Catalyst component for olefin polymerization as well as preparation method, catalyst and application thereof

Abstract

The invention provides a catalyst component for olefin polymerization, a preparation method of the catalyst component, a catalyst and application of the catalyst component. The catalyst component comprises a reaction product of a magnesium compound, an organic anhydride compound, a titanate compound, an alcohol compound and a titanium halide. The magnesium compound is a compound formed by dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organic phosphorus compound. The polymerization activity of the catalyst particles is high, polyethylene powder with high bulk density can be obtained through polymerization, the fine powder content of the polymer powder is low, and the requirement of an industrial production device for the catalyst is met.

Description

Technical Field

[0001] This invention belongs to the field of olefin polymerization, specifically relating to a catalyst component for olefin polymerization, its preparation method, the catalyst, and its application. Background Technology

[0002] Currently, slurry polymerization industrial production units have high requirements for the bulk density of polyethylene powder. This is because, in the slurry polymerization process, after centrifugal separation of the polymer / hexane slurry, high bulk density powder has a lower hexane carrying capacity, which helps reduce the energy consumption of powder drying and increase the load on the drying unit. In addition, high bulk density powder is conducive to the efficient operation of the powder conveying unit in industrial production units, enabling the production unit to achieve higher production loads.

[0003] To achieve high packing density, it is typically necessary to first prepare polyethylene catalyst particles with good morphology. For example, patent document CN105482002A introduced organic acid anhydrides / acetic esters / cyclic ketones as complex electron donors into the N-series polyolefin catalyst preparation system, thus preparing spherical / quasi-spherical polyethylene catalyst particles for the first time. However, the polymerization activity of the aforementioned spherical / quasi-spherical polyethylene catalysts is low, which cannot meet the requirements of industrial slurry polyethylene production units such as CX, Hostalen, ACP, and InnoveneS for high-activity catalysts and high-packing-density polymers.

[0004] Therefore, there is a need to develop a spherical / quasi-spherical polyethylene catalyst with a simple preparation process that can polymerize into powder particles with high bulk density and high polymerization activity. Summary of the Invention

[0005] The inventors unexpectedly discovered during their research that, by introducing organic acid anhydrides, titanate compounds, and alcohols as electron donors into the N-series polyolefin catalyst preparation system according to this invention, spherical or near-spherical solid particles (solid catalyst components) can be prepared through the halide reaction of magnesium complexes, organic acid anhydrides, titanate compounds, alcohols, and titanium. This type of catalyst has a simple preparation process, high polymerization activity, and can polymerize to obtain polyethylene powder with high bulk density.

[0006] A first aspect of the present invention is to provide a catalyst component for olefin polymerization, comprising a magnesium complex, an organic acid anhydride compound, a titanate compound, an alcohol compound, and a reaction product of a titanium halide; wherein the magnesium complex is a complex formed by dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organophosphorus compound.

[0007] In a preferred embodiment of the present invention, the catalyst component for olefin polymerization comprises a reaction product prepared according to the following steps:

[0008] (a) Dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to obtain a magnesium complex;

[0009] (b) The magnesium complex was reacted with an organic acid anhydride to obtain a reaction mixture;

[0010] (c) The reaction mixture obtained in step (b) is contacted with a titanium halide compound to obtain a reaction mixture;

[0011] (d) Contact the reaction mixture from step (c) with an alcohol compound and heat to precipitate solid particles;

[0012] (e) The reaction mother liquor and solid particles are preferably aged at 70-120°C to obtain the catalyst component; preferably, the catalyst component is obtained by washing with an inert solvent after aging.

[0013] In one or more of steps (c), (d), and (e), a titanate compound is added;

[0014] In this preferred embodiment, the catalyst component and the corresponding catalyst prepared according to the specific method steps described above have higher polymerization activity and can be polymerized to obtain polyethylene powder with higher bulk density.

[0015] In the above technical solution, "adding a titanate compound in one or more of steps (c), (d), and (e)" means that the titanate compound can be added in one of steps (c), (d), and (e), or the titanate compound can be added in two or three of the above three steps, and the present invention can be achieved in either case.

[0016] The inventors of this invention have discovered through research that, in a more preferred embodiment of this invention, the catalyst component comprises a reaction product prepared according to the following method:

[0017] (1) Dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to obtain a magnesium complex;

[0018] (2) The magnesium complex is reacted with organic acid anhydride compounds, and the reaction mixture is then contacted with titanium halides, followed by reaction with titanate compounds and alcohol compounds. After heating and aging treatment, the catalyst component is obtained.

[0019] According to an embodiment of the catalyst component of the present invention, the magnesium complex is a complex formed by dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organophosphorus compound.

[0020] In a preferred embodiment of the catalyst component of the present invention, the magnesium halide is selected from magnesium dihalide or a complex formed by magnesium dihalide with water, alcohol, or an electron donor; preferably, the magnesium dihalide is selected from at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, and magnesium diiodide, more preferably magnesium dichloride; and / or, the alcohol is selected from at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, and isooctanol; and / or, the electron donor is selected from at least one of ammonia, hydroxylamine, ether, and ester.

[0021] As an example, the magnesium halide is selected from at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, and magnesium diiodide, and / or a complex formed by at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, and magnesium diiodide with at least one of water, methanol, ethanol, propanol, butanol, pentanol, hexanol, isooctanol, ammonia, hydroxylamine, ether, and ester. The magnesium halide can be used alone or in combination.

[0022] According to a preferred embodiment of the catalyst component of the present invention, the organic epoxide compound is selected from C2-C4. 18 The organic epoxy compound is selected from at least one of aliphatic olefins, aliphatic dienes, halogenated aliphatic olefins or oxides of halogenated aliphatic dienes, glycidyl ethers and internal ethers; preferably, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, butyl glycidyl ether.

[0023] According to a preferred embodiment of the catalyst component of the present invention, the organophosphorus compound is selected from at least one of a hydrocarbon ester or a halohydrocarbon ester of phosphoric acid or phosphorous acid; preferably, the organophosphorus compound is selected from trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tri-tert-butyl phosphate, tri-n-pentyl phosphate, triisopentyl phosphate, tri-n-hexyl phosphate, triisohexyl phosphate, tri-n-heptyl phosphate, triisoheptyl phosphate, and phosphorus. The following is a list of at least one of trioctyl phosphate, triisooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, triisobutyl phosphite, tritert-butyl phosphite, tripentyl phosphite, triisopentyl phosphite, trihexyl phosphite, triheptanyl phosphite, triisoheptyl phosphite, trioctyl phosphite, triisooctyl phosphite, triphenyl phosphite, and dibutyl phosphite.

[0024] To ensure more complete dissolution, an inert diluent may optionally be added to the solvent system. Typically, this inert diluent is selected from aromatic compounds and / or alkane compounds. Preferably, the inert diluent is selected from aromatic compounds and / or alkane compounds; more preferably, the aromatic compounds include at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene, and / or their derivatives; the alkane compounds include at least one of straight-chain alkanes, branched alkanes, or cycloalkanes having 3 to 20 carbon atoms; any diluent that contributes to the dissolution of magnesium halides may be used. The aforementioned inert diluents may be used alone or in combination.

[0025] According to a preferred embodiment of the catalyst component of the present invention, the structure of the organic acid anhydride compound is shown in formula (1):

[0026] In equation (1), R5 and R6 may be the same or different, and each is independently hydrogen or C1-C. 10 Alkyl, C2-C 10 alkenyl, C2-C 10 alkynyl group, C3-C 10 cycloalkyl or C6-C 10 Aromatic hydrocarbon groups, and R5 and R6 can form rings in any way;

[0027] According to a preferred embodiment of the catalyst component of the present invention, C1-C 10 Examples of alkyl groups include C1, C2, C3, C4, C5, C6, C7, C8, C9 ... 10 Straight-chain or branched alkyl groups, preferably methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, etc. C2-C 10 Alkenyl groups include C2, C3, C4, C5, C6, C7, C8, C9 ... 10 Straight-chain or branched alkenyl groups, such as vinyl, propenyl, butenyl, etc. Examples of C3-C8 cycloalkyl groups include, but are not limited to, cyclopropyl, methylcyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl, etc. C6-C 20 Examples of aromatic hydrocarbon groups include, but are not limited to, phenyl, benzyl, dimethylphenyl, etc.

[0028] According to a preferred embodiment of the catalyst component of the present invention, the organic acid anhydride compound is selected from at least one of acetic anhydride, propionic anhydride, butyric anhydride, acrylic anhydride, phthalic anhydride, butylene anhydride and maleic anhydride.

[0029] According to a preferred embodiment of the catalyst component of the present invention, the titanium halide has the general formula Ti(OR8). a X b R8 is C1-C10 The aliphatic or aromatic hydrocarbon group, X is a halogen, preferably fluorine, chlorine or bromine, a is 0, 1 or 2, b is an integer from 1 to 4, and a+b=3 or 4.

[0030] According to a preferred embodiment of the catalyst component of the present invention, R8 is selected from C1-C6 alkyl, C2-C6 alkenyl, C3-C8 cycloalkyl, or C6-C 10 The aromatic hydrocarbon group. Preferably, R8 is selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclopropyl, methylcyclopropyl, n-pentyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl, and xylylyl.

[0031] According to a preferred embodiment of the catalyst component of the present invention, the titanium halide is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium monochlorotriethoxy, titanium trichloride, titanium dichlorodiethoxy, and titanium trichloromonethoxy.

[0032] According to a preferred embodiment of the catalyst component of the present invention, the titanate compound has the general formula Ti(OR). n n > 0; R is selected from C 1～ C 10 The compound is an aliphatic alkyl group. Specifically, it may be selected from one or more of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, isopropyl titanate, n-butyl titanate, isobutyl titanate, tetraoctyl titanate, and tetraisooctyl titanate. Preferably, the titanate ester compound is at least one of tetraethyl titanate and tetrabutyl titanate.

[0033] According to a preferred embodiment of the catalyst component of the present invention, the alcohol compound is selected from C1-C6. 18 The fatty alcohol or aromatic alcohol is preferably at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isooctanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, butanediol, hexanediol and isohexanediol, more preferably at least one of ethanol, butanol, isobutanol, tert-butanol, phenethyl alcohol and butanediol.

[0034] According to the present invention, the proportions of each raw material can be selected within a wide range. In a preferred embodiment of the present invention, relative to magnesium halide per mole of magnesium, the amount of organic epoxy compound is 0.2-10 mol; the amount of organic phosphorus compound is 0.1-10 mol; the amount of organic acid anhydride compound is 0.03-1 mol; the amount of titanate compound is 0.01-1 mol; the amount of alcohol compound is 0.1-4 mol; and the amount of titanium halide is 0.5-120 mol. In this preferred embodiment, the catalyst composition obtained corresponds to a catalyst with higher polymerization activity, and can polymerize to obtain polyethylene powder with higher bulk density.

[0035] More preferably, relative to magnesium halides per mole of magnesium, the amount of organic epoxy compound is 0.5-2.0 mol; the amount of organic phosphorus compound is 0.5-2.0 mol; the amount of organic acid anhydride compound is 0.1-0.3 mol; the amount of titanate compound is 0.05-0.20 mol; the amount of alcohol compound is 0.1-2.0 mol; and the amount of titanium halide is 5-20 mol.

[0036] Existing solvent extraction technologies typically use non-spherical catalyst particles, and their polymer powders also tend to be non-spherical. However, the method disclosed in CN105482002A allows for the preparation of spherical catalysts and polymer powders. Unfortunately, such catalysts exhibit relatively low polymerization activity and hydrogen sensitivity, limiting their applications. Therefore, the inventors continued their research and ultimately proposed the preparation method of this invention.

[0037] The inventors of this invention unexpectedly discovered through research that, when using titanate esters and alcohols, and following the specific preparation method of this invention, under more preferred formulation conditions, a catalyst with superior particle morphology can be obtained. Furthermore, this catalyst can polymerize to form spherical powder particles, which also possess a high packing density. The preferred formulation is as follows: relative to magnesium halide per mole of magnesium, the amount of organic epoxy compound is 0.5-1.5 mol; the amount of organic phosphorus compound is 0.5-1.5 mol; the amount of organic anhydride compound is 0.1-0.3 mol; the amount of titanate ester compound is 0.05-0.20 mol; the amount of alcohol compound is 0.1-1 mol; and the amount of titanium halide is 5-15 mol.

[0038] A second aspect of the present invention is to provide a method for preparing the catalyst component described in the first aspect, comprising reacting a magnesium complex, an organic acid anhydride compound, a titanate compound, an alcohol compound, and a titanium halide; preferably comprising the following steps:

[0039] (a) Dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to obtain a magnesium complex;

[0040] (b) The magnesium complex was reacted with an organic acid anhydride to obtain a reaction mixture;

[0041] (c) The reaction mixture obtained in step (b) is contacted with a titanium halide to obtain a reaction mixture;

[0042] (d) Contact the reaction mixture from step (c) with an alcohol compound and heat to precipitate solid particles;

[0043] (e) The reaction mother liquor and solid particles are preferably aged at 70-120°C to obtain the catalyst component; preferably, the catalyst component is washed with an inert solvent after aging.

[0044] In one or more of steps (c), (d), and (e), a titanate compound is added.

[0045] In a preferred embodiment of the present invention, the preparation method includes the following steps:

[0046] (1) Dissolve magnesium halide in a solvent system containing organic epoxy compounds and organic phosphorus compounds to obtain a magnesium complex;

[0047] (2) The magnesium complex is reacted with organic acid anhydride compounds, and the reaction mixture is then contacted with titanium halides, followed by reaction with titanate compounds and alcohol compounds. After heating and aging treatment, the catalyst component is obtained.

[0048] Preferably, the preparation method includes the following steps:

[0049] S1, dissolve magnesium halide in a solvent system containing organic epoxy compounds and organophosphorus compounds to form a homogeneous solution;

[0050] S2, react the solution obtained in step S1 with organic acid anhydride compounds, then contact the reaction product with titanium halides first, then with titanium ester compounds and alcohol compounds, and then raise the temperature to precipitate spherical or near-spherical solid particles in the mixture.

[0051] S3, the reaction mother liquor and solid particles are aged at 70-120℃ to obtain a mixture;

[0052] S4, Remove unreacted substances and solvent from the mixture obtained in step S3 to obtain the catalyst component.

[0053] In this application, high temperature can refer to a temperature above 70°C, preferably a temperature range of 70°C to 120°C.

[0054] In a preferred embodiment of the present invention, in step S1, magnesium halide and a solvent system containing organic epoxy compounds and organophosphorus compounds are reacted at 50-70°C for 1-3 hours to form a homogeneous solution; and / or,

[0055] In step S2, the reaction temperature of the solution obtained in step S1 with the organic acid anhydride compound is the same as or different from the temperature in step S1, preferably 50-70℃, and the reaction time is 0.5-2 hours. After that, the temperature of the reaction system is lowered to -60℃ to -20℃, and then it is contacted with titanium halides, titanate compounds and alcohol compounds. Then the temperature is gradually increased, preferably at a rate of 0.2-2℃ / min, to 70℃-120℃, and then aged for 1-4 hours.

[0056] The selection and proportioning of raw materials used in the preparation method are the same as those described in the first aspect of this invention, and will not be repeated here.

[0057] A third aspect of the present invention is to provide a catalyst for olefin polymerization, comprising the following components:

[0058] A): The catalyst component described in the first aspect or the catalyst component obtained according to the preparation method described in the second aspect;

[0059] B): The general formula is AlR' d X' 3-d Organoaluminum compounds, wherein R' is hydrogen or C l -C 20 Hydrocarbon group, X' is a halogen atom, preferably fluorine, chlorine or bromine, 0 <d≤3;

[0060] Preferably, the molar ratio of aluminum in component B) to titanium in component A) is (20-200):1, more preferably (50-100):1.

[0061] According to some embodiments of the present invention, R' can be a hydrogen group or a hydrocarbon group having 1-20 carbon atoms, particularly C. l -C 20 alkyl, C l -C 20 Aryl or C l -C 20 The aryl group. Specific compounds include alkylaluminum compounds such as Al(CH3)3, Al(CH2CH3)3, Al(i-Bu)3, AlH(CH2CH3)2, AlH(i-Bu)2, AlCl(CH2CH3)2, Al2Cl3(CH2CH3)3, AlCl(CH2CH3)2, and AlCl2(CH2CH3). Al(CH2CH3)3 and Al(i-Bu)3 are preferred.

[0062] According to some embodiments of the present invention, the molar ratio of aluminum in component B) to titanium in component A) is 5:1-500:1, more preferably 20:1-200:1, and most preferably 50:1-100:1.

[0063] In this specification, inert solvents include: isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene, and other saturated aliphatic or aromatic hydrocarbons.

[0064] In this specification, the term "aliphatic hydrocarbon group" refers to a straight-chain or branched chain hydrocarbon group consisting only of carbon and hydrogen atoms. Specific examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, vinyl, 1-propenyl, allyl, ethynyl, 1-propynyl, 2-propynyl, butynyl, etc.

[0065] In this specification, "aromatic hydrocarbon group" refers to a hydrocarbon group having a benzene ring, including aryl, aryl-substituted hydrocarbon groups, or hydrocarbon-substituted aryl groups, such as phenyl, benzyl, anthracene, and naphthyl.

[0066] A fourth aspect of the present invention is to provide the application of the catalyst described herein in ethylene polymerization.

[0067] Polymerization can be carried out using either slurry polymerization or gas-phase polymerization.

[0068] Slurry polymerization media include: isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene and other saturated aliphatic hydrocarbons or aromatic hydrocarbons and other inert solvents.

[0069] According to an embodiment of the present invention, the catalyst particles prepared by the catalyst components are spherical or near-spherical, with a polymerization activity ≥25000 g·polyethylene / g·catalyst and a bulk density ≥0.36 g / ml (specific reaction conditions are: hydrogen 0.28 MPa, ethylene 0.45 MPa, polymerization temperature 80°C, polymerization time 2 h).

[0070] By introducing organic acid anhydrides, titanate compounds, and alcohols as electron donors into the N-series polyolefin catalyst preparation system according to the method of this invention, and through the reaction of magnesium complexes, organic acid anhydrides, titanate compounds, alcohols, and titanium halides, spherical or near-spherical solid particles (solid catalyst components) containing magnesium and titanium can be prepared. These catalyst particles exhibit high polymerization activity and can polymerize to obtain polyethylene powder with high bulk density.

[0071] Compared with the prior art, the present invention has the following advantages:

[0072] (1) As described above, the catalyst particles of this invention have high polymerization activity and can be polymerized to obtain polyethylene powder with high bulk density.

[0073] (2) The present invention uses simple raw materials, the raw material sources are simple, the preparation method is simple and controllable, the cost is low, and the post-processing process is simple.

[0074] (3) This invention belongs to the category of dissolution-eluent catalysts. As can be verified, different particle sizes can be obtained by using different conditions. Thus, catalysts with a relatively wide particle size range can be obtained by following the method of this invention. This is an important manifestation of the superiority of this invention. It can produce catalyst products with specific particle sizes to meet the needs of different markets.

[0075] In summary, this invention improves the performance of existing Ziegler-Natta type olefin polymerization catalyst particles using simple raw materials, at a lower cost, and has extremely high value for widespread application. Attached Figure Description

[0076] Figure 1 This is an electron microscope image of the catalyst particles from Example 1.

[0077] Figure 2 This is an electron microscope image of the catalyst particles in Example 2.

[0078] Figure 3 This is an electron microscope image of the catalyst particles in Example 3.

[0079] Figure 4 This is an electron microscope image of the catalyst particles in Comparative Example 1.

[0080] Depend on Figure 1-3 and Figure 4 As can be seen from the comparison, the embodiments of the present invention can obtain spherical / quasi-spherical catalyst particles with very uniform particle morphology. Detailed Implementation

[0081] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0082] Test method:

[0083] 1. Determination of catalyst / polymer powder morphology: Hitachi S-4800 scanning electron microscope was used.

[0084] 2. Determination of polymer bulk density: The apparent density, volume factor and pourability of plastics are determined using the test method (ASTM D1895).

[0085] 3. Particle size distribution of catalyst components: determined using a Malvern laser particle size and shape analyzer.

[0086] 4. The relative weight percentage of titanium in the catalyst component was determined by spectrophotometry.

[0087] 5. The method for detecting the content of fine powder >75μm in the obtained polymer powder is as follows: the particle size of the powder is determined by a vibrating sieve with a sieve standard of GB / T 6003.1—2012. The measured percentage content is a mass percentage.

[0088] The following embodiments are examples of the present invention in more detail, but the present invention is not limited to these embodiments.

[0089] Example 1

[0090] (1) Preparation of catalyst component A1

[0091] 4.8 g magnesium chloride, 110 ml toluene, 4 ml epichlorohydrin, and 12.5 ml tri-n-butyl phosphate were added to a reactor. The mixture was reacted for 3 hours at 350 rpm and 60°C. Then, 1.4 g phthalic anhydride was added, and the mixture was kept at this temperature for another hour. The temperature was then lowered to -30°C. 65 ml titanium tetrachloride was added dropwise, followed by 1 ml tetrabutyl titanate and 6 ml ethanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 90°C and kept at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain a solid catalyst component with good flowability. The titanium content and particle size are shown in Table 1.

[0092] (2) Polymerization reaction

[0093] A 2L stainless steel reactor was fully purged with high-purity nitrogen, then 1L of hexane and 2.0mL of 1M triethylaluminum were added, followed by catalyst component A1 (containing 0.4 mg of titanium) prepared by the above method. The temperature was raised to 70℃, and hydrogen was introduced to bring the pressure inside the reactor to 0.28MPa (gauge pressure). Ethylene was then introduced to bring the total pressure inside the reactor to 0.73MPa. Polymerization was carried out at 80℃ for 2 hours. The polymerization results are shown in Table 2.

[0094] (3) Electron micrographs: Electron micrographs of the catalyst particles can be found in [reference needed]. Figure 1 .

[0095] Example 2

[0096] (1) Preparation of catalyst component A2

[0097] 4.8 g magnesium chloride, 100 ml toluene, 4 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reactor. The reaction was carried out for 2 hours at 58°C and 400 rpm. Then, 1.4 g phthalic anhydride was added, and the mixture was kept at this temperature for another hour. The temperature was then lowered to -35°C. 75 ml titanium tetrachloride was added dropwise, followed by 1 ml tetrabutyl titanate and 6 ml ethanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 90°C and kept at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain a solid catalyst component with good flowability. The titanium content and particle size are shown in Table 1.

[0098] (2) Polymerization reaction: catalyst component A2 was used instead of catalyst component A1, and other conditions were the same as in Example 1. The polymerization results are shown in Table 2.

[0099] (3) Electron micrographs: Electron micrographs of the catalyst particles can be found in [reference needed]. Figure 2 .

[0100] Example 3

[0101] (1) Preparation of catalyst component A3

[0102] 4.8 g magnesium chloride, 100 ml toluene, 5.0 ml epichlorohydrin, and 20.0 ml tri-n-butyl phosphate were added to a reactor. The reaction was carried out for 2 hours at 55°C and 350 rpm. Then, 1.4 g phthalic anhydride was added, and the mixture was kept at this temperature for another hour. The temperature was then lowered to -40°C. 70 ml titanium tetrachloride was added dropwise, followed by 0.7 ml tetraethyl titanate and 5 ml ethanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 85°C and kept at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed repeatedly with toluene (an inert diluent) and hexane (an organic solvent) and dried to obtain a solid catalyst component with good flowability. The titanium content and particle size are shown in Table 1.

[0103] (2) Polymerization reaction: catalyst component A3 was used instead of catalyst component A1, and other conditions were the same as in Example 1. The polymerization results are shown in Table 2.

[0104] (3) Electron micrographs: Electron micrographs of the catalyst particles can be found in [reference needed]. Figure 3 .

[0105] Example 4

[0106] (1) Preparation of catalyst component A4

[0107] 4.8 g magnesium chloride, 110 ml toluene, 6.0 ml epichlorohydrin, and 14.0 ml triisobutyl phosphate were added to a reactor. The reaction was carried out for 2 hours at 56°C with a stirring speed of 400 rpm. Then, 1.2 g phthalic anhydride was added, and the mixture was kept at this temperature for another hour. The temperature was then lowered to -40°C. First, 80 ml titanium tetrachloride was added dropwise, followed by 1.5 ml tetrabutyl titanate and 6.0 ml ethanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 85°C and kept at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain a solid catalyst component with good flowability. The titanium content and particle size are shown in Table 1.

[0108] (2) Polymerization reaction: catalyst component A4 was used instead of catalyst component A1, and other conditions were the same as in Example 1. The polymerization results are shown in Table 2.

[0109] Example 5

[0110] (1) Preparation of catalyst component A5

[0111] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml triisobutyl phosphate were added to a reactor. The reaction was carried out for 2 hours at 59°C and 400 rpm. Then, 1.2 g phthalic anhydride was added, and the mixture was kept at this temperature for another hour. The temperature was then lowered to -40°C. 70 ml titanium tetrachloride was added dropwise, followed by 1.0 ml tetrabutyl titanate, 4 ml ethanol, and 1 ml n-butanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 85°C and held at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed repeatedly with toluene (an inert diluent) and hexane (an organic solvent) and dried to obtain a solid catalyst component with good flowability. The titanium content and particle size are shown in Table 1.

[0112] (2) Polymerization reaction:

[0113] A 2L stainless steel reactor was fully purged with high-purity nitrogen, then 1L of hexane and 1.0ml of 1M triethylaluminum were added, followed by solid catalyst component A5 (containing 0.6 mg of titanium) prepared by the above method. The temperature was raised to 80℃, and ethylene was introduced to bring the total pressure inside the reactor to 1.0 MPa (gauge pressure). Polymerization was carried out at 80℃ for 2 hours. The polymerization results are shown in Table 2.

[0114] Example 6

[0115] (1) Preparation of catalyst component A6

[0116] 4.8 g magnesium chloride, 100 ml toluene, 4.0 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reactor. The reaction was carried out for 2 hours at 58°C and a stirring speed of 260 rpm. Then, 1.4 g phthalic anhydride was added, and the mixture was kept at this temperature for another hour. The temperature was then lowered to -30°C. First, 85 ml titanium tetrachloride was added dropwise, followed by 1.0 ml tetrabutyl titanate, 4 ml ethanol, and 2 ml butanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 85°C and kept at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, and then dried to obtain a solid catalyst component with good flowability. The titanium content and particle size are shown in Table 1.

[0117] (2) Polymerization reaction: catalyst component A6 was used instead of catalyst component A5, and other conditions were the same as in Example 5. The polymerization results are shown in Table 2.

[0118] Example 7

[0119] The catalyst component was prepared according to the method of Example 1, except that 3-methylphthalic anhydride was used instead of phthalic anhydride in Example 1.

[0120] The polymerization reaction was carried out using the same method as in Example 1, and it was found that the performance of the catalyst component in Example 7 was close to that in Example 1.

[0121] Example 8

[0122] The catalyst component was prepared according to the method of Example 2, except that isobutyl titanate was used instead of n-butyl titanate in Example 2.

[0123] The polymerization reaction was carried out using the same method as in Example 2, and it was found that the performance of the catalyst component in Example 8 was similar to that in Example 2.

[0124] Example 9

[0125] The catalyst component was prepared according to the method of Example 4, except that 1-butanol was used instead of ethanol in Example 4.

[0126] The polymerization reaction was carried out using the same method as in Example 4, and it was found that the performance of the catalyst component in Example 9 was similar to that in Example 4.

[0127] Example 10

[0128] The catalyst components were prepared according to the method in Example 3, except that 0.4 ml of tetraethyl titanate and 3 ml of ethanol were added.

[0129] The polymerization reaction was carried out using the same method as in Example 3. The polymerization results are shown in Table 2.

[0130] Example 11

[0131] The catalyst component was prepared according to the method in Example 1, except that the preparation steps were as follows:

[0132] 4.8 g magnesium chloride, 110 ml toluene, 4 ml epichlorohydrin, and 12.5 ml tri-n-butyl phosphate were added to a reactor. The reaction was carried out for 3 hours at 350 rpm and 60°C. Then, 1.4 g phthalic anhydride was added, and the mixture was kept at this temperature for another hour. The temperature was then lowered to -30°C, and 1 ml tetrabutyl titanate was added dropwise, followed by 65 ml titanium tetrachloride and 6 ml ethanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 90°C and kept at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, and then dried to obtain a solid catalyst component with good flowability. The polymerization reaction was carried out using the same method as in Example 1. The polymerization results are shown in Table 2.

[0133] Comparative Example 1

[0134] (1) Preparation of catalyst component B1

[0135] 4.8 g magnesium chloride, 110 ml toluene, 4 ml epichlorohydrin, and 12.5 ml tri-n-butyl phosphate were added to a reactor. The mixture was reacted for 3 hours at 350 rpm and 60°C. Then, 1.4 g phthalic anhydride was added, and the mixture was kept at this temperature for another hour. The temperature was then lowered to -30°C, and 65 ml titanium tetrachloride was added dropwise, followed by 6 ml ethanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 90°C and kept at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, and then dried to obtain a solid catalyst component with good flowability. The titanium content and particle size are shown in Table 1.

[0136] (2) Polymerization reaction: catalyst component B1 was used instead of catalyst component A1, and other conditions were the same as in Example 1. The polymerization results are shown in Table 2.

[0137] (3) Electron micrographs: Electron micrographs of the catalyst particles can be found in [reference needed]. Figure 4 .

[0138] Comparative Example 2

[0139] (1) Preparation of catalyst component B2

[0140] 4.8 g magnesium chloride, 100 ml toluene, 4 ml epichlorohydrin, and 15 ml tri-n-butyl phosphate were added to a reactor. The mixture was reacted for 2 hours at 58°C and a stirring speed of 400 rpm. Then, 1.4 g phthalic anhydride was added, and the reaction was continued at this temperature for another hour. The temperature was then lowered to -35°C, and 75 ml titanium tetrachloride was added dropwise, followed by 1.2 ml ethyl benzoate and 6 ml ethanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 90°C and held at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed repeatedly with inert diluent toluene and organic solvent hexane, then dried to obtain a solid catalyst component with good flowability. The titanium content and particle size are shown in Table 1.

[0141] (2) Polymerization reaction: catalyst component B2 was used instead of catalyst component A1, and other conditions were the same as in Example 1. The polymerization results are shown in Table 2.

[0142] Comparative Example 3

[0143] (1) Preparation of catalyst component B3

[0144] 4.8 g magnesium chloride, 100 ml toluene, 5.0 ml epichlorohydrin, and 20.0 ml tri-n-butyl phosphate were added to a reactor. The mixture was reacted for 2 hours at 350 rpm and 55°C. Then, 1.4 g phthalic anhydride was added, and the mixture was kept at this temperature for another hour. The temperature was then lowered to -40°C, and 70 ml titanium tetrachloride was added dropwise. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 85°C and kept at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, and then dried to obtain a solid catalyst component with good flowability. The titanium content and particle size are shown in Table 1.

[0145] (2) Polymerization reaction: catalyst component B3 was used instead of catalyst component A1, and other conditions were the same as in Example 1. The polymerization results are shown in Table 2.

[0146] Comparative Example 4

[0147] (1) Preparation of catalyst component B4

[0148] 4.8 g magnesium chloride, 110 ml toluene, 4 ml epichlorohydrin, and 12.5 ml tri-n-butyl phosphate were added to a reaction vessel. The mixture was reacted for 3 hours at 350 rpm and 60°C. The temperature was then lowered to -30°C, and 65 ml titanium tetrachloride was added dropwise, followed by 6 ml ethanol. The temperature was then gradually increased (controlled within the range of 0.2-2°C / min) to 90°C and held at that temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed repeatedly with toluene (an inert diluent) and hexane (an organic solvent) and dried to obtain a solid catalyst component with good flowability.

[0149] (2) Polymerization reaction: catalyst component B4 was used instead of catalyst component A1, and other conditions were the same as in Example 1. The polymerization results are shown in Table 2.

[0150] Table 1

[0151]

[0152]

[0153] As shown in Table 1, adding titanate compounds during the catalyst preparation process can increase the titanium content of the catalyst, and titanate compounds can optimize the active sites of the catalyst.

[0154] Meanwhile, as can be seen from Examples 1-6 of this application, the present invention belongs to the dissolution-eluent type catalyst, and obtaining a relatively wide particle size range is an important manifestation of the superiority of the present invention. Thus, catalyst products with specific particle sizes can be produced for different needs.

[0155] Table 2

[0156]

[0157]

[0158] As shown in Table 2, a comparison of Examples 1-11 and Comparative Examples 1-3 shows that the catalyst of the present invention exhibits higher polymerization activity. This is because titanate compounds can modify the active sites of the catalyst. A comparison of Examples 1-11 and Comparative Example 4 shows that the polymer powder of the present invention has a significantly higher bulk density. This is because titanate compounds can modify the particle morphology of the catalyst, resulting in more compact catalyst particles. The polymer powder of the present invention has a low content of fine powder larger than 75 μm. In industrial plants, the amount of catalyst added can be reduced to produce the same grade of resin product, while simultaneously increasing the plant's production load. The catalyst of the present invention meets the requirements of industrial production plants for high polymerization activity, high powder bulk density, and low fine powder content.

[0159] When verifying the polymerization activity of catalyst components, the polymerization conditions have a significant impact on the results. For example, the polymerization conditions for the catalyst described in CN106478845A differ from those in this application. Those skilled in the art can clearly determine from the polymerization conditions that the catalyst activity in CN106478845A is far lower than that in this application. Compared to CN106478845A, the advantages of this invention are further: using titanate esters and alcohols as raw materials for catalyst preparation, under preferred specific feeding sequence conditions, the polymerization activity of the catalyst is improved while maintaining a near-spherical particle morphology, and the bulk density of the polymer powder can reach 0.35 g / cm³.3 The above can meet the requirements of industrial production equipment for high polymerization activity of catalysts, high powder bulk density and low fine powder content.

[0160] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

[0161] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

[0162] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0163] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0164] The endpoints and any values ​​of the ranges disclosed in this application are not limited to the precise ranges or values; such ranges or values ​​should be understood to include values ​​close to them. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In principle, various technical solutions can be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0165] In the context of this specification, except where expressly stated otherwise, any matters or issues not mentioned shall apply directly to those known in the art without any modification.

[0166] Furthermore, any implementation described herein can be freely combined with one or more other implementations described herein, and the resulting technical solutions or technical ideas shall be regarded as part of the original disclosure or original record of the present invention, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider the combination to be obviously unreasonable.

Claims

1. A catalyst component for the polymerization of olefins comprising the reaction product of a magnesium complex, an organic acid anhydride compound, a titanate compound, an alcohol compound, a halide of titanium; said magnesium complex being a complex formed by dissolving magnesium halide in a solvent system containing an organic epoxide compound and an organic phosphorus compound. The resulting reaction product is prepared according to the following steps:

2. The catalyst component of claim 1, characterized by (a) dissolving magnesium halide in a solvent system containing an organic epoxide compound and an organic phosphorus compound to obtain a magnesium complex; (b) reacting the magnesium complex with an organic acid anhydride compound to obtain a reaction mixture; (c) contacting the reaction mixture obtained in step (b) with a halide of titanium to obtain a reaction mixture; (d) contacting the reaction mixture in step (c) with an alcohol compound and warming to precipitate solid particles; (e) aging the reaction mother liquor and the solid particles, preferably at a temperature of 70 to 120°C, to obtain said catalyst component; wherein the titanate compound is added in one or more of steps (c), (d), (e); Preferably, the catalyst component comprises the reaction product prepared according to the following method: (1) dissolving magnesium halide in a solvent system containing an organic epoxide compound and an organic phosphorus compound to obtain a magnesium complex; (2) reacting the magnesium complex with an organic acid anhydride compound, then contacting the resulting reaction mixture with a halide of titanium, and then reacting with a titanate compound, an alcohol compound, and warming and aging to obtain said catalyst component.

3. The catalyst component according to claim 1 or 2, wherein: said magnesium halide is selected from magnesium dihalide or a complex of magnesium dihalide with at least one of water, an alcohol, and an electron donor; preferably, said magnesium dihalide is selected from at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, magnesium diiodide; and / or, said alcohol is selected from at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, iso-octanol; and / or, said electron donor is selected from at least one of ammonia, hydroxylamine, an ether, an ester.

4. The catalyst component according to claim 1 or 2, wherein: said organic phosphorus compound is selected from at least one of a hydrocarbyl or halogenated hydrocarbyl ester of orthophosphoric acid or of phosphorous acid; preferably, said organic phosphorus compound is selected from at least one of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, tri-i-propyl phosphate, tri-n-butyl phosphate, tri-i-butyl phosphate, tri-t-butyl phosphate, tri-n-pentyl phosphate, tri-i-pentyl phosphate, tri-n-hexyl phosphate, tri-i-hexyl phosphate, tri-n-heptyl phosphate, tri-i-heptyl phosphate, tri-n-octyl phosphate, tri-i-octyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, tri-i-propyl phosphite, tri-n-butyl phosphite, tri-i-butyl phosphite, tri-t-butyl phosphite, tri-n-pentyl phosphite, tri-i-pentyl phosphite, tri-n-hexyl phosphite, tri-i-hexyl phosphite, tri-n-heptyl phosphite, tri-i-heptyl phosphite, tri-n-octyl phosphite, tri-i-octyl phosphite, triphenyl phosphite, and di-n-butyl phosphite. said organic epoxide compound is selected from at least one of an oxide of a C2-C 18 aliphatic olefin, an aliphatic diene, a halogenated aliphatic olefin, or a halogenated aliphatic diene; preferably, said organic epoxide compound is selected from at least one of an oxirane, an oxetane, a butylene oxide, butadiene oxide, an epichlorohydrin, a glycidyl methacrylate, a glycidyl ethyl ether, a glycidyl butyl ether; and / or, ​ 5. The catalyst component of claim 1 or 2, wherein: optionally, an inert diluent is added into the solvent system; preferably, the inert diluent is selected from aromatic compounds and / or alkanes; more preferably, the aromatic compounds include at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and / or derivatives thereof; and / or, the alkanes include at least one of straight-chain alkanes, branched alkanes or cyclic alkanes having 3-20 carbon atoms; and / or, the structure of the organic acid anhydride compound is shown in formula (1): In formula (1), R5and R6are the same or different, and each independently is hydrogen, C1-C 10 alkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C3-C 10 cycloalkyl, or C6-C 10 aromatic hydrocarbon group, and R5and R6may optionally form a ring; and / or, The titanium halide has the general formula Ti(OR8) a X b wherein R8 is a C1-C 10 aliphatic or aromatic hydrocarbon group, X is a halogen, preferably fluorine, chlorine or bromine, a is 0, 1 or 2, b is an integer from 1 to 4, and a+b = 3 or 4.

6. The catalyst component of claim 1 or 2, wherein: The general formula of the titanate compound is Ti(OR) n , n > 0, R is a C1-C 10 aliphatic alkyl group; and / or, said alcohol compound is selected from at least one of the group consisting of C1-C 18 aliphatic or aromatic alcohols, preferably at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isooctanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and isohexylene glycol, more preferably at least one of ethanol, butanol, isobutanol, phenethyl alcohol, butylene glycol.

7. The catalyst component of claim 1 or 2, wherein: the amount of the organic phosphorus compound is 0.1-10 moles per mole of magnesium halide; the amount of the organic acid anhydride compound is 0.03-1 mole; the amount of the titanate compound is 0.01-1 mole; the amount of the alcohol compound is 0.1-4 moles; the amount of the titanium halide is 0.5-120 moles; preferably, the amount of the organic phosphorus compound is 0.5-2 moles per mole of magnesium halide; the amount of the organic acid anhydride compound is 0.1-0.3 mole; the amount of the titanate compound is 0.05-0.2 mole; the amount of the alcohol compound is 0.1-2 moles; the amount of the titanium halide is 5-20 moles.

8. A method for preparing the catalyst component of any one of claims 1-7, comprising reacting a magnesium complex, an organic acid anhydride compound, a titanate compound, an alcohol compound and a titanium halide; preferably, comprising the following steps: (a) dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organic phosphorus compound to obtain a magnesium complex; (b) reacting the magnesium complex with an organic acid anhydride compound to obtain a reaction mixture; (c) contacting the reaction mixture obtained in step (b) with a titanium halide to obtain a reaction mixture; (d) contacting the reaction mixture in step (c) with an alcohol compound, and then heating to precipitate solid particles; (e) aging the reaction mother liquor and the solid particles, preferably at a temperature of 70-120°C, to obtain the catalyst component; wherein the titanate compound is added in one or more of steps (c), (d) and (e).

9. The method of claim 8, wherein comprising the following steps: (1) dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organic phosphorus compound to obtain a magnesium complex; (2) reacting the magnesium complex with an organic acid anhydride compound, and then contacting the resulting reaction mixture with a titanium halide, and then reacting with a titanate compound and an alcohol compound, and then heating and aging to obtain the catalyst component.

10. The method of claim 9, wherein, the method comprises the following steps: S1. dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organic phosphorus compound, and forming a uniform solution; S2, the solution obtained in step S1 is reacted with an organic acid anhydride compound, and then the reaction product is contacted with a titanium halide, a titanate compound and an alcohol compound, and then the mixture is warmed to precipitate spherical or spherical-like solid particles; S3, the reaction mother liquor and the solid particles are aged at 70-120°C to obtain a mixture; S4, the mixture obtained in step S3 is treated to remove unreacted substances and solvents to obtain the catalyst component; Preferably: In step S1, the magnesium halide and the solvent system containing the organic epoxy compound and the organic phosphorus compound are reacted at 50-70°C for 1-3 hours to form a uniform solution; and / or, In step S2, the reaction temperature of the solution obtained in step S1 with the organic acid anhydride compound is the same as or different from the temperature in step S1, preferably 50-70°C, and the reaction time is 0.5-2 hours, then the temperature of the reaction system is lowered to -60°C to -20°C, and then contacted with the titanium halide, the titanate compound and the alcohol compound; then gradually warmed, preferably at a rate of 0.2-2°C / min, to 70-120°C, and then aged for 1-4 hours.

11. A catalyst for olefin polymerization, comprising the following components: A): the catalyst component according to any one of claims 1-7 or obtained by the preparation method according to any one of claims 8-10; B) : an organoaluminum compound of the formula AlR' d X' 3-d wherein R' is hydrogen or a C l -C 20 hydrocarbyl group, X' is a halogen atom, preferably fluorine, chlorine or bromine, and 0 < d < 3. Preferably, the molar ratio of aluminum in component B) to titanium in component A) is (20-200):1, preferably (50-100):

1.

12. Use of the catalyst component according to any one of claims 1-7 or obtained by the preparation method according to any one of claims 8-10 or the catalyst according to claim 11 in ethylene polymerization.

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