Catalyst component for olefin polymerization and preparation method thereof, catalyst and olefin polymerization method

Abstract

The present invention relates to a catalyst for olefin polymerization, and discloses a catalyst component for olefin polymerization and a preparation method thereof, a catalyst and an olefin polymerization method. The catalyst component comprises: a magnesium compound selected from: ① a magnesium compound having a structural formula of MgR 1 R 2 ② Magnesium dihalide or its group R 6 OR 7 The replaced derivative; titanium compound; such as formula CX n H 3‑n COOCH2R 8 The halogenated acetate compounds shown in the formula, wherein R 8 The catalyst component is a hydrocarbon group or a halogenated hydrocarbon group with 1-8 carbon atoms, n is an integer of 0≤n≤3, and X is a halogen. The catalyst obtained by combining the catalyst component with an organic aluminum compound has high catalytic activity and hydrogen adjustment sensitivity in olefin polymerization applications, and can obtain a polymer with a higher melt index.

Description

Technical Field

[0001] The present invention relates to a catalyst for olefin polymerization, and more particularly to a catalyst component for olefin polymerization and a preparation method thereof, a catalyst and an olefin polymerization method. Background Art

[0002] In recent years, polyolefin polymer materials have long become one of the most important materials in today's society, and the development speed is very fast. In particular, the rapid development of the polyolefin industry worldwide in recent decades shows that the development and progress of catalyst technology for olefin polymerization has promoted the development of basic research and industrialization technology of polyolefins to the greatest extent. In particular, in the development process of polyethylene, the research on catalysts has always occupied an important position in the synthesis and production of polyethylene. Among them, titanium catalysts have been widely used and continuously developed due to their high catalytic efficiency and low price.

[0003] At present, there are many studies and reports on catalyst performance improvement, mainly focusing on the following aspects: catalytic efficiency, particle morphology control, copolymerization ability, molecular weight and molecular weight distribution, etc. For the production of general-purpose polyolefin resins, on the basis of further improving catalyst performance, simplifying catalyst preparation process, reducing catalyst cost, and developing environmentally friendly technology to improve efficiency and enhance competitiveness is a development direction. For example, the electron donor compound with benzoate structure used in Chinese patent application CN200310102239.1, the aromatic monoester or diester compounds such as diisobutyl phthalate or ethyl benzoate used in U.S. patent application US4784983, the cyclic polyester-containing compound used in Chinese patent application CN200780026685.5, the halogenated hydrocarbon used in Chinese patent application CN201110258837.2, the pyrrolidone compound used in Chinese patent application CN201710474232.4, the mixed electron donor of diester compound and dibasic aliphatic carboxylic acid ester or aromatic carboxylic acid ester used in Chinese patent application CN200510000482.1, etc.

[0004] With the development of the polyolefin industry, it is necessary to continuously develop more and better electron donors to further improve the catalytic performance of catalysts, especially to improve the hydrogen sensitivity of catalysts during high hydrogen polymerization, so as to meet the higher requirements of the polyolefin industry for catalysts. Summary of the invention

[0005] The present invention aims at the problem that the activity of polyolefin catalysts in the prior art is insufficient, especially the low sensitivity to hydrogen regulation during hydrogen polymerization, and provides a catalyst component for olefin polymerization and a preparation method thereof, a catalyst and an olefin polymerization method.

[0006] The inventors of the present invention surprisingly found through a large number of experimental studies during the development of polyethylene catalysts that a group of compounds such as the formula CX n H 3-n COOCH2R 8 The specific halogenated acetate compound (R 8 is a hydrocarbon group or a halogenated hydrocarbon group with 1 to 8 carbon atoms, and n is an integer of 0≤n≤3) when used as an internal electron donor, the comprehensive performance of the existing polyethylene catalyst, especially the hydrogen adjustment sensitivity of the catalyst, can be significantly improved; and the raw material of the halogenated acetate compound is simple and easy to obtain, and can be directly added or prepared in the catalyst synthesis process from the corresponding formula CX n H 3-n An acetyl halide represented by the formula COX (n is an integer of 0≤n≤3, X is a halogen, preferably Cl) and an alcohol represented by the formula HOCH2R (R 8 The obtained catalyst has a high catalyst activity, and the polymer prepared under the same conditions has a high melt index and hydrogen adjustment sensitivity.

[0007] Based on the above findings, one of the objects of the present invention is to provide a catalyst component for olefin polymerization, comprising:

[0008] 1) A magnesium compound, wherein the magnesium compound is selected from at least one of the following components:

[0009] ①The structural formula is MgR 1 R 2 Magnesium alkyl, R 1 and R 2 are the same or different, each selected from substituted or unsubstituted C1-C 10 A hydrocarbon group, wherein the substituent is selected from at least one of a hydroxyl group, a carboxyl group, a halogen atom and an alkoxy group;

[0010] ② Magnesium dihalide or a halogen atom in the magnesium dihalide molecular formula is replaced by a group R 6 OR 7 The replaced derivative, R 6 , R 7 Each is selected from substituted or unsubstituted C1-C 10 A hydrocarbon group, wherein the substituent is selected from a hydroxyl group, a carboxyl group, a halogen atom and / or an alkoxy group;

[0011] 2) Titanium compounds;

[0012] 3) Such as CX n H 3-n COOCH2R 8 The halogenated acetate compounds shown in the formula, wherein R 8is a hydrocarbon group or a halogenated hydrocarbon group having 1 to 8 carbon atoms, n is an integer of 0≤n≤3, and when n is 0, R 8 is a halogenated hydrocarbon group of 1 to 8 carbon atoms; X is a halogen.

[0013] According to the present invention, X is a halogen, for example, it may be F, Cl, Br, I, preferably Cl and / or Br, and more preferably Cl.

[0014] According to the present invention, C1-C 10 Alkyl refers to C1-C 10 Straight chain alkyl or C3-C 10 The branched chain alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, and n-decyl. 10 Examples of cycloalkyl groups may include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, and 4-n-butylcyclohexyl. 10 Examples of aryl groups may include, but are not limited to, phenyl, 4-methylphenyl, and 4-ethylphenyl. 10 Examples of alkenyl groups may include, but are not limited to, vinyl and allyl. 10 Examples of alkynyl groups may include, but are not limited to, ethynyl and propargyl. 10 Examples of the aralkyl group may include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl, and phenyl-isopropyl.

[0015] In the present invention, "substituted C1-C 10 "Hydrocarbon" means "C1-C 10 A hydrogen atom (preferably one hydrogen atom) or a carbon atom on the "hydrocarbon group" is substituted by the substituent.

[0016] The hydrocarbon group described in the catalyst component ① of the present invention can be an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or an aralkyl group. In a preferred embodiment of the present invention, R 1 and R 2 Selected from substituted or unsubstituted C1-C 10 of alkyl.

[0017] In a preferred embodiment of the present invention, the structural formula is MgR 1 R 2 The alkyl magnesium is at least one selected from dimethyl magnesium, diethyl magnesium, n-butylethyl magnesium, di-n-butyl magnesium and butyloctyl magnesium.

[0018] The magnesium dihalide is selected from at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide, preferably magnesium dichloride.

[0019] According to the present invention, R 6 and R 7 Each is selected from substituted or unsubstituted C1-C 10 The substituent is selected from a hydroxyl group, a carboxyl group, a halogen atom or an alkoxy group.

[0020] In a preferred embodiment of the present invention, one halogen atom in the magnesium dihalide molecular formula is replaced by a group R 6 The replaced derivative is selected from at least one of CH3MgX and CH3CH2MgX; and / or,

[0021] In the magnesium dihalide molecular formula, one halogen atom is replaced by the group OR 7 The substituted derivative is selected from MgX(OCH2CH3) and / or MgX(OBu), wherein X is a halogen, for example, at least one of CH3MgCl and CH3CH2MgCl, and at least one of MgCl(OCH2CH3) and MgCl(OBu).

[0022] According to the present invention, the general structural formula of the titanium compound is TiX m (OR) 4-m , where: X is halogen, R is C1-C 14 Aliphatic hydrocarbon or C6-C 14 An aromatic hydrocarbon group, m is an integer of 0-4; preferably, the titanium compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetraethoxytitanium, tetrabutoxytitanium, triethoxytitanium monochloride, diethoxytitanium dichloride and triethoxytitanium monochloride, preferably at least one of titanium tetrachloride, tetraethoxytitanium and tetrabutoxytitanium.

[0023] The catalyst component of the present invention is described in the formula CX n H 3-n COOCH2R 8 The halogenated acetic acid ester compound shown (n is an integer of 0≤n≤3), R 8is a hydrocarbon group or a halogenated hydrocarbon group having 1 to 8 carbon atoms, preferably an aliphatic hydrocarbon group or a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms or an aromatic hydrocarbon group or a substituted aromatic hydrocarbon group having 7 to 8 carbon atoms. When X is Cl, for example, it can be: CH3COOCH2CCl3, CH3COOCH2CH2Cl, CH3COOCH2CH2CH2Cl, CH3COOCHCH2ClCH2Cl, CH3COOCHCH2ClCH2Cl, CH3COOCH2CH2CH2CH2Cl, CH2ClCOOCH2CCl3, CH2ClCOOCH2CH2Cl, CH2ClCOOCH2CH2CH2Cl, CH2ClCOOCH2CH2ClCH2Cl, CH2ClCOOCH2CH2ClCH2Cl, CH2ClCOOCH2CH2CH2Cl, CH2ClCOOCH2C6H5, CH 2ClCOOCH2CH2C6H5, CHCl2COOCH2CCl3, CHCl2COOCH2CH2Cl, CHCl2COOCH2CH2CH2Cl, CHCl2COOCHCH2ClCH2Cl, CHCl2COOCH2CH2CH2C H2Cl, CHCl2COOCH2C6H5, CHCl2COOCH2CH2C6H5, CCl3COOCH2CCl3, CCl3COOCH2CH2Cl, CCl3COOCH2CH2CH2Cl, CCl3COOCHCH2ClCH2Cl , CCl3COOCH2CH2CH2CH2Cl, CCl3COOCH2C6H5, CCl3COOCH2CH2C6H5; the halogenated acetate compound is preferably CH3COOCH2CCl3, CH3COOCH2CH2Cl, CH3COOCHCH2ClCH2Cl, CH3COOCH2CH2CH2CH2Cl, CH2ClCOOCH2CCl3, CH2ClCOOCH2CH2Cl, CH2ClCOOCH2CH2CH2Cl, CH2ClCOOCH2CH2ClCH2Cl, At least one of CH2ClCOOCH2CH2CH2CH2Cl, CHCl2COOCH2CCl3, CHCl2COOCH2CH2Cl, CHCl2COOCH2CH2CH2Cl, CHCl2COOCHCH2ClCH2Cl, CHCl2COOCHCH2ClCH2Cl, CHCl2COOCH2CH2CH2Cl, CCl3COOCH2CCl3, CCl3COOCH2CH2Cl, CCl3COOCH2CH2CH2Cl, CCl3COOCH2CH2CH2Cl, CCl3COOCHCH2ClCH2Cl, CCl3COOCH2CH2CH2Cl, and CCl3COOCH2CH2CH2Cl.

[0024] The halogenated acetic acid ester compound can be directly added as an internal electron donor, or can be added in the catalyst synthesis process by the corresponding formula CXn H 3-n Acetyl halide represented by COX (n is an integer of 0≤n≤3, X is a halogen, preferably Cl) and HOCH2R 8 The alcohol (R 8 is a hydrocarbon group or a halogenated hydrocarbon group having 1 to 8 carbon atoms) is generated in situ by the reaction.

[0025] In a preferred embodiment of the present invention, based on 1 mol of magnesium in the magnesium compound, the content of the halogenated acetate compound is 0.001-10 mol, preferably 0.01-5 mol; and / or the content of the titanium compound is 0.2-100 mol, preferably 1-20 mol.

[0026] In a preferred embodiment of the present invention, the magnesium compound is derived from a liquid component containing the magnesium compound; preferably, the liquid component containing the magnesium compound contains one or more of liquid hydrocarbons, organic alcohols, organic epoxy compounds and organic phosphorus compounds.

[0027] In a preferred embodiment of the present invention, when the catalyst component contains the magnesium compound in ①, the liquid component containing the magnesium compound contains liquid hydrocarbon; and / or,

[0028] In the case where the catalyst component contains the magnesium compound in ②, the liquid component containing the magnesium compound contains an organic alcohol, an optional organic epoxy compound and an optional organic phosphorus compound; and / or,

[0029] In the case where the catalyst component contains the magnesium compound in ②, the liquid component containing the magnesium compound contains an organic epoxy compound and an organic phosphorus compound.

[0030] In the present invention, "and / or" means that it can be a single situation or two situations can exist at the same time.

[0031] In a preferred embodiment of the present invention, it is characterized in that the solid catalyst component A comprises the reaction product of the following components:

[0032] 1) A liquid component containing magnesium, selected from at least one of the following components:

[0033] ① Alkyl magnesium or a solution thereof dispersed in a liquid hydrocarbon, wherein the general formula of the alkyl magnesium is MgR 1 R 2 , R 1 and R 2 may be the same or different, and each is selected from substituted or unsubstituted C1-C 10 A hydrocarbon group, wherein the substituent is selected from a hydroxyl group, a carboxyl group, a halogen atom or an alkoxy group;

[0034] ② Magnesium dihalide or a halogen atom in the magnesium dihalide molecular formula is replaced by a group R 6 OR 7 The product obtained by dissolving the replaced derivative in an organic alcohol, an optional organic epoxy compound and an optional organic phosphorus compound, wherein R 6 , R 7 Each is selected from substituted or unsubstituted C1-C 10 A hydrocarbon group, wherein the substituent is selected from a hydroxyl group, a carboxyl group, a halogen atom or an alkoxy group;

[0035] ③ Magnesium dihalide or a halogen atom in the magnesium dihalide molecular formula is replaced by a group R 6 OR 7 The replaced derivative is dispersed in an organic phosphorus compound and an organic epoxy compound to obtain a product; wherein R 6 , R 7 Each is selected from substituted or unsubstituted C1-C 10 A hydrocarbon group, wherein the substituent is selected from a hydroxyl group, a carboxyl group, a halogen atom or an alkoxy group;

[0036] 2) Such as CX n H 3-n COOCH2R 8 At least one of the halogenated acetic acid ester compounds shown, R 8 is a hydrocarbon group or a halogenated hydrocarbon group having 1 to 8 carbon atoms, n is an integer of 0≤n≤3; and when n is 0, R 8 is a halogenated hydrocarbon group with 1 to 8 carbon atoms; the halogenated acetic acid ester compound can be directly added as an internal electron donor, or can be generated in situ during the catalyst synthesis process by reacting the corresponding acetyl halide with the corresponding alcohol;

[0037] 3) Titanium compounds.

[0038] According to the present invention, the organic alcohol is selected from C1-C 12 Fatty alcohols, C7-C 12 and at least one of the substituted alcohols derived from the corresponding aliphatic alcohols or aromatic alcohols; preferably at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, benzyl alcohol and phenylethyl alcohol; more preferably at least one of ethanol, isopropanol, butanol, 2-ethylhexanol, benzyl alcohol and phenylethyl alcohol.

[0039] According to the present invention, the organic epoxy compound is selected from at least one of aliphatic olefins, aliphatic dienes, halogenated aliphatic olefins or oxides, glycidyl ethers and internal ethers of halogenated aliphatic dienes having 2 to 8 carbon atoms; preferably selected from at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether and tetrahydrofuran; more preferably selected from at least one of ethylene oxide, propylene oxide, epichlorohydrin and tetrahydrofuran.

[0040] According to the present invention, the organophosphorus compound is selected from the group consisting of triester phosphate compounds and / or phosphite compounds; for example, it may be at least one of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, tri-isopropyl phosphate, tri-n-butyl phosphate, tri-isobutyl phosphate, tri-tert-butyl phosphate, tri-n-pentyl phosphate, tri-isopentyl phosphate, tri-n-hexyl phosphate, tri-isohexyl phosphate, tri-n-heptyl phosphate, tri-isoheptyl phosphate, tri-n-octyl phosphate, tri-isooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, tri-isopropyl phosphite, tri-n-butyl phosphite, tri-isobutyl phosphite, tri-tert-butyl phosphite, tri-n-pentyl phosphite, tri-isopentyl phosphite, tri-n-hexyl phosphite, tri-isohexyl phosphite, tri-n-heptyl phosphite, tri-isoheptyl phosphite, tri-n-octyl phosphite, tri-isooctyl phosphite, triphenyl phosphite and di-n-butyl phosphite. Preferably, the organic phosphorus compound is at least one selected from triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite and di-n-butyl phosphite.

[0041] In a preferred embodiment of the present invention, the organophosphorus compound is at least one selected from triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite and di-n-butyl phosphite.

[0042] The second object of the present invention is to provide a method for preparing the catalyst component described above, comprising mixing the magnesium compound with an optional liquid hydrocarbon, as well as an optional organic alcohol, an optional organic epoxy compound and an optional organic phosphorus compound to obtain a liquid component containing the magnesium compound; and mixing and contacting the liquid component containing the magnesium compound with the halogenated acetate compound and a titanium compound to obtain the catalyst component.

[0043] According to the present invention, the selection range of the amount of each raw material is relatively wide. In a preferred embodiment of the present invention, based on 1 mol of magnesium content in the magnesium compound, the feeding amount of the halogenated acetate compound is 0.001-10 mol, preferably 0.01-5 mol, and more preferably 0.02-4 mol; and / or the feeding amount of the titanium compound is 0.2-100 mol, preferably 0.5-50 mol, and more preferably 1-20 mol.

[0044] In a more preferred embodiment of the present invention, based on 1 mol of magnesium content in the magnesium compound, the feeding amount of the halogenated acetate compound is 0.001-10 mol, preferably 0.01-5 mol; and / or, the feeding amount of the titanium compound is 0.2-100 mol, preferably 0.5-50 mol; and / or, the feeding amount of the organic alcohol is 0-10 mol, preferably 0-4 mol; and / or, the feeding amount of the organic epoxy compound is 0-10 mol, preferably 0-4 mol; and / or, the feeding amount of the organic phosphorus compound is 0-10 mol, preferably 0-5 mol.

[0045] According to the present invention, preferably, the liquid component containing the magnesium compound is obtained by at least one of the following methods:

[0046] 1) directly adding the alkyl magnesium described in ① or a liquid hydrocarbon solution containing the alkyl magnesium to obtain a liquid component containing the magnesium compound;

[0047] 2) mixing the magnesium compound in ② with an organic alcohol, an optional organic epoxy compound and an optional organic phosphorus compound, preferably at a mixing temperature of 40-80° C. for 0.01-10 hours to obtain a liquid component containing the magnesium compound;

[0048] 3) Mixing the magnesium compound in ② with an organic phosphorus compound and an organic epoxy compound, preferably at a mixing temperature of 40-80° C. for 0.01-10 hours, to obtain the liquid component containing the magnesium compound.

[0049] According to the present invention, in method 1), the liquid hydrocarbon acts as a solvent or a diluent, and therefore, the present invention has no particular limitation on the amount of the liquid hydrocarbon. According to the present invention, the liquid hydrocarbon is an aliphatic hydrocarbon or an aromatic hydrocarbon, specifically at least one of hexane, heptane, octane, nonane, decane, 1,2-dichloroethane, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene and chlorobenzene.

[0050] In a more preferred embodiment of the present invention, in method 2), based on the content of magnesium in the magnesium compound, the content of organic alcohol is 0.01-10 moles, preferably 0.02-4 moles; the content of organic epoxy compound is 0-10 moles, preferably 0-4 moles; and the content of organic phosphorus compound is 0-10 moles, preferably 0-5 moles.

[0051] In a more preferred embodiment of the present invention, in method 3), the content of the organic phosphorus compound is 0.01-10 moles, preferably 0.02-5 moles, per mole of magnesium in the magnesium compound; and the content of the organic epoxy compound is 0.01-10 moles, preferably 0.02-4 moles.

[0052] There are many options for the order of adding materials in the present invention. In a preferred embodiment of the present invention, the liquid component containing the magnesium compound is first mixed and contacted with the halogenated acetate compound, and then the obtained mixture is mixed and contacted with the titanium compound.

[0053] The halogenated acetate compounds are derived from directly added halogenated acetate compounds and / or are generated in situ by esterification reaction between corresponding acetyl halides and corresponding alcohols.

[0054] In a preferred embodiment of the present invention, the mixed contact is carried out under nitrogen and / or an inert atmosphere, for example, nitrogen, argon, and a mixture of nitrogen and argon.

[0055] In a preferred embodiment of the present invention, the step of washing and drying the catalyst components obtained after the mixed contact is also included. The present invention has no particular limitation on the washing solvent, for example, it can be an aliphatic hydrocarbon or an aromatic hydrocarbon, such as n-hexane, n-heptane, n-octane, n-decane and toluene, etc., which can achieve the present invention. The present invention also has no particular limitation on the drying conditions.

[0056] In a preferred embodiment of the present invention, the catalyst component can be prepared by, but is not limited to, the following method:

[0057] Method 1:

[0058] 1) in the presence of an inert solvent such as a liquid hydrocarbon, the alkyl magnesium is contacted with a titanium compound and a halogenated acetate compound at a certain temperature for reaction, and then subjected to a high temperature (e.g., 20-150° C.) treatment to produce a precipitate; 2) unreacted substances and the solvent are removed, and the precipitate is washed to obtain the solid catalyst component.

[0059] Method 2:

[0060] 1) reacting a magnesium-containing compound with an organic epoxy compound, an organic phosphorus compound and an alcohol compound in the presence of an inert solvent (the reaction temperature is preferably 40-80° C. and the reaction time is 0.1-10 hours) to form a uniform solution; 2) reacting the uniform solution obtained in step 1) with a halogenated acetate compound, and then contacting and reacting with a titanium compound to generate a precipitate; 3) removing unreacted substances and solvents, washing the precipitate, and obtaining the solid catalyst component.

[0061] Method 3:

[0062] 1) reacting a magnesium-containing compound with an alcohol compound in the presence of an inert solvent (the reaction temperature is preferably 50-150° C. and the reaction time is 0.1-10 hours) to form a uniform solution; 2) reacting the uniform solution obtained in step 1) with a halogenated acetate compound, and then contacting and reacting with a titanium compound to generate a precipitate; 3) removing unreacted substances and solvents, washing the precipitate, and obtaining the solid catalyst component.

[0063] Method 4:

[0064] 1) reacting a magnesium-containing compound with an organic epoxy compound and an organic phosphorus compound in the presence of an inert solvent (the reaction temperature is preferably 40-80° C. and the reaction time is 0.1-10 hours) to form a uniform solution; 2) reacting the uniform solution obtained in step 1) with a halogenated acetate compound, and then contacting and reacting with a titanium compound to generate a precipitate; 3) removing unreacted substances and solvents, washing the precipitate, and obtaining the solid catalyst component.

[0065] According to the present invention, there is no particular limitation on the above-mentioned inert solvent, as long as it can facilitate the dissolution or dilution of the above-mentioned raw materials of the present invention and does not react. For example, the inert solvent can be a liquid hydrocarbon, and the liquid hydrocarbon is preferably an aliphatic hydrocarbon or an aromatic hydrocarbon, such as one or more of hexane, heptane, octane, nonane, decane, 1,2-dichloroethane, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene and chlorobenzene, which can realize the present invention.

[0066] In a more preferred embodiment of the present invention, the preparation method comprises: mixing a liquid component containing a magnesium compound with a halogenated acetate compound in a solution for a contact reaction at (-30)-150°C for 0.6-600 min, cooling the obtained mixture to (-30)-80°C, and mixing and contacting with a titanium compound at (-30)-80°C for 0.6-600 min; then heating to 20-150°C, maintaining for 0.6-600 min, and filtering out the liquid;

[0067] Preferably, the method further comprises the step of contacting the obtained product with a titanium compound at (-30)-150° C. for multiple times after filtering out the liquid, and the contact time for each time is preferably 0.6-600 min.

[0068] The above preparation method is an example description of the catalyst components of the present invention. When actually adding materials, the halogenated acetate compound of the present invention can also be added as an internal electron donor after the titanium compound is added. In addition, the above components are only the basic components of the present invention, and the actual synthesis is not limited to these basic components. If necessary, other internal electron donors and additives can also be considered to be added at the same time, which will not be pointed out one by one in the present invention.

[0069] The third object of the present invention is to provide a catalyst component prepared by the preparation method described above.

[0070] Through the above steps, a component of the catalyst system of the present invention is prepared, and the component can be used in the form of a solid or a suspension.

[0071] A fourth object of the present invention is to provide a catalyst comprising an organoaluminum compound and the catalyst component described above.

[0072] On the basis of the above, the present invention further provides a catalyst system for olefin polymerization, the catalyst system comprising the following components: component A: the catalyst component as described above; component B: an organic aluminum compound. The catalyst component A and component B (organic aluminum compound) of the present invention can be directly applied to the polymerization system, or can be pre-complexed and then applied to the polymerization system.

[0073] The molar ratio of the aluminum in the organoaluminum compound to the titanium in the catalyst component has a wide selection range. In a preferred embodiment of the present invention, the molar ratio of the aluminum in the organoaluminum compound to the titanium in the catalyst component is 5-1000, preferably 20-800. That is, the molar ratio of the aluminum in component B of the catalyst system of the present invention to the titanium in component A is 5-1000, preferably 20-800.

[0074] According to the present invention, preferably, the organoaluminum compound has the general formula AlR' y X 3-y , R' is a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group, an aralkyl group and an aryl group; AlR' y X 3-ywherein X is a halogen, preferably chlorine and / or bromine; y is an integer of 0≤y≤3; preferably, the organoaluminum compound is at least one of trialkylaluminum, alkylaluminum hydride and alkylaluminum chloride; more preferably, it is at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride, ethylaluminum dichloride, diethylaluminum monohydride and diisobutylaluminum monohydride; further preferably, it is triethylaluminum and / or triisobutylaluminum.

[0075] A fifth object of the present invention is to provide an olefin polymerization method, which comprises: contacting one or more olefins with the catalyst described above under olefin polymerization reaction conditions;

[0076] and / or, contacting one or more olefins with an organoaluminum compound and the catalyst components described above under olefin polymerization conditions.

[0077] The catalyst component A and component B (organoaluminum compound) of the present invention can be directly applied to the polymerization system, or can be pre-complexed and then applied to the polymerization system.

[0078] The catalyst of the present invention can be applied to the polymerization of various olefins, for example, it can be used for the homopolymerization of ethylene, and it can also be used for the copolymerization of ethylene and α-olefin. When copolymerizing ethylene and α-olefin, the comonomers can be propylene, butene, pentene, hexene, octene, and 4-methyl-1-pentene.

[0079] Olefin polymerization can be carried out in liquid phase or gas phase. In liquid phase polymerization, saturated aliphatic hydrocarbons such as propane, hexane, heptane, cyclohexane, isobutane, isopentane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene or other inert solvents such as aromatic hydrocarbons can be used as reaction medium, and prepolymerization can be carried out before polymerization. The polymerization method can be intermittent, semi-continuous or continuous.

[0080] Preferably, the polymerization temperature is room temperature (eg 0°C-25°C)-150°C, preferably 50°C-100°C.

[0081] In order to adjust the molecular weight of the polymer, preferably, the olefin polymerization reaction is carried out in the presence of hydrogen, that is, hydrogen is used as a molecular weight regulator. The catalyst of the present invention has a high sensitivity to hydrogen regulation during high hydrogen polymerization, and can obtain a polymer with a higher melt index.

[0082] Compared with the prior art, the present invention has the following obvious advantages:

[0083] (1) First, the halogenated acetic acid ester compound raw material used in the present invention is simple and easy to obtain. It can be directly added or in the preparation process of certain specific catalysts, the corresponding acetyl halide and the corresponding alcohol are reacted to generate in situ in the system (when in situ generation is adopted, the addition amounts of the two do not need to maintain an equimolar ratio) to obtain the catalyst component, and then obtain the catalyst. The preparation method is simple and controllable, and has a high value for popularization and application;

[0084] (2) Secondly, when the halogenated acetate compound is used as an internal electron donor in the catalyst component of the present invention, the comprehensive performance of the existing polyethylene catalyst can be significantly improved, and the activity of the catalyst is significantly improved;

[0085] (3) In olefin polymerization, the catalyst of the present invention exhibits higher hydrogen sensitivity under high hydrogen polymerization conditions, and can produce polymers with higher melt index under the same reaction conditions. DETAILED DESCRIPTION

[0086] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0087] In the following examples and comparative examples: Determination of polymer melt index (MI): measured according to ASTM D1238-99, load 2.16 kg, at 190°C.

[0088] The method for detecting the catalyst activity is: polymerization is carried out under the polymerization conditions of the embodiment. After the polymerization is completed, the weight of the obtained polymer is divided by the weight of the added catalyst. The ratio is the catalyst activity under the polymerization conditions.

[0089] Unless otherwise specified, the raw materials used in the following examples are all commercially available.

[0090] Example 1

[0091] (1) Preparation of solid catalyst component a

[0092] In a reactor that has been repeatedly replaced with high-purity nitrogen, 40 mL of a heptane solution of di-n-butyl magnesium (1 M) was mixed with 1.0 mL of phenylethanol at 30 ° C, kept at a constant temperature for 5 minutes, and then 0.027 mol of CH2ClCOOCH2CH3 was added dropwise, maintained for 0.5 hours, and then slowly dropped into 40 mL of titanium tetrachloride at -5 ° C. After the addition was completed, the temperature was kept constant for 1 hour, and then the system was gradually heated to 80 ° C and kept at a constant temperature for 2 hours. Stop stirring, let it stand, remove the supernatant, wash it with toluene and hexane several times, and then dry it to obtain a solid catalyst component a with good fluidity.

[0093] Comparative Example 1

[0094] (1) Preparation of solid catalyst component a*

[0095] In a reactor that has been repeatedly replaced with high-purity nitrogen, 40 mL of a heptane solution of di-n-butyl magnesium (1 M) is slowly dripped into 40 mL of titanium tetrachloride at -5°C. After the addition is completed, the temperature is kept constant for 1 hour. The system is gradually heated to 80°C and kept constant for 2 hours. Stop stirring, let it stand, remove the supernatant, wash it with toluene and hexane several times, and then dry it to obtain a solid catalyst component a* with good fluidity.

[0096] Example 2

[0097] (1) Preparation of solid catalyst component b

[0098] 4.0 g of anhydrous magnesium chloride, 60 mL of toluene, 3.0 mL of epichlorohydrin, 9.0 mL of tri-n-butyl phosphate, and 2.8 mL of 2,2-dichloroethanol were added sequentially to a reactor that had been repeatedly replaced with high-purity nitrogen, and reacted at a constant temperature of 60 ° C for 2 hours. The system was cooled to -10 ° C, 4.0 mL of 2,2-dichloroacetyl chloride was slowly added dropwise, maintained for half an hour, and then 45 mL of titanium tetrachloride was added, maintained for 1 hour, and gradually heated to 85 ° C, and maintained at a constant temperature for 1 hour. Stop stirring, let it stand, remove the supernatant, wash it with toluene and hexane several times, and then dry it to obtain a solid catalyst component b with good fluidity.

[0099] Comparative Example 2

[0100] (1) Preparation of solid catalyst component b*

[0101] 4.0 g of anhydrous magnesium chloride, 60 mL of toluene, 3.0 mL of epichlorohydrin, and 9 mL of tri-n-butyl phosphate were sequentially added to a reactor that had been repeatedly replaced with high-purity nitrogen, and the reaction was carried out at a constant temperature of 60°C for 2 hours. The system was cooled to -10°C, 4.0 mL of ethyl acetate was slowly added dropwise for half an hour, 45 mL of titanium tetrachloride was slowly added dropwise for 1 hour, and the temperature was gradually raised to 85°C and kept constant for 1 hour. Stirring was stopped, the mixture was allowed to stand, the supernatant was removed, and the mixture was washed with toluene and hexane for several times and then dried to obtain a solid catalyst component b* with good fluidity.

[0102] Example 3

[0103] (1) Preparation of solid catalyst component c

[0104] 4.0 g of anhydrous magnesium chloride, 50 mL of toluene, 3.0 mL of epichlorohydrin, 8.0 mL of tri-n-butyl phosphate, and 5.0 mL of ethanol were sequentially added to a reactor that had been repeatedly replaced with high-purity nitrogen, and reacted for 2 hours at a temperature of 70°C. The system was cooled to 50°C, and a mixed solution of (0.2 mL of trichloroacetyl chloride + 10 mL of toluene) was slowly added dropwise. After the addition was completed, the system was cooled to -15°C, and then 30 mL of titanium tetrachloride was added, and the temperature was gradually raised to 110°C, and the temperature was kept constant for 1 hour. Stirring was stopped, the mixture was allowed to stand, the supernatant was removed, and the mixture was washed with toluene and hexane for several times and then dried to obtain a solid catalyst component c with good fluidity.

[0105] Comparative Example 3

[0106] (1) Preparation of solid catalyst component c*

[0107] 4.0 g of anhydrous magnesium chloride, 50 mL of toluene, 3.0 mL of epichlorohydrin, 8.0 mL of tri-n-butyl phosphate, and 4.9 mL of ethanol were added sequentially into a reactor that had been repeatedly replaced with high-purity nitrogen, and reacted for 2 hours at a temperature of 70°C. The system was cooled to -15°C, and then 30 mL of titanium tetrachloride was added, and the temperature was gradually raised to 110°C and kept constant for 1 hour. Stirring was stopped, and the mixture was allowed to stand. The supernatant was removed, and the mixture was washed with toluene and hexane for several times and then dried to obtain a solid catalyst component c* with good fluidity.

[0108] Example 4

[0109] (1) Preparation of solid catalyst component d

[0110] In a reactor that has been repeatedly replaced with high-purity nitrogen, 4.0 grams of anhydrous magnesium chloride and 60 mL of n-decane are added in sequence, and 22 mL of 2-ethylhexanol is added under stirring, and the temperature is raised to 130°C and maintained for 1 hour. The system is cooled to 30°C, and a mixed solution of (0.5 mL of 2,2,2-trichloroacetyl chloride + 10 mL of toluene + 0.4 mL of 1,3-dichloroisopropanol) is slowly added dropwise. After the addition is completed, the system is cooled to -15°C, and then 30 mL of titanium tetrachloride is added, and the temperature is gradually raised to 110°C and kept constant for 1 hour. Stop stirring, let it stand, remove the supernatant, wash it with hexane several times, and then dry it to obtain a solid catalyst component d with good fluidity.

[0111] Comparative Example 4

[0112] (1) Preparation of solid catalyst component d*

[0113] In a reactor that has been repeatedly replaced with high-purity nitrogen, 4.0 g of anhydrous magnesium chloride and 60 mL of n-decane are added in sequence, and 22 mL of 2-ethylhexanol is added under stirring, and the temperature is raised to 130°C and maintained for 1 hour. The system is cooled to 30°C, and 0.9 mL of ethyl acetate is slowly added dropwise. After the addition is completed, the system is cooled to -15°C, and then 30 mL of titanium tetrachloride is added, and the temperature is gradually raised to 110°C and kept constant for 1 hour. Stop stirring, let it stand, remove the supernatant, wash it with hexane several times, and then dry it to obtain a solid catalyst component d* with good fluidity.

[0114] Example 5

[0115] (1) Preparation of solid catalyst component e

[0116] In a reactor that has been repeatedly replaced with high-purity nitrogen, 4.0 grams of anhydrous magnesium chloride and 50 mL of toluene are added in sequence, 18 mL of n-butanol and 4.0 mL of tributyl phosphate are added under stirring, the temperature is raised to 100°C, maintained for 2 hours, the system is cooled to 30°C, and a mixed solution of (1.0 mL of 2,2-dichloroacetyl chloride + 10 mL of toluene + 1.0 mL of 1,3-dichloropropanol) is slowly added dropwise. After the addition is completed, the system is cooled to -15°C, and then 50 mL of titanium tetrachloride is added, maintained for 2 hours, gradually heated to 110°C, and kept at a constant temperature for 1 hour. Stop stirring, let stand, remove the supernatant, wash with hexane several times and dry, and obtain a solid catalyst component e with good fluidity.

[0117] Comparative Example 5

[0118] (1) Preparation of solid catalyst component e*

[0119] In a reactor that has been repeatedly replaced with high-purity nitrogen, 4.0 g of anhydrous magnesium chloride and 50 mL of toluene are added in sequence, 18 mL of n-butanol and 4.0 mL of tributyl phosphate are added under stirring, the temperature is raised to 100°C, maintained for 2 hours, the system is cooled to -15°C, and then 50 mL of titanium tetrachloride is added, maintained for 2 hours, gradually raised to 110°C, and kept at a constant temperature for 1 hour. Stop stirring, let stand, remove the supernatant, wash with hexane several times and dry, and obtain a solid catalyst component e* with good fluidity.

[0120] Example 6

[0121] (1) Preparation of solid catalyst component f

[0122] In a reaction kettle that has been repeatedly replaced with high-purity nitrogen, 4.0 g of anhydrous magnesium chloride, 70 ml of toluene, 3.5 ml of epichlorohydrin, and 10.5 ml of tributyl phosphate are added in sequence at a temperature of 60°C, and the reaction is carried out for 1 hour. 0.062 mol of CHCl2COOCH2CCl3 is added and maintained for 0.5 hour. 6 mL of 2,2-dichloroacetyl chloride is slowly added dropwise and maintained for 0.5 hour. The temperature is lowered to -20°C, 45 ml of titanium tetrachloride is added dropwise and maintained for 1 hour. 2.0 mL of ethyl orthosilicate is added dropwise and maintained for 1 hour. The temperature is gradually increased to 110°C, and the temperature is kept constant at 110°C for 1 hour. Stirring is stopped, the mixture is allowed to stand, the supernatant is removed, and the mixture is washed with hexane for multiple times and then dried to obtain a solid catalyst component f with good fluidity.

[0123] Comparative Example 6

[0124] (1) Preparation of solid catalyst component f*

[0125] In a reaction kettle that has been repeatedly replaced with high-purity nitrogen, 4.0 g of anhydrous magnesium chloride, 70 ml of toluene, 3.5 ml of epichlorohydrin, and 10.5 ml of tributyl phosphate are added in sequence at a temperature of 60°C, and the reaction is carried out for 1 hour. 6.0 mL of ethyl acetate is added, and the reaction is maintained for 0.5 hour. The temperature is lowered to -20°C, 45 ml of titanium tetrachloride is added dropwise, and 2 mL of ethyl orthosilicate is added dropwise, and the reaction is maintained for 1 hour. The temperature is gradually increased to 85°C, and the temperature is kept constant at 110°C for 1 hour. Stirring is stopped, the mixture is allowed to stand, the supernatant is removed, and the mixture is washed with hexane for multiple times and then dried to obtain a solid catalyst component f* with good fluidity.

[0126] Example 7

[0127] The catalyst component was prepared according to the method of Example 1, except that only CH2ClCOOCH2CH3 was replaced by an equal molar amount of CH2ClCOOCH2C6H5.

[0128] Comparative Example 7

[0129] (1) Preparation of solid catalyst component f**

[0130] In a reaction kettle that has been repeatedly replaced with high-purity nitrogen, 4.0 g of anhydrous magnesium chloride, 70 ml of toluene, 3.5 ml of epichlorohydrin, and 10.5 ml of tributyl phosphate are added in sequence at a temperature of 60°C, reacted for 1.5 hours, cooled to -20°C, 45 ml of titanium tetrachloride and 2.0 mL of ethyl orthosilicate are added dropwise, maintained for 1 hour, gradually heated to 85°C, and kept constant at 110°C for 1 hour, stirring was stopped, the mixture was allowed to stand, the supernatant was removed, the mixture was washed with hexane for multiple times and then dried to obtain a solid catalyst component f** with good fluidity.

[0131] Experimental example

[0132] Ethylene polymerization: After fully replacing H2 in a stainless steel kettle with a volume of 2 liters, 1000 mL of hexane and 1.0 mL of a 1 mol / L triethylaluminum hexane solution were added thereto, and 35 mg of the solid catalyst components prepared in the above examples and comparative examples were respectively measured, and the temperature was raised to 70°C and hydrogenated to 0.58 MPa (gauge pressure), and then ethylene was introduced to make the pressure in the kettle reach 0.73 MPa (gauge pressure), and polymerization was carried out at 85°C for 2 hours. The test results are shown in Table 1.

[0133] Table 1

[0134] serial number <![CDATA[Activity (10 4 gPE / gcat)]]> <![CDATA[MI 2.16 (g / 10min)]]> Example 1 0.73 530 Comparative Example 1 0.54 280 Example 2 0.78 560 Comparative Example 2 0.62 270 Example 3 0.64 430 Comparative Example 3 0.52 260 Example 4 0.71 460 Comparative Example 4 0.54 220 Example 5 0.76 510 Comparative Example 5 0.44 240 Example 6 0.75 560 Comparative Example 6 0.54 200 Example 7 0.66 540 Comparative Example 7 0.50 210

[0135] It can be seen from the corresponding embodiments and comparative examples (such as Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, etc.) in the data in the above table that the addition of the specific halogenated acetate compound of the present invention can make the obtained catalyst have higher polymerization activity under the same polymerization conditions, and the obtained polymer has a higher melt index.

Claims

1. A catalyst component for olefin polymerization, produced by reacting the following components: 1) A liquid component containing a magnesium compound, wherein the magnesium compound is selected from at least one of the following components: ①The structural formula is MgR 1 R 2 Magnesium alkyl, R 1 and R 2 are the same or different, each selected from substituted or unsubstituted C1-C 10 A hydrocarbon group, wherein the substituent is selected from at least one of a hydroxyl group, a carboxyl group, a halogen atom and an alkoxy group; ② Magnesium dihalide or a halogen atom in the magnesium dihalide molecular formula is replaced by a group R 6 OR 7 The replaced derivative, R 6 , R 7 Each is selected from substituted or unsubstituted C1-C 10 A hydrocarbon group, wherein the substituent is selected from a hydroxyl group, a carboxyl group, a halogen atom and / or an alkoxy group; In the case where the catalyst component contains the magnesium compound in ①, the liquid component containing the magnesium compound consists of the magnesium compound and liquid hydrocarbon; In the case where the catalyst component contains the magnesium compound in ②, the liquid component containing the magnesium compound consists of the magnesium compound and an organic alcohol, an optional organic epoxy compound and an optional organic phosphorus compound, or, In the case where the catalyst component contains the magnesium compound in ②, the liquid component containing the magnesium compound is composed of the magnesium compound, an organic epoxy compound and an organic phosphorus compound; 2) Titanium compounds; 3) CX n H 3-n COOCH2R 8 The halogenated acetate compounds shown in the formula, wherein R 8 is a hydrocarbon group or a halogenated hydrocarbon group having 1 to 8 carbon atoms, n is an integer of 0≤n≤3, and when n is 0, R 8 is a halogenated hydrocarbon group of 1 to 8 carbon atoms; X is a halogen; Based on 1 mol of magnesium in the magnesium compound, the content of the halogenated acetate compound is 0.001-10 mol; and the content of the titanium compound is 0.2-100 mol.

2. The catalyst component according to claim 1, characterized in that: The structural formula is MgR 1 R 2 The alkyl magnesium is at least one selected from dimethyl magnesium, diethyl magnesium, n-butyl ethyl magnesium, di-n-butyl magnesium and butyl octyl magnesium; The magnesium dihalide is selected from at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide; In the magnesium dihalide molecular formula, one halogen atom is replaced by a group R 6 The replaced derivative is selected from at least one of CH3MgX and CH3CH2MgX; In the magnesium dihalide molecular formula, one halogen atom is replaced by the group OR 7 The substituted derivative is selected from MgX(OCH2CH3) and / or MgX(OBu).

3. The catalyst component according to claim 1, characterized in that: The general structural formula of the titanium compound is TiX m (OR) 4-m , where: X is halogen, R is C1-C 14 Aliphatic hydrocarbon or C6-C 14 Aromatic hydrocarbon group, m is an integer of 0-4.

4. The catalyst component according to claim 1, characterized in that: The titanium compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetraethoxide, titanium tetrabutoxide, titanium triethoxide monochloride, titanium diethoxide dichloride and titanium triethoxide monochloride.

5. The catalyst component according to claim 1, characterized in that: The titanium compound is at least one of titanium tetrachloride, titanium tetraethoxide and titanium tetrabutoxide.

6. The catalyst component according to claim 1, characterized in that: Such as CX n H 3-n COOCH2R 8 The halogenated acetate compounds shown, R 8 It is one of an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 7 to 8 carbon atoms, and a substituted aromatic hydrocarbon group having 7 to 8 carbon atoms.

7. The catalyst component according to claim 1, characterized in that: The halogenated acetate compound is at least one of CH3COOCH2CCl3, CH3COOCH2CH2Cl, CCl3COOCH2CCl3, CH3COOCHCH2ClCH2Cl, CH3COOCH2CH2CH2CH2Cl, CH2ClCOOCH2CCl3, CH2ClCOOCH2CH2Cl, CH2ClCOOCH2CH2CH2Cl, CH2ClCOOCHCH2ClCH2Cl, CHCl2COOCH2CCl3, CH2ClCOOCH2CH2Cl, CH2ClCOOCH2CH2CH2Cl, CH2ClCOOCHCH2ClCH2Cl, CHCl2COOCH2CH2Cl, CHCl2COOCH2CH2Cl, CHCl2COOCH2CH2ClCH2Cl, CCl3COOCH2CH2Cl, CHCl2COOCH2CH2CH2Cl, CCl3COOCH2CH2Cl, CHCl2COOCH2CH2CH2Cl, CCl3COOCH2CH2Cl, CHCl2COOCH2CH2CH2Cl, CCl3COOCH2CH2Cl, CCl3COOCH2CH2ClCH2Cl and CCl3COOCH2CH2CH2CH2Cl.

8. The catalyst component according to any one of claims 1 to 7, characterized in that: Based on 1 mol of magnesium in the magnesium compound, the content of the halogenated acetate compound is 0.01-5 mol; and / or the content of the titanium compound is 1-20 mol.

9. The catalyst component according to claim 1, characterized in that: The organic alcohol is selected from C1-C 12 Fatty alcohols, C7-C 12 Aromatic alcohol; and at least one of the substituted alcohols derived from the corresponding fatty alcohol or aromatic alcohol; and / or, The organic epoxy compound is selected from at least one of oxides, glycidyl ethers and internal ethers of aliphatic olefins, aliphatic dienes, halogenated aliphatic olefins or halogenated aliphatic dienes having 2 to 8 carbon atoms; and / or, The organic phosphorus compound is selected from phosphate triester compounds and / or phosphite compounds.

10. The catalyst component according to claim 1, characterized in that: The organic alcohol is at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, benzyl alcohol and phenylethyl alcohol; and / or, The organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether and tetrahydrofuran; and / or, The organic phosphorus compound is selected from phosphate triester compounds and / or phosphite compounds.

11. The catalyst component according to claim 10, characterized in that: The organic alcohol is at least one of ethanol, isopropanol, butanol, 2-ethylhexanol, benzyl alcohol and phenylethyl alcohol; and / or, The organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, epichlorohydrin and tetrahydrofuran.

12. A method for preparing the catalyst component according to any one of claims 1 to 11, comprising mixing the magnesium compound with an optional liquid hydrocarbon, and an optional organic alcohol, an optional organic epoxy compound and an optional organic phosphorus compound to obtain a liquid component containing the magnesium compound; and mixing and contacting the liquid component containing the magnesium compound with the halogenated acetate compound and a titanium compound to obtain the catalyst component.

13. The preparation method according to claim 12, characterized in that: Based on 1 mol of magnesium content in the magnesium compound, the feeding amount of the halogenated acetate compound is 0.001-10 mol; and / or, the feeding amount of the titanium compound is 0.2-100 mol; and / or, the feeding amount of the organic alcohol is 0-10 mol; and / or, the feeding amount of the organic epoxy compound is 0-10 mol; and / or, the feeding amount of the organic phosphorus compound is 0-10 mol.

14. The preparation method according to claim 13, characterized in that: Based on 1 mol of magnesium content in the magnesium compound, the feeding amount of the halogenated acetate compound is 0.01-5 mol; and / or, the feeding amount of the titanium compound is 0.5-50 mol; and / or, the feeding amount of the organic alcohol is 0-4 mol; and / or, the feeding amount of the organic epoxy compound is 0-4 mol; and / or, the feeding amount of the organic phosphorus compound is 0-5 mol.

15. The preparation method according to claim 12, characterized in that include: The liquid component containing the magnesium compound is obtained by at least one of the following methods: 1) directly adding the alkyl magnesium described in ① or a liquid hydrocarbon solution containing the alkyl magnesium to obtain a liquid component containing a magnesium compound; 2) mixing the magnesium compound in ② with an organic alcohol, an optional organic epoxy compound and an optional organic phosphorus compound to obtain a liquid component containing the magnesium compound; 3) The magnesium compound in ② is mixed with an organic phosphorus compound and an organic epoxy compound to obtain a liquid component containing a magnesium compound.

16. The preparation method according to claim 15, characterized in that include: In method 2), the magnesium compound in ② is mixed with an organic alcohol, an optional organic epoxy compound and an optional organic phosphorus compound at a mixing temperature of 40-80° C. for 0.01-10 hours to obtain a liquid component containing the magnesium compound; In method 3), the magnesium compound in ② is mixed with an organic phosphorus compound and an organic epoxy compound at a mixing temperature of 40-80° C. for 0.01-10 hours to obtain a liquid component containing the magnesium compound.

17. The preparation method according to claim 15, characterized in that: In method 2), based on the magnesium content of the magnesium compound, the content of the organic alcohol is 0.01-10 moles; the content of the organic epoxy compound is 0-10 moles; the content of the organic phosphorus compound is 0-10 moles; and / or, In method 3), the content of the organic phosphorus compound is 0.01-10 moles per mole of magnesium in the magnesium compound; and the content of the organic epoxy compound is 0.01-10 moles.

18. The preparation method according to claim 17, characterized in that: In method 2), based on the magnesium content of the magnesium compound, the content of the organic alcohol is 0.02-4 moles; the content of the organic epoxy compound is 0-4 moles; the content of the organic phosphorus compound is 0-5 moles; and / or, In method 3), the content of the organic phosphorus compound is 0.02-5 moles per mole of magnesium in the magnesium compound; and the content of the organic epoxy compound is 0.02-4 moles.

19. The preparation method according to any one of claims 12 to 18, characterized in that: Firstly, a liquid component containing a magnesium compound is mixed and contacted with a halogenated acetate compound for reaction, and then the obtained mixture is mixed and contacted with a titanium compound; and / or, The halogenated acetate compound is derived from the halogenated acetate compound added directly and / or is generated in situ by esterification reaction between the corresponding acetyl halide and the corresponding alcohol; and / or, The mixed contact is carried out under nitrogen and / or inert atmosphere; and / or, The method also includes the steps of washing and drying the catalyst components obtained after the mixed contact.

20. The preparation method according to claim 19, characterized in that: The liquid component containing the magnesium compound is mixed and contacted with the halogenated acetate compound in the solution at -30-150°C for 0.6-600 minutes, and the obtained mixture is cooled to -30-80°C, and mixed and contacted with the titanium compound at -30-80°C for 0.6-600 minutes; then the temperature is raised to 20-150°C, maintained for 0.6-600 minutes, and the liquid is filtered out.

21. The preparation method according to claim 20, characterized in that: The method further comprises the step of contacting the obtained product with a titanium compound at -30 to 150° C. for multiple times after filtering out the liquid.

22. The preparation method according to claim 20, characterized in that: The method further comprises the step of contacting the obtained product with a titanium compound at -30-150° C. for multiple times after filtering out the liquid, with each contact time being 0.6-600 minutes.

23. A catalyst component prepared by the preparation method according to any one of claims 12 to 22.

24. A catalyst comprising an organoaluminum compound and the catalyst component according to any one of claims 1 to 11 and 23.

25. The catalyst according to claim 24, characterized in that: The molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is 5-1000; and / or, The organoaluminum compound has the general formula AlR ’ y X 3-y , R ’ is a hydrocarbon group having 1 to 20 carbon atoms; AlR ’ y X 3-y wherein X is a halogen; and y is an integer of 0≤y≤3.

26. The catalyst according to claim 25, characterized in that: The molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is 20-800; and / or, The organoaluminum compound has the general formula AlR ’ y X 3-y , R ’ is a hydrocarbon group having 1 to 20 carbon atoms, and is one of an alkyl group, an aralkyl group and an aryl group; AlR ’ y X 3-y wherein X is a halogen, which is chlorine and / or bromine; and y is an integer of 0≤y≤3.

27. The catalyst according to claim 25, characterized in that: The organoaluminum compound is at least one of trialkylaluminum, alkylaluminum hydride and alkylaluminum chloride.

28. The catalyst according to claim 25, characterized in that: The organoaluminum compound is at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride, ethylaluminum dichloride, diethylaluminum monohydrogen and diisobutylaluminum monohydrogen.

29. A method for olefin polymerization, the method comprising: contacting one or more olefins with the catalyst of any one of claims 24 to 28 under olefin polymerization conditions; Or, one or more olefins are contacted with an organoaluminum compound and the catalyst component according to any one of claims 1 to 12 and 24 under olefin polymerization conditions.

30. The olefin polymerization method according to claim 29, characterized in that: The olefin polymerization reaction is carried out in the presence of hydrogen; The molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is 5-1000; and / or, The organoaluminum compound has the general formula AlR ’ y X 3-y , R ’ is a hydrocarbon group having 1 to 20 carbon atoms, and is one of an alkyl group, an aralkyl group and an aryl group; AlR ’ y X 3-y wherein X is a halogen; and y is an integer of 0≤y≤3.

31. The olefin polymerization method according to claim 30, characterized in that: The organoaluminum compound is at least one of trialkylaluminum, alkylaluminum hydride and alkylaluminum chloride.

32. The olefin polymerization method according to claim 30, characterized in that: The organoaluminum compound is at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride, ethylaluminum dichloride, diethylaluminum monohydrogen and diisobutylaluminum monohydrogen.