyst suspension is reduced to room temperature, the suspension is allowed to stand and it is allowed to precipitate, and then it is washed 3 times with 50 ml of hexane. After washing is completed by drying, a brown solid free-flowing powdery substance is obtained having an average particle size of 56.2 μm.

Elemental analysis (ICP): 9.48 wt.% Ti, 20.84 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 3.

Example 8

"The temperature is rapidly increased to 50 ° C over 10 minutes" is replaced by "the temperature is increased rapidly to 10 ° C over 10 minutes. Other conditions are the same as in Example 7 and the average particle size is 85.2 μm.

Elemental analysis (ICP): 5.12 wt.% Ti, 12.81 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 3.

Example 9

When preparing the catalyst, instead of 1.0 ml of isooctanol, 0.6 ml of n-butanol is used, instead of 1 ml, 3 ml of hexane solution (10 g / l) of the polystyrene-polybutadiene triblock copolymer is added and the temperature is quickly increased to 50 ° C over 10 minutes C "replace with" the temperature is slowly raised to room temperature and then heated to 50 ° C. " Other conditions are the same as in example 7, and the average particle size is 24.3 microns. Elemental analysis (ICP): 11.66 wt.% Ti, 24.39 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 3.

Reference Example 3

The conditions are the same as in Example 7, except that the polystyrene-polybutadiene triblock copolymer hexane solution is not added. The resulting catalyst has an average particle size of 79.46 μm, and the particle size distribution is a wider multimodal distribution.

Elemental analysis (ICP): 9.73 wt.% Ti, 21.06 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 3.

Table 3 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 (g / 10 min) Bulk Density (g / ml) Example 7 Polymerization of Ethylene A 7.5 104.4 0.33 Polymerization of Ethylene B 25,2 2.17 0.33 Example 8 Polymerization of Ethylene A 5.9 93.26 0.30 Polymerization of Ethylene B 10.8 1,64 0.31 Example 9 Polymerization of Ethylene A 9.3 38.45 0.33 Polymerization of Ethylene B 30.5 0.74 0.34 Reference Example 3 Polymerization of Ethylene A 6.4 87.38 0.28 Polymerization of Ethylene B 22.6 1.49 0.29

From the data presented in Table 3 for examples and a comparative example, it can be seen that if SBS is used as the precipitate forming a joint precipitate, the particle shape of the obtained catalyst and polymers is good, the particle size distribution is narrow, bulk density (OD a) polymer resin is high and overall catalyst performance is good.

Example 10

30 ml of hexane, 3.15 ml of a hexane solution of dibutylmagnesium (1M) and 1.0 ml of isooctanol are successively measured and mixed, the temperature is raised to 50 ° C and the reaction mixture is kept under stirring for 0.5 h and a clear solution is obtained. Then 2 ml of a hexane solution (10 g / l) of a polystyrene-polybutadiene triblock copolymer (Kraton, FG1901X, in which the polybutadiene content is 70%) is added, the temperature is lowered to -50 ° C and 1.6 ml of a hexane solution of aluminum ethyl dichloride are added sequentially. (2M) and 0.35 ml of titanium tetrachloride. After keeping the reaction mixture at low temperature for 0.5 h, the temperature is allowed to slowly and spontaneously rise to room temperature and then the reaction is carried out at 50 ° C for 2 hours. The temperature of the catalyst suspension is lowered to room temperature, the suspension is allowed to stand and it is allowed to precipitate and then it is washed 3 times with hexane in 50 ml portions. After washing is completed by drying, a brown solid free-flowing powdery substance is obtained having an average particle size of 15.6 μm. A photograph of the catalyst component obtained by electron microscopy is shown in figure 1.

Elemental analysis (ICP): 11.04 wt.% Ti, 12.64 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 4.

Example 11

Instead of 2 ml, 4 ml of a hexane solution (10 g / l) of a polystyrene-polybutadiene triblock copolymer is used, and other conditions are the same as in Example 10. The average particle size is 7.69 μm.

Elemental analysis (ICP): 10.02 wt.% Ti, 14.20 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 4.

Example 12

"The reaction mixture is kept at low temperature for 0.5 h and the temperature is allowed to slowly rise to room temperature spontaneously" change to "after completion of the addition, the temperature is raised to 50 ° C over 10 minutes." Other conditions are the same as in example 10, and the average particle size is 21.5 μm.

Elemental analysis (ICP): 12.65 wt.% Ti, 9.86 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 4.

Propylene polymerization procedure: 800 ml of hexane, 2.5 mmol of triethylaluminium, 0.125 mmol of diphenyldimethoxysilane (DDS) and 20 mg of the catalyst components obtained in Example 12 are added to a 2 L steel reactor completely filled with gaseous propylene. 0.4 is added. l (under normal conditions) of hydrogen, then propylene is added to maintain a pressure in the reactor of 0.6 MPa, and the temperature is raised to 70 ° C. The polymerization is carried out for 2 hours, then the pressure is released and the products are discharged. The corresponding stereoregularity of the obtained polymers (the content of the substance remaining after extraction with boiling heptane in the extractor for 6 hours) is 91.7% and the specific polymerization results are shown in table 4.

Example 13

Instead of 2 ml, 3 ml of a hexane solution (10 g / l) of a polystyrene-polybutadiene triblock copolymer are used, and other conditions are the same as in Example 10. The average particle size of the obtained catalyst components is 9.03 μm. The particle size distribution of the catalyst components is shown in FIG. 2.

Elemental analysis (ICP): 9.02 wt.% Ti, 12.75 wt.% Mg.

The polymerization procedures for ethylene A and B are the same as those described in Example 1, and the polymerization results are shown in Table 4. The size distribution of polymer particles obtained by the sieve separation method is shown in Table 5.

Reference Example 4

The conditions are the same as in Example 10, except that 2 ml of a hexane solution of a polystyrene-polybutadiene triblock copolymer is not added (Kraton, FG1901X, in which the polybutadiene content is 70%). The resulting catalyst has an average particle size of 124.8 μm, and the particle size distribution is wider and contains a large number of peaks.

Elemental analysis (ICP): 11.36 wt.% Ti, 12.89 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 4.

Table 4 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 (g / 10 min) Bulk Density (g / ml) Example 10 Polymerization of Ethylene A 9.5 24.73 0.30 Polymerization of Ethylene B 27.3 0.77 0.31 Example 11 Polymerization of Ethylene A 14.0 38.41 0.30 Polymerization of Ethylene B 72,2 1.41 0.32 Example 12 Polymerization of Ethylene A 12.6 89.34 0.30 Polymerization of Ethylene B 31.6 0.61 0.31 Propylene Polymerization 32,4 2,4 0.38 Example 13 Polymerization of Ethylene A 22.9 70.54 0.29 Polymerization of Ethylene B 48,4 2.77 0.30 Reference Example 4 Polymerization of Ethylene A 11.5 25.64 0.25 Polymerization of Ethylene B 25.8 0.65 0.27

From the data for examples and comparative example presented in Table 4, it can be seen that if triblock copolymers of polystyrene-polybutadiene are used as the precipitating agents during the preparation of the catalyst, the particle shape of the obtained catalyst and polymers is good, the particle size distribution is narrow The bulk density (OD) of the polymer resin is high and the overall catalyst performance is good.

Table 5 Polymerization Conditions The distribution of particles of polyethylene (PE) in size, corresponding to example 13 (wt.%) <20 mesh 20-40 mesh 40-60 mesh 60-80 mesh 80-100 mesh 100-140 mesh 140-200 mesh > 200 mesh Polymerization of Ethylene A 1,04 2.94 14.12 48.80 22.35 7.44 2.28 1,03 Polymerization of Ethylene B 1,61 2.93 40.40 40.56 10.12 3.03 1.01 0.35

From the data presented in table 5, it can be seen that the particle size of the polymer contained in the catalyst obtained in example 13 is mainly in the range from 40 to 100 mesh, the particle size distribution is narrow and contains a smaller amount of fine powder. The size distribution of polymer particles contained in the specified catalyst obtained by the method of separation on the sieves is the same as the particle size distribution diagram (figure 2).

Example 14

30 ml of hexane, 3.15 ml of a hexane solution of dibutylmagnesium (1M) and 1.0 ml of isooctanol are successively measured and mixed, the temperature is raised to 50 ° C and the reaction mixture is kept under stirring for 0.5 h and a clear solution is obtained. After adding 0.2 ml of benzoyl chloride and 3 ml of a hexane solution (10 g / l) of a polystyrene-polybutadiene triblock copolymer (Kraton, FG1901X, in which the polybutadiene content is 70%), the temperature is lowered to -50 ° C and 1.6 is added sequentially ml of a hexane solution of aluminum ethyl dichloride (2M) and 0.35 ml of titanium tetrachloride. After keeping the reaction mixture at low temperature for 0.5 h, the temperature is allowed to slowly and spontaneously rise to room temperature and then the reaction is carried out at 50 ° C for 2 hours. The temperature of the catalyst suspension is lowered to room temperature, the suspension is allowed to stand and it is allowed to precipitate and then it is washed 3 times with hexane in 50 ml portions. After washing is completed by drying, a brown solid free-flowing powdery substance is obtained having an average particle size of 8.74 microns.

Elemental analysis (ICP): 10.58 wt.% Ti, 13.61 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 6.

Example 15

When preparing the catalyst, instead of 0.2 ml, 0.5 ml of benzoyl chloride is used, and instead of a hexane solution of aluminum ethyl dichloride, a hexane solution of aluminum isobutyl dichloride is used. Other conditions are the same as in example 14, and the average particle size is 13.2 μm.

Elemental analysis (ICP): 9.66 wt.% Ti, 12.13 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 6.

Example 16

In preparing the catalyst, 0.2 ml of acetyl chloride is used instead of 0.2 ml of benzoyl chloride and the other conditions are the same as described in Example 14. The average particle size is 7.94 μm.

Elemental analysis (ICP): 10.02 wt.% Ti, 13.54 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 6.

Example 13 '(comparative)

Upon receipt of the catalyst do not add 0.2 ml of benzoyl chloride and other conditions are the same as in example 14. The average particle size is 9.03 microns.

Table 6 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 (g / 10 min) Bulk Density (g / ml) Example 14 Polymerization of Ethylene A 24.2 105.24 0.30 Polymerization of Ethylene B 39.6 3.17 0.30 Example 15 Polymerization of Ethylene A 27.5 118.3 0.29 Polymerization of Ethylene B 41.3 3,58 0.31 Example 16 Polymerization of Ethylene A 23.8 91.3 0.30 Polymerization of Ethylene B 37.9 2.98 0.31 Example 13 '(comparative) Polymerization of Ethylene A 22.9 70.54 0.29 Polymerization of Ethylene B 48,4 2.77 0.30

From the data in Table 6 for examples and a comparative example, it can be seen that if acyl chloride is used in the preparation of the catalyst and SBS is used as the precipitating agent, the particle shape of the obtained catalyst and polymers is good, the particle size distribution is narrow; the sensitivity of the polymer resin to hydrogen is better; the overall performance of the catalyst is good, it is useful for the development of new polymer products with unique characteristics.

Example 17

30 ml of hexane, 3.15 ml of a hexane solution of dibutylmagnesium (1M) and 1.0 ml of isooctanol are successively measured and mixed, the temperature is raised to 50 ° C and the reaction mixture is kept under stirring for 0.5 h and a clear solution is obtained. Then add 0.7 ml of tetraethylorthosilicate and 3 ml of a hexane solution (10 g / l) of a polystyrene-polybutadiene triblock copolymer (Kraton, FG1901X, in which the polybutadiene content is 70%), the temperature is lowered to -50 ° C and 1 is added sequentially. 6 ml of a hexane solution of aluminum ethyl dichloride (2M) and 0.35 ml of titanium tetrachloride. After keeping the reaction mixture at low temperature for 0.5 h, the temperature is allowed to slowly and spontaneously rise to room temperature and then the reaction is carried out at 50 ° C for 2 hours. The temperature of the catalyst suspension is lowered to room temperature, the suspension is allowed to stand and it is allowed to precipitate and then it is washed 3 times with hexane in 50 ml portions. After washing is completed by drying, a brown solid free-flowing powdery substance is obtained having an average particle size of 11.5 μm.

Elemental analysis (ICP): 10.13 wt.% Ti, 8.57 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as those described in example 1, and the polymerization results are shown in table 7.

Example 18

In the preparation of the catalyst, instead of 0.7 ml, 1.0 ml of tetraethylorthosilicate is used and "the reaction mixture is kept for 0.5 h at low temperature and allowed to slowly rise to room temperature spontaneously" is replaced by "after completion of the addition, the temperature is within 10 minutes increase to 50 ° C ", other conditions are the same as in example 17. The average particle size is 24.7 microns.

Elemental analysis (ICP): 10.33 wt.% Ti, 12.46 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as those described in example 1, and the polymerization results are shown in table 7.

Example 19

In the preparation of the catalyst, 0.5 ml of isooctanol is used instead of 1.0 ml and 1.0 ml of tetraethylorthosilicate is used instead of 0.7 ml, and the other conditions are the same as in Example 17. The average particle size is 15.9 μm.

Elemental analysis (ICP): 8.89 wt.% Ti, 11.09 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as those described in example 1, and the polymerization results are shown in table 7.

Example 13 "(comparative)

Upon receipt of the catalyst do not add 0.7 ml of tetraethylorthosilicate and other conditions are the same as in example 17. The average particle size is 9.03 microns.

Reference Example 5

When preparing the catalyst, the polystyrene-polybutadiene triblock copolymer hexane solution was not added, and other conditions are the same as in Example 17. The resulting catalyst has an average particle size of 93.35 μm, and the particle size distribution is a wider multimodal distribution.

Elemental analysis (ICP): 9.24 wt.% Ti, 12.92 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as those described in example 1, and the polymerization results are shown in table 7.

Table 7 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 (g / 10 min) Bulk Density (g / ml) Example 17 Polymerization of Ethylene A 3,1 21.01 0.34 Polymerization of Ethylene B 16.1 0.80 0.35 Example 18 Polymerization of Ethylene A 5,4 85.83 0.33 Polymerization of Ethylene B 15,2 2.40 0.37 Example 19 Polymerization of Ethylene A 6.8 18.7 0.34 Polymerization of Ethylene B 12,2 0.65 0.36 Example 13 "(comparative) Polymerization of Ethylene A 22.9 70.54 0.29 Polymerization of Ethylene B 48,4 2.77 0.30 Reference Example 5 Polymerization of Ethylene A 2.9 18.47 0.28 Polymerization of Ethylene B 11.3 0.69 0.28

From the data for examples and comparative example presented in Table 7, it can be seen that if silane is used in the preparation of the catalyst, the particle shape of the obtained catalyst and polymers is good, the particle size distribution is narrow, the bulk density (OD) of the polymer resin is high and general catalyst performance is good.

Example 20

30 ml of hexane, 3.15 ml of a hexane solution of dibutylmagnesium (1M) and 1.0 ml of isooctanol are successively measured and mixed, the temperature is raised to 50 ° C and the reaction mixture is kept under stirring for 0.5 h and a clear solution is obtained. Then add 3 ml of a hexane solution (10 g / l) of a polybutadiene-block-polyethylene oxide copolymer (the content of polybutadiene is 45 wt.%), The temperature is lowered to -50 ° C and 3.15 ml of boron trichloride and 0.35 ml of tetrachloride are successively added. titanium. After the addition is complete, the temperature is rapidly increased to 50 ° C over 10 minutes and the reaction mixture is maintained for 2 hours. The temperature of the catalyst suspension is reduced to room temperature, the suspension is allowed to stand and it is allowed to precipitate, and then it is washed 3 times with 50 ml of hexane. After washing is completed by drying, a brown solid free-flowing powdery substance is obtained having an average particle size of 33.6 μm.

Elemental analysis (ICP): 11.53 wt.% Ti, 15.69 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 8.

Example 21

When preparing the catalyst, instead of 0.35 ml, 1 ml of tetrachloride is used and other conditions are the same as in Example 20. The average particle size is 25.8 μm.

Elemental analysis (ICP): 11.27 wt.% Ti, 13.05 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 8.

Example 22

When preparing the catalyst, the polybutadiene content in the polybutadiene-block-polyethylene oxide copolymer instead of 45 wt.% Is 75 wt.% And other conditions are the same as in Example 20. The average particle size is 15.9 μm.

Elemental analysis (ICP): 10.12 wt.% Ti, 14.32 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 8.

Comparative example 1 '

When preparing the catalyst, a hexane solution of a polybutadiene-block-polyethylene oxide copolymer was not added, and other conditions are the same as in Example 20. The resulting catalyst has an average particle size of 68.53 μm, and the particle size distribution is a wider multimodal distribution.

Table 8 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 (g / 10 min) Bulk Density (g / ml) Example 20 Polymerization of Ethylene A 5,4 93.26 0.29 Polymerization of Ethylene B 19.7 2.08 0.31 Example 21 Polymerization of Ethylene A 8.9 89.42 0.31 Polymerization of Ethylene B 27.8 1,67 0.32 Example 22 Polymerization of Ethylene A 9.5 83,45 0.31 Polymerization of Ethylene B 32.6 1,03 0.32 Comparative example 1 ' Polymerization of Ethylene A 5.7 72.59 0.28 Polymerization of Ethylene B 18.5 1.72 0.28

From the data for examples and comparative example presented in Table 8, it can be seen that if SBS is used as modifying additives in the preparation of the catalyst, the particle shape of the obtained catalyst and polymers is good, the particle size distribution is narrow, the bulk density (OD) of the polymer resin is high and overall catalyst performance is good.

Example 23

30 ml of hexane, 3.15 ml of a hexane solution of dibutylmagnesium (1M) and 1.0 ml of isooctanol are successively measured and mixed, the temperature is raised to 50 ° C and the reaction mixture is kept under stirring for 0.5 h and a clear solution is obtained. Then add 2 ml of a hexane solution (10 g / l) of a polybutadiene-block-polyethylene oxide copolymer (polybutadiene content is 75 wt.%), The temperature is lowered to -50 ° C and 0.6 ml of phosphorus trichloride and 0.35 ml of tetrachloride are successively added. titanium. After the addition is complete, the temperature is rapidly increased to 50 ° C over 10 minutes and the reaction mixture is maintained for 2 hours. The temperature of the catalyst suspension is reduced to room temperature, the suspension is allowed to stand and it is allowed to precipitate, and then it is washed 3 times with 50 ml of hexane. After washing is completed by drying, a brown solid free-flowing powdery substance is obtained having an average particle size of 15.7 μm.

Elemental analysis (ICP): 9.35 wt.% Ti, 13.14 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 9.

Example 24

Instead of 2 ml, 6 ml of a hexane solution of a polybutadiene-block-polyethylene oxide copolymer is used, and instead of 0.6 ml of phosphorus trichloride, 0.6 ml of phosphorus oxychloride is used. Other conditions are the same as in example 23, and the average particle size is 7.56 μm.

Elemental analysis (ICP): 11.37 wt.% Ti, 13.24 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 9.

Example 25

When preparing the catalyst, 3.0 ml of isooctanol is used instead of 1.0 ml, "the temperature is rapidly increased to 50 ° C over 10 minutes" is replaced by "the temperature is slowly raised to room temperature and then heated to 50 ° C." Other conditions are the same as in example 23, and the average particle size is 14.6 μm.

Elemental analysis (ICP): 10.75 wt.% Ti, 14.18 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 9.

Comparative example 2 '

When preparing the catalyst, a hexane solution of a polybutadiene-block-polyethylene oxide copolymer was not added, and other conditions are the same as in Example 23. The resulting catalyst has an average particle size of 64.76 μm, and the particle size distribution is a wider multimodal distribution.

Table 9 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 (g / 10 min) Bulk Density (g / ml) Example 23 Polymerization of Ethylene A 7.8 81,398 0.30 Polymerization of Ethylene B 18.3 1,67 0.31 Example 24 Polymerization of Ethylene A 13.6 87.61 0.31 Polymerization of Ethylene B 28.9 1,57 0.32 Example 25 Polymerization of Ethylene A 9.1 34.25 0.30 Polymerization of Ethylene B 21.3 1.81 0.30 Comparative example 2 ' Polymerization of Ethylene A 5.9 68.32 0.26 Polymerization of Ethylene B 14.6 1,67 0.27

From the data for examples and comparative example presented in Table 9, it can be seen that if polybutadiene-block-polyethylene oxide copolymers are used as modifying additives in the preparation of the catalyst, the particle shape of the obtained catalyst and polymers is good, the particle size distribution is narrow, bulk density (OD) polymer resin is high and overall catalyst performance is good.

Example 26

30 ml of hexane, 3.15 ml of a hexane solution of dibutylmagnesium (1M) and 1.0 ml of isooctanol are successively measured and mixed, the temperature is raised to 50 ° C and the reaction mixture is kept under stirring for 0.5 h and a clear solution is obtained, then 2 ml of a hexane solution (10 g / l) of a polybutadiene-block-polyethylene oxide copolymer (the polybutadiene content is 75 wt.%), The temperature is lowered to -10 ° C and 0.36 ml of silicon tetrachloride and 0.35 ml of titanium tetrachloride are successively added. After the addition is complete, the temperature is rapidly increased to 50 ° C over 10 minutes and the reaction mixture is maintained for 2 hours. The temperature of the catalyst suspension is reduced to room temperature, the suspension is allowed to stand and it is allowed to precipitate, and then it is washed 3 times with 50 ml of hexane. After washing is completed by drying, a brown solid free-flowing powdery substance is obtained having an average particle size of 37.4 μm.

Elemental analysis (ICP): 10.06 wt.% Ti, 19.29 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 10.

Example 27

Upon preparation of the catalyst, the step "the temperature within 10 min is rapidly increased to 50 ° C" is replaced by the step "the temperature is increased to 50 ° C in the programmed mode for 120 min" and other conditions are the same as in example 26. The average particle size is 43.7 microns.

Elemental analysis (ICP): 6.24 wt.% Ti, 13.55 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 10.

Example 28

When preparing the catalyst, instead of 1.0 ml of isooctanol, 0.6 ml of n-butanol is used, instead of 2 ml, 10 ml of a hexane solution (10 g / l) of a polybutadiene-block-polyethylene oxide copolymer is used, and other conditions are the same as in Example 26. The average particle size is 18.7 microns.

Elemental analysis (ICP): 11.54 wt.% Ti, 23.69 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 10.

Comparative example 3 '

When preparing the catalyst, a hexane solution of a polybutadiene-block-polyethylene oxide copolymer is not added and other conditions are the same as in Example 26. The obtained catalyst has an average particle size of 79.46 μm, and the particle size distribution is a wider multimodal distribution.

Table 10 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 (g / 10 min) Bulk Density (g / ml) Example 26 Polymerization of Ethylene A 8.6 101.5 0.33 Polymerization of Ethylene B 27.7 2,32 0.34 Example 27 Polymerization of Ethylene A 6.1 74.36 0.31 Polymerization of Ethylene B 10.7 1.85 0.31 Example 28 Polymerization of Ethylene A 11,4 105.7 0.34 Polymerization of Ethylene B 32,7 1.99 0.34 Comparative example 3 ' Polymerization of Ethylene A 6.4 87.38 0.28 Polymerization of Ethylene B 22.6 1.49 0.29

From the data in Table 10 for examples and a comparative example, it can be seen that if polybutadiene-block-polyethylene oxide copolymers are used in the preparation of the catalyst, the particle shape of the obtained catalyst and polymers is good, the particle size distribution is narrow, the bulk density (OD) of the polymer the resin is high and overall catalyst performance is good.

Example 29

30 ml of hexane, 3.15 ml of a hexane solution of dibutylmagnesium (1M) and 1.0 ml of isooctanol are added and stirred sequentially, the temperature is raised to 50 ° C and the reaction mixture is kept under stirring for 0.5 h and a clear solution is obtained. Then add 3 ml of a hexane solution (10 g / l) of a polybutadiene-block-polyethylene oxide copolymer (the polybutadiene content is 75 wt.%), The temperature is lowered to -50 ° C and 1.6 ml of a hexane solution of aluminum ethyl dichloride (2M) is added sequentially and 0.35 ml of titanium tetrachloride. After keeping the reaction mixture at low temperature for 0.5 h, the temperature is allowed to slowly and spontaneously rise to room temperature. Then the reaction was carried out at 50 ° C for 2 hours. The temperature of the catalyst suspension was lowered to room temperature, the suspension was allowed to stand and it was allowed to precipitate, and then it was washed 3 times with 50 ml of hexane. After washing is completed by drying, a brown solid free-flowing powdery substance is obtained having an average particle size of 17.3 μm.

Elemental analysis (ICP): 10.83 wt.% Ti, 13.57 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 11.

Example 30

When preparing the catalyst, instead of 3 ml, 6 ml of a hexane solution (10 g / l) of a polybutadiene-block-polyethylene oxide copolymer are used and other conditions are the same as in Example 29. The average particle size is 5.68 μm.

Elemental analysis (ICP): 10.34 wt.% Ti, 14.02 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 11.

Example 31

Upon receipt of the catalyst, the stage "the reaction mixture is kept for 0.5 h at low temperature and the temperature is allowed to slowly rise to room temperature spontaneously" is replaced by the stage "after the addition is complete, the temperature is increased to 50 ° C for 10 minutes" and other conditions are the same as in example 29. The average particle size is 23.7 microns.

Elemental analysis (ICP): 12.36 wt.% Ti, 10.57 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 11.

The procedure for the polymerization of propylene is the same as described in example 12: 800 ml of hexane, 2.5 mmol of triethylaluminum, 0.125 mmol of diphenyldimethoxysilane (DDS) and 20 mg of catalyst components are added to a 2 L steel reactor, which is completely filled with gaseous propylene. obtained in example 3, then add 0.4 l (under normal conditions) of hydrogen, then add propylene to maintain the pressure in the reactor equal to 0.6 MPa, and the temperature is raised to 70 ° C. The polymerization is carried out for 2 hours, then the pressure is released and the products are discharged. The corresponding stereoregularity of the obtained polymers (the content of the substance remaining after extraction with boiling heptane) is 95.3%, and the specific polymerization results are shown in table 11.

Reference Example 4 '

The conditions are the same as in Example 29, except that a hexane solution of a polybutadiene-block-polyethylene oxide copolymer is not added. The resulting catalyst has an average particle size of 124.8 μm, and the particle size distribution is wider and contains a large number of peaks.

Table 11 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 (g / 10 min) Bulk Density (g / ml) Example 29 Polymerization of Ethylene A 9.3 35.64 0.32 Polymerization of Ethylene B 28.5 1.09 0.32 Example 30 Polymerization of Ethylene A 15.8 40.56 0.31 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 (g / 10 min) Bulk Density (g / ml) Polymerization of Ethylene B 53.7 1.25 0.32 Example 31 Polymerization of Ethylene A 11.7 78.84 0.31 Polymerization of Ethylene B 32,3 0.89 0.33 Propylene Polymerization 35.6 1.98 0.40 Reference Example 4 ' Polymerization of Ethylene A 11.5 25.64 0.25 Polymerization of Ethylene B 25.8 0.65 0.27

From the data in Table 11 for examples and a comparative example, it can be seen that if polybutadiene-block-polyethylene oxide copolymers are used as modifying additives in the preparation of the catalyst, the particle shape of the obtained catalyst and polymers is good, the particle size distribution is narrow, bulk density (OD) polymer resin is high and overall catalyst performance is good.

Example 32

30 ml of hexane, 3.15 ml of a hexane solution of dibutylmagnesium (1M) and 1.0 ml of isooctanol are successively measured and mixed, the temperature is raised to 50 ° C and the reaction mixture is kept under stirring for 0.5 h and a clear solution is obtained. Then, benzoyl chloride and 3 ml of a hexane solution (10 g / l) of a polybutadiene-block-polyethylene oxide copolymer (the content of polybutadiene is 75 wt.%) Are added 0.2 ml, the temperature is lowered to -50 ° C and 1.6 ml of a hexane solution are added successively aluminum ethyl dichloride (2M) and 0.35 ml of titanium tetrachloride. After keeping the reaction mixture at low temperature for 0.5 h, the temperature is allowed to slowly and spontaneously rise to room temperature and then the reaction is carried out at 50 ° C for 2 hours. The temperature of the catalyst suspension is lowered to room temperature, the suspension is allowed to stand and it is allowed to precipitate and then it is washed 3 times with hexane in 50 ml portions. After washing is completed by drying, a brown solid free-flowing powdery substance is obtained having an average particle size of 11.23 microns.

Elemental analysis (ICP): 11.14 wt.% Ti, 13.32 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 12.

Example 33

When preparing the catalyst, instead of 0.2 ml, 0.5 ml of benzoyl chloride is used, and instead of 1.6 ml of a hexane solution of aluminum ethyl dichloride, 1.6 ml of a hexane solution of aluminum isobutyl dichloride is used, and other conditions are the same as in example 32. The average particle size is 13.8 microns.

Elemental analysis (ICP): 10.18 wt.% Ti, 12.05 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 12.

Example 34

In preparing the catalyst, 0.2 ml of acetyl chloride is used instead of 0.2 ml of benzoyl chloride and the other conditions are the same as in Example 32. The average particle size is 9.88 μm.

Elemental analysis (ICP): 10.37 wt.% Ti, 12.89 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 12.

Example 29 '(comparative)

Benzoyl chloride is not added in the preparation of the catalyst, and other conditions are the same as in Example 32. The average particle size is 17.3 μm.

Table 12 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 (g / 10 min) Bulk Density (g / ml) Example 32 Polymerization of Ethylene A 18.2 93.69 0.30 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 (g / 10 min) Bulk Density (g / ml) Polymerization of Ethylene B 33.5 3.06 0.30 Example 33 Polymerization of Ethylene A 24.7 98.8 0.29 Polymerization of Ethylene B 38,2 3.36 0.31 Example 34 Polymerization of Ethylene A 21.6 86.7 0.30 Polymerization of Ethylene B 36,4 2.78 0.30 Example 29 '(comparative) Polymerization of Ethylene A 9.3 35.64 0.32 Polymerization of Ethylene B 28.5 1.09 0.32

From the data for examples and comparative example presented in Table 12, it can be seen that if acyl chloride is used in the preparation of the catalyst, the particle shape of the obtained catalyst and polymers is good, the particle size distribution is narrow; the sensitivity of the polymer resin to hydrogen is better; the overall performance of the catalyst is good, it is useful for the development of new polymer products with unique characteristics.

Example 35

30 ml of hexane, 3.15 ml of a hexane solution of dibutylmagnesium (1M) and 1.0 ml of isooctanol are successively measured and mixed, the temperature is raised to 50 ° C and the reaction mixture is kept under stirring for 0.5 h and a clear solution is obtained. Then 0.6 ml of tetraethylorthosilicate and 3 ml of a hexane solution (10 g / l) of a polybutadiene-block-polyethylene oxide copolymer (polybutadiene content of 75 wt.%) Are added, the temperature is lowered to -50 ° C and 1.6 ml of a hexane solution are added sequentially aluminum ethyl dichloride (2M) and 0.35 ml of titanium tetrachloride. After keeping the reaction mixture at low temperature for 0.5 h, the temperature is allowed to slowly and spontaneously rise to room temperature and then the reaction is carried out at 50 ° C for 2 hours. The temperature of the catalyst suspension is lowered to room temperature, the suspension is allowed to stand and it is allowed to precipitate and then it is washed 3 times with hexane in 50 ml portions. After washing is completed by drying, a brown solid free-flowing powdery substance is obtained having an average particle size of 20.1 μm.

Elemental analysis (ICP): 11.63 wt.% Ti, 12.95 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 13.

Example 36

In the preparation of the catalyst, instead of 0.6 ml, 1 ml of tetraethylorthosilicate is used; in the preparation of the catalyst, the stage “after keeping the reaction mixture at a low temperature for 0.5 h is allowed to slowly and rise to room temperature spontaneously” is replaced by the stage “after completion of the addition, the temperature in within 10 min, increase to 50 ° C "and other conditions are the same as in example 35. The average particle size is 27.6 microns.

Elemental analysis (ICP): 10.84 wt.% Ti, 12.12 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 13.

Example 37

In the preparation of the catalyst, 0.5 ml of isooctanol is used instead of 1.0 ml and 1.0 ml of tetraethylorthosilicate is used instead of 0.7 ml and the other conditions are the same as in Example 35. The average particle size is 23.8 μm.

Elemental analysis (ICP): 9.72 wt.% Ti, 10.57 wt.% Mg.

The polymerization procedures of ethylene A and B are the same as described in example 1, and the polymerization results are shown in table 13.

Example 29 '(comparative)

Upon receipt of the catalyst do not add 0.6 ml of tetraethylorthosilicate and other conditions are the same as in example 35. The average particle size is 17.3 microns.

Comparative Example 5 "

When preparing the catalyst, a hexane solution of a polybutadiene-block-polyethylene oxide copolymer is not added and other conditions are the same as in Example 35. The obtained catalyst has an average particle size of 93.35 μm, and the particle size distribution is a wider multimodal distribution.

Table 13 Type of polymerization Activity (kg polymer / g catalyst) IR _2.16 (g / 10 min) Bulk Density (g / ml) Example 35 Polymerization of Ethylene A 4.6 23.27 0.35 Polymerization of Ethylene B 21.3 0.76 0.36 Example 36 Polymerization of Ethylene A 7.8 91.39 0.34 Polymerization of Ethylene B 21.6 2,32 0.36 Example 37 Polymerization of Ethylene A 7.1 17.4 0.34 Polymerization of Ethylene B 12.8 0.68 0.35 Example 29 '(comparative) Polymerization of Ethylene A 9.3 35.64 0.32 Polymerization of Ethylene B 28.5 1.09 0.32 Comparative Example 5 " Polymerization of Ethylene A 2.9 18.47 0.28 Polymerization of Ethylene B 11.3 0.69 0.28

From the data for examples and comparative example presented in Table 13, it can be seen that if silane is used in the preparation of the catalyst, the particle shape of the obtained catalyst and polymers is good, the particle size distribution is narrow, the bulk density (OD) of the polymer resin is high and general catalyst performance is good.

Claims (27)

1. A component of a catalyst for the polymerization of olefins, containing the reaction product of at least one organomagnesium compound, at least one titanium-containing compound, at least one hydroxy-containing compound, at least one chlorine-containing compound, and at least one polybutadiene block copolymer ,
wherein said organomagnesium compound has the formula (I), MgR ¹ _n Cl _2-n, wherein R ¹ is C ₂ -C ₂₀ -gidrokarbilnuyu group, and may have a saturated or unsaturated straight chain, branched chain or cyclic alkyl, and 0 <n≤2;
where the specified titanium-containing compound is described by the formula (II), Ti (OR ² ) _m Cl _4-m , in which R ² denotes a C ₂ -C ₂₀ -carbonyl group, and may have a saturated or unsaturated linear chain, branched chain or cyclic chain, and 0≤m≤4;
wherein said hydroxy-containing compound is described by formula (III), HOR ³ , in which R ³ is a C ₂ -C ₂₀ hydrocarbyl group, and may have a saturated or unsaturated linear chain, branched chain or cyclic chain, and
wherein said chlorine-containing compound is selected from the group consisting of a chlorine-containing organic compound, boron trichloride, trichlorophenylsilane, silicon tetrachloride, phosphorus trichloride, phosphorus pentachloride, methyldichlorophosphate and phosphorus oxychloride. 2. The catalyst component of claim 1, wherein said polybutadiene block copolymer is a polystyrene-block-polybutadiene copolymer or a polybutadiene-block-polyethylene oxide copolymer and comprises a diblock copolymer, triblock copolymer and derivatives thereof, in which the block may optionally have a linear a structure, a structure containing branched chains, or a star-shaped structure, and the polybutadiene content in said polybutadiene block copolymers is from 3 to 97 wt. % 3. The catalyst component according to claim 1, wherein said chlorine-containing organic compound is a chlorine-containing organoboron compound of the formula (IV), BR ⁴ _p Cl _3-p , in which R ⁴ is a C ₂ -C ₂₀ alkyl group or alkoxy group and 0 <p <3. 4. The catalyst component according to claim 1, wherein said chlorine-containing organic compound is a chlorine-containing organophosphorus compound of the formula (V), O _d PR ⁵ _q Cl _3-q , in which R ⁵ is a C ₂ -C ₂₀ alkyl group or alkoxy, 0 <q <3 and d is 0 or 1. 5. The catalyst component according to claim 1, wherein said chlorine-containing organic compound is a chlorine-containing organosilicon compound of the formula (VI), SiR ⁶ _e Cl _4-e , in which R ⁶ is a C ₂ -C ₂₀ alkyl group or alkoxy group and 0 <e <4. 6. The catalyst component according to claim 1, wherein said chlorine-containing organic compound is a chlorine-containing organoaluminum compound described by formula (VII) AlR ⁷ _f Cl _3-f , in which R ⁷ is a C ₂ -C ₂₀ hydrocarbyl group and 0.5 ≤f≤2.5. 7. The catalyst component according to any one of paragraphs. 1-6, where in the reaction of obtaining the catalyst component using an acyl chloride, said acyl chloride is selected from the group consisting of formyl chloride, acetyl chloride, and is described by formula (VIII), R ⁸ COCl, in which R ⁸ is a C ₂ -C ₂₀ hydrocarbyl group and may have a saturated or unsaturated linear chain, branched chain or cyclic chain. 8. The catalyst component according to any one of paragraphs. 1-6, where silane is additionally used in the reaction to obtain a catalyst component, said silane is described by formula (IX), Si (OR ⁹ ) _g Cl _4-g , in which R ⁹ is a C ₂ -C ₂₀ hydrocarbyl group, and may have saturated or unsaturated linear chain, branched chain or cyclic chain and 0 <g≤4. 9. The catalyst component according to any one of paragraphs. 1-6, in which the specified organomagnesium compound is described by formula (I), in which R ¹ denotes a C ₂ -C ₂₀ -alkyl group. 10. The catalyst component of claim 9, wherein said organomagnesium compound is at least one compound selected from the group consisting of dibutyl magnesium, diisobutyl magnesium, dioctyl magnesium, butyl octyl magnesium, ethyl ethyl chloride and magnesium butyl chloride. 11. The catalyst component according to any one of paragraphs. 1-6, in which in formula (II), which describes a titanium-containing compound, m is 4 or 0. 12. The catalyst component of claim 11, wherein said titanium-containing compound is at least one compound selected from the group consisting of titanium tetrachloride, tetraethyl titanate and tetrabutyl titanate. 13. The catalyst component according to any one of paragraphs. 1-6, wherein said hydroxy-containing compound is at least one compound selected from the group consisting of n-butanol, n-hexanol, isooctanol, benzyl alcohol and phenylethanol. 14. The catalyst component of claim 3, wherein said chlorine-containing organoboron compound is at least one compound selected from the group consisting of dichloromethylboron, dichloroethylboron, dichlorobutylboron, dichloromethoxyboron, dichloroethoxyboron and dichlorobutoxyboron. 15. The catalyst component of claim 4, wherein said chlorine-containing organophosphorus compound is at least one compound selected from the group consisting of dichloromethyl phosphorus, dichloroethyl phosphorus, dichlorobutyl phosphorus, ethyl dichlorophosphate and butyl dichlorophosphate. 16. The catalyst component according to claim 5, wherein said chlorine-containing organosilicon compound is at least one compound selected from the group consisting of trichloromethylsilane, trichloroethylsilane, trichloroctylsilane, trichloromethoxysilane, trichloroethoxysilane, trichlorobutoxysilane, dichlorodimethylene dichlorodimethylene. 17. The catalyst component according to claim 6, in which the specified chlorine-containing organoaluminum compound is described by the formula (VII), AlR ⁷ _f Cl _3-f , in which R ⁷ denotes a straight-chain or branched chain C ₂ -C ₆ -carbonyl group . 18. The catalyst component of claim 17, wherein said chlorine-containing organoaluminum compound is at least one compound selected from the group consisting of dichloroethyl aluminum, ethyl sesquichloride aluminum, diethyl aluminum chloride and dichloroisobutyl aluminum. 19. The catalyst component of claim 7, wherein said acyl chloride is at least one compound selected from the group consisting of propionyl chloride, butyryl chloride, benzoyl chloride, phenylacetyl chloride, phenylpropionyl chloride and phenylbutyryl chloride. 20. The catalyst component of claim 8, wherein said silane is at least one compound selected from the group consisting of chlorotrimethoxysilane, chlorotriethoxysilane, chlorotributoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, dichlorodibutoxysilane, tetraethyl butyl orthosilyl orthosilane. 21. The catalyst component according to any one of paragraphs. 1-6, in which the specified polybutadiene block copolymer, the polybutadiene content is from 10 to 90 wt. % 22. The method of obtaining the specified component of the catalyst according to any one of paragraphs. 1-6, comprising the following stages:
step a) reacting an organomagnesium compound with a hydroxy-containing compound to obtain a clear solution;
step b) dispersing the polybutadiene block copolymer in a C ₄ -C ₂₀ alkane or aromatic solvent to obtain a solution, which is then reacted with the clear solution obtained in step a), and a mixture is obtained;
and
step c) sequentially adding to the mixture obtained in step b) a chlorine-containing compound and a titanium-containing compound to obtain a catalyst component. 23. The method of obtaining the specified component of the catalyst according to claim 7 or 8, comprising the following stages:
step a) reacting an organomagnesium compound with a hydroxy-containing compound to obtain a clear solution;
stage b) dispersing the polybutadiene block copolymer in a C ₄ -C ₂₀ alkane or aromatic solvent to obtain a solution which is then reacted with the indicated acyl chloride or the indicated silane and a clear solution obtained in stage a), and a mixture is obtained;
step c) sequentially adding to the mixture obtained in step b) a chlorine-containing compound and a titanium-containing compound to obtain a catalyst component. 24. The production method of claim 23, wherein said titanium-containing compound is used in an amount of 0.01 to 10 moles, said hydroxy-containing compound is used in an amount of 0.1 to 20 moles, said chlorine-containing compound is used in an amount comprising from 0.1 to 50 moles, said acyl chloride or said silane is used in an amount of from 0.001 to 20 moles in terms of 1 mol of an organomagnesium compound, and the content of said polybutadiene block copolymer in the reaction the onone system is regulated in the range from 0.001 to 100 g / l. 25. The production method according to claim 24, wherein said titanium-containing compound is used in an amount of 0.05 to 5 moles, said hydroxy-containing compound is used in an amount of 0.2 to 10 moles, said chlorine-containing compound is used in an amount comprising from 0.5 to 20 moles, said acyl chloride or said silane is used in an amount of from 0.01 to 10 moles in terms of 1 mol of an organomagnesium compound, and the content of said polybutadiene block copolymer in the reaction This system is regulated in the range from 0.01 to 50 g / l. 26. A catalyst designed for homopolymerization or copolymerization of olefins containing the reaction products of the following components:
(a) the specified component of the catalyst intended for the polymerization of olefins, according to any one of paragraphs. 1-6;
(b) at least one of the organoaluminum compounds represented by the formula AlR ''_'3 in which R''' _3, which may be identical or different from one another can denote C ₁ -C ₈ -alkyl groups, or one two of which may be substituted with chlorine. 27. The use of said catalyst according to claim 26 for homopolymerization or copolymerization of olefins, wherein said olefin is ethylene, propylene, butylene, hexene or octene.

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