Catalyst component for olefin polymerization, preparation method of catalyst component, catalyst and application of catalyst

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 is prepared by reacting raw materials including a magnesium compound, a precipitation aid, a titanium-containing compound, an acetate compound, an organic alcohol compound, an organic aluminum compound N and an electron donor compound. The catalyst provided by the invention is used for preparing special / ultra-high molecular weight polyolefin through olefin polymerization reaction, and the prepared polymer has the advantages of controllable molecular weight, narrow molecular weight distribution, low hexane extract content, low large particle and fine powder content, low branching degree, high sphericity and better low entanglement performance.

Description

Technical Field

[0001] The present invention relates to the technical field of olefin polymerization, and more particularly to a catalyst component for olefin polymerization and a preparation method thereof, as well as a catalyst obtained from the catalyst component and application thereof. Background Art

[0002] Ultra high molecular weight polyethylene (UHMWPE) is a special polyethylene product with a molecular weight greater than 1.5 million. It has comprehensive properties that are unmatched by ordinary polyethylene and other engineering plastics, such as wear resistance, impact resistance, self-lubrication, corrosion resistance, low temperature resistance, hygiene and non-toxicity, non-adhesion, non-water absorption, and low density. The difficulty in processing UHMWPE has hindered its large-scale application.

[0003] Very high molecular weight polyethylene (VHMWPE) is a polyethylene product with a molecular weight between 300,000 and 1.5 million. It has excellent mechanical properties, ultra-high impact strength and good wear resistance.

[0004] Compared with ultra-high molecular weight polyethylene, ultra-high molecular weight polyethylene has better molding and processing performance and can be used in applications where the performance is better than that of ordinary polyethylene and the cost is not high. Its downstream applications usually include pressed sheets, extruded profiles, pipes, battery separators, sintered filter materials, and modified extrusion-grade UHMWPE pellets. A new use of ultra-high molecular weight polyethylene is for wet-process lithium-ion battery separators, especially separators produced by wet-process biaxial stretching. After biaxial stretching, the separator has higher longitudinal and transverse strength.

[0005] Currently, most of the widely used high-end special / ultra-high molecular weight polyethylene products come from abroad. The key factors required for high-end polyethylene products include:

[0006] 1. Sufficiently high molecular weight and narrow molecular weight distribution;

[0007] 2. It has lower hexane extractable content and ash content;

[0008] 3. The content of large particles and fine powder is small.

[0009] For example, when polyethylene products are used in fields such as lithium battery separators or artificial joints, lower ash content can improve the product's resistance to penetration and reduce its impact on the human body; small amounts of large particles and fine powder can ensure stability and continuity in the production process and improve product performance.

[0010] At the same time, researchers have found that when the polymer particles are uniform, the molecular weight distribution is narrow, the hexane extractable content is low, the sphericity is high, the content of large particles and fine powder is small, the branching degree is low and the entanglement is low, the special / ultra-high molecular weight polyethylene is processed by plunger extrusion, compression molding, dry / wet biaxial stretching, and is easier to process and has higher quality. At present, most commercialized ultra-high molecular weight polyethylene or ultra-high molecular weight polyethylene is prepared by Ziegler-Natta catalyst (ZN catalyst for short), and the polyethylene products prepared by this catalyst are difficult to meet the above requirements. Summary of the invention

[0011] In order to solve the above problems, the present invention provides a catalyst component for olefin polymerization, a preparation method thereof and a catalyst. The catalyst provided by the present invention not only has high activity and bulk density, but also has a controllable molecular weight, a narrow molecular weight distribution, a low hexane extract content, a low content of large particles and fine powder, a low degree of branching, a high degree of sphericity, and good low entanglement performance.

[0012] Firstly, an object of the present invention is to provide a catalyst component for olefin polymerization.

[0013] Specifically, the catalyst component includes the reaction product of raw materials including the following components: a magnesium complex, a precipitation aid, a titanium-containing compound, an acetate compound, an organic alcohol compound, an organic aluminum compound N and an electron donor compound; wherein the electron donor compound includes an electron donor compound a and / or an electron donor compound b.

[0014] Further, in the catalyst components, the components are calculated per mole of magnesium in the magnesium complex as follows:

[0015]

[0016]

[0017] And the molar amounts of electron donor a and electron donor b are not 0 at the same time.

[0018] Further, the general formula (I) of the electron donor compound a is as follows:

[0019]

[0020] R1 and R2 are independently methyl or ethyl, and R3 and R4 are independently hydrogen or methyl. Specifically, the electron donor compound a is one or a combination of 2,2-dimethyl-1,3-diethoxy-propane, 2,2-dimethyl-1,3-dimethoxy-propane, 1-ethoxy-3-methoxy-propane, and 2,2-dimethyl-1-ethoxy-3-methoxy-propane.

[0021] Further, the general formula (II) of the electron donor compound b is as follows:

[0022]

[0023] R5 and R6 are independently methyl or ethyl; R7, R8, R9, R 10 The same or different, independently hydrogen, halogen, C1~C 10 Straight chain alkyl, C1~C 10 Branched alkyl, C1~C 10 Preferably, R7, R8, R9, R 10 The electron donor compound b is one of fluorine, chlorine, bromine, iodine, C1-C6 straight chain alkyl, C1-C6 branched chain alkyl, and C1-C6 alkoxy. Specifically, the electron donor compound b is one of or a combination of o-phenylenedimethyl ether, o-phenylenediethyl ether, and 1-ethoxy-2-methoxybenzene.

[0024] Furthermore, when the electron donor compound is a mixture of an electron donor compound a and an electron donor compound b, the molar ratio of the electron donor compound a to the electron donor compound b is 0.01-100; preferably 0.05-20; more preferably 0.1-20.

[0025] Furthermore, in the present invention, the magnesium complex is prepared by the following method: dissolving a magnesium halide compound in a solvent system including an organic epoxy compound and an organic phosphorus compound to obtain the magnesium complex.

[0026] Preferably, based on each mole of magnesium, the organic epoxide is 0.01 to 1 mole; preferably 0.03 to 0.5 mole; the organic phosphide added is 0.01 to 1 mole; preferably 0.01 to 0.3 mole.

[0027] Preferably, the magnesium halide compound may be one or a combination of magnesium halide, a complex of magnesium halide and water, alcohol or electron donor Y, phenoxymagnesium chloride, isopropoxymagnesium chloride and butoxymagnesium chloride.

[0028] More preferably, the magnesium halide is one or a combination of magnesium dichloride, magnesium dibromide, magnesium difluoride and magnesium diiodide.

[0029] More preferably, the complex of magnesium halide and alcohol or electron donor Y is a complex of magnesium dihalide and methanol, ethanol, propanol, butanol, pentanol, hexanol, isooctyl alcohol, ammonia compounds, hydroxylamine compounds, ether compounds, or ester compounds.

[0030] Preferably, the organic epoxy compound is a compound containing C2 to C 18The organic epoxy compound is one or a combination of aliphatic olefins, dienes, halogenated aliphatic olefins, oxides, glycidyl ethers, and internal ethers. Specifically, the organic epoxy compound is one or a combination of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, and butyl glycidyl ether.

[0031] Preferably, the organic phosphorus compound is one or a combination of a hydrocarbon ester of orthophosphoric acid or phosphorous acid, and a halogenated hydrocarbon ester of orthophosphoric acid or phosphorous acid.

[0032] Specifically, the organophosphorus compound is one or a combination of 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, tri-n-octyl phosphate, triisooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, tri-tert-butyl phosphite, tri-n-pentyl phosphite, triisopentyl phosphite, tri-n-hexyl phosphite, triisohexyl phosphite, tri-n-heptyl phosphite, triisoheptyl phosphite, tri-n-octyl phosphite, triisooctyl phosphite, triphenyl phosphite, and di-n-butyl phosphite.

[0033] Furthermore, in the present invention, the precipitation aid is one or a combination of organic acid, organic acid anhydride, organic ether and organic ketone.

[0034] Preferably, the precipitation aid is a C2-C 20 One or a combination of organic acids, organic anhydrides, organic ethers and organic ketones.

[0035] Specifically, the precipitation aid is one or a combination of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether, and pentyl ether. Particularly preferably, the precipitation aid is phthalic anhydride.

[0036] Furthermore, the general formula of the titanium-containing compound in the present invention is Ti(OR 4 ) e X 1 f ; Among them, R 4 Contains C1~C 10 Aliphatic hydrocarbon or C6~C 14 The aromatic hydrocarbon group preferably contains C1 to C6 alkyl, C2 to C6 alkenyl, C3 to C 10 Cycloalkyl, C6~C 10 An aromatic hydrocarbon group, for example, R4 X may be one of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclopropyl, methylcyclopropyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl, and xylyl; 1 is a halogen, preferably one of fluorine, chlorine, bromine and iodine; e is an integer of 0 to 2, f is an integer of 1 to 4, and e+f=3 or 4.

[0037] Specifically, the titanium-containing compound is one or a combination of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium trichloride, tetraethoxytitanium, triethoxytitanium monochloride, diethoxytitanium dichloride, and triethoxytitanium trichloride.

[0038] Furthermore, in the present invention, the general formula of the acetate compound is CH3COOR 3 , where R 3 Contains C1~C 10 Alkyl, C2~C 10 Alkenyl, C3~C 10 Cycloalkyl, C2~C 10 Alkynyl, C6~C 10 An aromatic hydrocarbon group, for example, R 3 It can be one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-octyl, cyclopropyl, methylcyclopropyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl, and xylyl.

[0039] Specifically, the acetate compound is one or a combination of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, and n-octyl acetate.

[0040] Furthermore, in the present invention, the general formula of the organic alcohol compound is R 5 OH, where R 5 Contains C1~C 10 Alkyl groups, for example, R 5 It may be one of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl and isooctyl.

[0041] Specifically, the alcohol compound is one or a combination of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, n-hexanol, n-octanol, and isooctyl alcohol.

[0042] Furthermore, in the present invention, the general formula of the organoaluminum compound N is AlR 6 n X 2 3-n ; Among them, R 6 is hydrogen, contains C1~C 20 One or a combination of hydrocarbon groups; X2 is a halogen; and n is an integer of 0≤n≤3.

[0043] Specifically, the organoaluminum compound N is one or a combination of triethylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, sesquiethylaluminum, isobutylaluminum dichloride, triisobutylaluminum, diisopropylaluminum monochloride, methyl-n-propylaluminum monochloride, and diphenylaluminum monochloride.

[0044] Secondly, the second object of the present invention is to provide a method for preparing the catalyst component for olefin polymerization which is one of the objects of the present invention.

[0045] The method comprises the following steps:

[0046] Step 1, dissolving a magnesium halide compound in an organic epoxy compound, an organic phosphorus compound and an inert diluent A to react to form a solution system containing a magnesium complex;

[0047] Step 2, adding a precipitation aid to the solution system obtained in step 1 to continue the reaction;

[0048] Step 3: then lower the temperature of the reaction system in step 2, add the titanium-containing compound and continue the reaction;

[0049] Step 4: subsequently adding a mixed solution of an inert diluent B containing an acetate compound and an organic alcohol compound to the reaction system of step 3 at once or in steps to continue the reaction;

[0050] Step 5, adding an electron donor compound to the reaction system of step 4 to continue the reaction;

[0051] Step 6: Wash the mixture obtained in step 5 with an inert diluent A, and then add an organoaluminum compound N to continue the reaction to obtain a catalyst component.

[0052] Furthermore, in step 1, the reaction conditions for preparing the magnesium-containing complex are: temperature of 40-80° C., preferably 50-70° C.; time of 1-5 h, preferably 1-3 h; and the amount of inert diluent A added per mole of magnesium is 0.01-5 moles, preferably 0.4-2 moles.

[0053] Furthermore, the inert diluent A used in the present invention is one or a combination of aromatic hydrocarbon compounds and alkane compounds; wherein the aromatic hydrocarbon compound is one or a combination of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and their derivatives; the alkane compound is one or a combination of C3 to C 20 One or a combination of straight-chain alkanes, branched-chain alkanes or cycloalkanes having carbon atoms.

[0054] Furthermore, in step 2, the reaction conditions for adding the precipitation aid are: temperature of 40 to 80° C., preferably 50 to 70° C.; and time of 0.5 to 3 h.

[0055] Furthermore, in step three, the reaction conditions for adding the titanium-containing compound are: temperature of -60 to -30°C; time of 0.5 to 3 hours. It is worth mentioning that in this step three, the titanium-containing compound is added dropwise into the reaction kettle for 0.5 to 3 hours. After cooling and adding the titanium-containing compound, the subsequent components can be added.

[0056] Further, in step 4, the amount of the inert diluent B added is 0.001 to 2 moles, preferably 0.05 to 0.5 moles, per mole of magnesium; wherein the inert diluents of the acetate compound and the organic alcohol compound are added to the reaction system of step 3 in whole or in batches under the following conditions:

[0057] When the reaction conditions are used for one-time addition, the temperature is -60 to 30°C, preferably -20 to 20°C; the time is 0.5 to 3h, preferably 1 to 2h;

[0058] When adding in batches, the reaction conditions are as follows: the acetate compound and the organic alcohol compound are added in an inert diluent B mixed solution in at least two batches; preferably: after the first batch is added, the mixture is reacted at a constant temperature for 0.5 to 1 hour, then the temperature is gradually raised to 0 to 30° C., and then the remaining mixed solution is added, and the mixture is reacted at a constant temperature for 0.5 to 1 hour, and then the temperature is gradually raised to 60 to 100° C., and then the mixture is reacted at a constant temperature for 1 to 3 hours; the heating rate of the system is preferably 0.2 to 2° C. / min.

[0059] Furthermore, the inert diluent B used in the present invention is one or a combination of halogenated aromatic compounds and halogenated alkane compounds; wherein the halogenated aromatic compounds are aromatic hydrocarbons containing C6 to C8 and their derivatives, for example, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and their derivatives, monobromobenzene, dibromobenzene, tribromobenzene, monobromotoluene and their derivatives; the halogenated alkane compounds are aromatic hydrocarbons containing C3 to C8 and their derivatives. 20 The halogenated hydrocarbons may be selected from the group consisting of straight-chain halogenated alkanes, branched halogenated alkanes, and halogenated cycloalkanes, for example, may be selected from the group consisting of dichloromethane, chloroform, tetrachloromethane, ethyl bromide, and ethyl chloride, or a combination thereof.

[0060] Furthermore, in step five, the reaction conditions for adding the electron donor are: temperature of 70 to 95° C.; preferably 80 to 90° C.; time of 0.5 to 3 h; preferably 1 to 2 h.

[0061] Furthermore, in step six, the reaction conditions for adding the organoaluminum compound N are: temperature of -10 to 100°C; preferably 0 to 20°C; time of 0.5 to 3 hours; preferably 1 to 2 hours.

[0062] Among them, in Step 6, after the reaction of the organoaluminum compound N is completed, the reaction system is allowed to stand, the unreacted substances and the solvent are removed, and a solid catalyst component is obtained.

[0063] Thirdly, the third object of the present invention is to provide a catalyst for olefin polymerization, and the catalyst comprises the following components:

[0064] Component 1, the catalyst component for olefin polymerization of the first object of the present invention or the catalyst component prepared by the method of the second object of the present invention;

[0065] Component 2, organoaluminum compound D.

[0066] Among them, the molar ratio of titanium atoms in Component 1 to aluminum atoms in Component 2 is 0.1:1 to 20:1; preferably 0.5:1 to 10:1; more preferably 0.5:1 to 5:1.

[0067] Further, the general formula of the organoaluminum compound D is AlR 7 d X 3 3-d ; where R 7 is one or a combination of hydrogen and a hydrocarbon group containing C1 to C 20 ; X 3 is a halogen; preferably one of fluorine, chlorine, and bromine; d is an integer of 0 < d ≤ 3.

[0068] Specifically, the organoaluminum compound D is one or a combination of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum, diisobutylaluminum, monochlorodiethylaluminum, sesquiethylaluminum, and dichloroethylaluminum.

[0069] Finally, the fourth object of the present invention is to provide an application of the catalyst for olefin polymerization of the third object of the present invention. The catalyst of the third object of the present invention can be used in an olefin polymerization reaction. Specifically, it is used in an olefin polymerization reaction to prepare special / ultra-high molecular weight polyolefins. The obtained special / ultra-high molecular weight polyolefins have a molecular weight greater than 500,000, a particle size distribution between 75 and 500 μm with a mass fraction ≥ 99%, a span of powder particles ≤ 0.8, a branching degree ≤ 0.5 SCB / 1000C, and have good low entanglement properties.

[0070] Preferably, in the olefin polymerization reaction, the general formula of at least one olefin in the raw material olefins is CH2=CHR, where R is one of hydrogen and an alkyl group of C1 to C6.

[0071] It is worth mentioning that in the olefin polymerization reaction, the raw material olefin can be a homopolymer system of ethylene; it can also be a copolymer system of ethylene and / or α-olefin and other comonomers; wherein the comonomer is preferably one or a combination of propylene, butene, pentene, hexene, octene, and 4-methyl-1-pentene.

[0072] Preferably, the olefin polymerization reaction can be carried out by slurry polymerization or gas phase polymerization; wherein the medium of the slurry polymerization is one or a combination of isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene and xylene.

[0073] Preferably, the conditions for olefin polymerization are:

[0074] Reaction pressure: 0.2-1.5Mpa; preferably 0.5-1Mpa;

[0075] Reaction temperature: 70-100°C; preferably 75-85°C;

[0076] Reaction time: 1.5 to 8 hours, preferably 1.5 to 3 hours.

[0077] Compared with the prior art, the present invention has the following beneficial effects:

[0078] 1. After the electron donor compound is introduced into the ZN catalyst system, the active center for generating low molecular weight PE components can be reduced, thereby increasing the molecular weight of the polymer product, and the molecular weight of the polymer can be controlled by adjusting the addition amount.

[0079] 2. In the present invention, when the acetate compound and the organic alcohol compound are added to the reaction, the inert diluent B is used for dilution. Since the polarity of the inert diluent B is different from that of the inert diluent A, and under the synergistic effect of the acetate compound and the organic alcohol compound, the dissolution state of the catalyst particles is affected, so that the prepared catalyst has better sphericity and better particle morphology. On the other hand, the dilution effect of the inert solvent slows down the reaction rate, and the active center of the catalyst is more uniformly modified, the effective titanium content is increased, and the activity of the catalyst is better.

[0080] 3. The present invention optimizes the method of adding acetate compounds, organic alcohol compounds and electron donor compounds when introducing them into the catalyst components. The inventor unexpectedly discovered that after the acetate compounds and organic alcohol compounds are first mixed in an inert solvent and diluted and then added in batches or all at once, and then the electron donor compound is added, the performance of the obtained catalyst is improved, the obtained polymer has a relatively low degree of branching, and has better disentanglement performance and better processing performance.

[0081] 4. The present invention simultaneously introduces an organic aluminum compound N into the catalyst component, and after treatment, a solid particle catalyst containing magnesium and titanium is obtained, which has higher catalyst performance. In the olefin polymerization reaction, the obtained polymer has a narrow molecular weight distribution, less large particles and fine powder content, and high sphericity. DETAILED DESCRIPTION

[0082] 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.

[0083] The raw materials used in the examples and comparative examples, unless otherwise specified, are disclosed in the prior art, for example, they can be directly purchased or obtained according to the preparation methods disclosed in the prior art.

[0084] In the present invention, the testing method is as follows:

[0085] 1. Determination of polymer bulk density: The test method for apparent density, volume factor and pourability of plastics (ASTM D1895) is used for determination.

[0086] 2. Polymer molecular weight test: Determined according to ASTM D4020-18.

[0087] 3. Determination of polymer sphericity: The sphericity was determined using a Camsizer particle size analyzer from Retsch GmbH, Germany.

[0088] 4. Determination of polymerization activity: It is calculated by dividing the mass of the powder obtained by polymerization by the amount of catalyst added.

[0089] 5. Determination of polymer particle size distribution: Use standard sieve for sieving.

[0090] 6. Determination of polymer span value: measured by Microtrac laser particle size and shape analyzer.

[0091] 7. Determination of polymer sequence distribution and branching degree: Determined on a Bruker 400MHz NMR instrument. Test solvent C6D4Cl2, test temperature 125°C, scan times 5000-6000 times, sampling time 5 seconds, Φ=10mm sample tube. Qualitative and quantitative analysis of branching is calculated by relevant software analysis.

[0092] Example 1

[0093] (1) Preparation of catalyst components

[0094] Add 4.0 g of magnesium chloride, 60 ml of toluene, 3.0 ml of epichlorohydrin, and 9 ml of tri-n-butyl phosphate to the reactor and react for 2 hours at a temperature of 70 ° C. Then add 2 g of phthalic anhydride and continue to react for 1 hour. Cool the system to -20 ° C, slowly add 70 ml of titanium tetrachloride, then add 3 ml of ethyl acetate, 3 ml of ethanol, and 50% of 20 ml of a mixed solution of monochlorobenzene, keep the temperature constant for 1 hour, gradually increase the temperature to 10 ° C, then add the remaining mixed solution, keep the temperature constant for 1 hour, gradually increase the temperature to 85 ° C, and keep the temperature constant for 1 hour. Add 1 ml of 2,2-dimethyl-1,3-diethoxy-propane and continue to keep the temperature constant for 1 hour. Stop stirring, let it stand, and wash twice with an inert diluent of toluene. Add 60 ml of hexane to the reactor, cool it to 0 ° C, slowly add 10 ml of a 0.9M monochlorodiethylaluminum heptane solution, react for 0.5 hours, and heat it to 50 ° C for 1 hour. Stop stirring, let it stand, the suspension will quickly separate into layers, remove the upper clear liquid, wash it with inert diluent toluene and organic solvent hexane for many times, and then dry it to obtain a solid catalyst component with good fluidity.

[0095] (2) Preparation of polymer

[0096] A 2L stainless steel reactor was fully replaced with high-purity nitrogen, and then 1L of hexane and 1.0ml of 1M triethylaluminum were added, and then the solid catalyst component (containing 0.6mg of titanium) prepared by the above method was added. The temperature was raised to 70°C, hydrogen was introduced to make the pressure in the reactor reach 0.28Mpa, ethylene was introduced to make the total pressure in the reactor reach 0.73Mpa (gauge pressure), and polymerization was carried out at 80°C for 2 hours. The polymerization results are shown in Table 1.

[0097] Example 2

[0098] (1) Preparation of catalyst components

[0099] Add 4.0 g of magnesium chloride, 90 ml of toluene, 3.0 ml of ethylene oxide, and 9 ml of triisobutyl phosphate into the reactor and react for 4 hours at 60 ° C. Then add 2 g of phthalic anhydride and continue to react for 2 hours. Cool the system to -35 ° C, slowly drop 70 ml of titanium tetrachloride, then add 3 ml of isopropyl acetate, 3 ml of ethanol, and 40% of 20 ml of dichlorobenzene mixed solution, keep the temperature constant for 0.5 hours, gradually increase the temperature to 20 ° C, then add the remaining mixed solution, keep the temperature constant for 1 hour, gradually increase the temperature to 85 ° C, and keep the temperature constant for 1 hour. Add 1 ml of 2,2-dimethyl-1,3-diethoxy-propane and continue to keep the temperature constant for 1 hour. Stop stirring, let it stand, and wash twice with inert diluent toluene. Add 60 ml of hexane to the reactor, cool it to -10°C, slowly add 10 ml of 0.9M triethylaluminum heptane solution, react for 0.5 hours, heat it to 50°C and react for 1 hour. Stop stirring, let it stand, the suspension will quickly separate, remove the supernatant, wash it with inert diluent toluene and organic solvent hexane several times, and then dry it to obtain a solid catalyst component with good fluidity.

[0100] (2) Preparation of polymer

[0101] Same as Example 1, the polymerization results are shown in Table 1.

[0102] Example 3

[0103] (1) Preparation of catalyst components

[0104] Add 4.5g of magnesium chloride, 90ml of toluene, 3.0ml of epichlorohydrin, and 9ml of trimethyl phosphate to the reactor and react for 4 hours at a temperature of 60°C. Then add 4g of phthalic anhydride and continue to react for 1 hour. Cool the system to -30°C, slowly drop 80ml of titanium tetrachloride, then add 4ml of ethyl acetate, 3ml of n-butanol, and 30% of a mixed solution of chloroform, keep the temperature constant for 1 hour, gradually increase the temperature to 10°C, then add the remaining mixed solution, gradually increase the temperature to 85°C, and keep the temperature constant for 1 hour. Add 1ml of 2,2-dimethyl-1,3-diethoxy-propane and 1ml of o-phenylenedimethyl ether, and continue to keep the temperature constant for 1 hour. Stop stirring, let it stand, and wash twice with an inert diluent of toluene. Add 60ml of hexane to the reactor, cool it to 0°C, slowly add 10ml of a 0.9M solution of diethylaluminum monochloride in heptane, react for 1 hour, and heat it to 50°C for 1 hour. Stop stirring, let it stand, the suspension will quickly separate into layers, remove the upper clear liquid, wash it with inert diluent toluene and organic solvent hexane for many times, and then dry it to obtain a solid catalyst component with good fluidity.

[0105] (2) Preparation of polymer

[0106] Same as Example 1, the polymerization results are shown in Table 1.

[0107] Example 4

[0108] (1) Preparation of catalyst components

[0109] Add 4.8g of magnesium chloride, 100ml of toluene, 3.0ml of epichlorohydrin, and 9ml of triethyl phosphate to the reactor and react for 2 hours at 80°C. Then add 5g of phthalic anhydride and continue to react for 1 hour. Cool the system to -10°C, slowly add 90ml of titanium tetrachloride, then gradually increase the temperature to 0°C, then add 3ml of ethyl acetate, 3ml of ethanol, and 30ml of a mixed solution of monochlorobenzene, keep the temperature constant for 1 hour, gradually increase the temperature to 85°C, and keep the temperature constant for 1 hour. Add 1ml of 2,2-dimethyl-1,3-diethoxy-propane and 1ml of diethyl ether, and continue to keep the temperature constant for 1 hour. Stop stirring, let it stand, and wash twice with inert diluent toluene. Add 60ml of hexane to the reactor, cool to 0°C, slowly add 10ml of 0.9M monochlorodiethylaluminum heptane solution, react for 0.5 hour, and heat to 50°C for 1 hour. Stop stirring, let it stand, the suspension will quickly separate into layers, remove the upper clear liquid, wash it with inert diluent toluene and organic solvent hexane for many times, and then dry it to obtain a solid catalyst component with good fluidity.

[0110] (2) Preparation of polymer

[0111] Same as Example 1, the polymerization results are shown in Table 1.

[0112] Example 5

[0113] (1) Preparation of catalyst components

[0114] Add 4.0 g of magnesium chloride, 120 ml of toluene, 5.0 ml of epichlorohydrin, and 15 ml of tri-n-butyl phosphate to the reactor and react for 3 hours at a temperature of 50 ° C. Then add 2 g of phthalic anhydride and continue to react for 1 hour. Cool the system to -20 ° C, slowly add 50 ml of titanium tetrachloride, then add 4 ml of ethyl acetate, 4 ml of isooctyl alcohol, and 30 ml of chloroform mixed solution, keep the temperature constant for 1 hour, gradually increase the temperature to 85 ° C, and keep the temperature constant for 1 hour. Add 1 ml of 2,2-dimethyl-1,3-diethoxy-propane and 1 ml of o-phenylenedimethyl ether, and continue to keep the temperature constant for 1 hour. Stop stirring, let it stand, and wash twice with inert diluent toluene. Add 60 ml of hexane to the reactor, cool to 0 ° C, slowly add 10 ml of 0.9M monochlorodiethylaluminum heptane solution, react for 0.5 hours, and heat to 50 ° C for 1 hour. Stop stirring, let it stand, the suspension will quickly separate into layers, remove the upper clear liquid, wash it with inert diluent toluene and organic solvent hexane for many times, and then dry it to obtain a solid catalyst component with good fluidity.

[0115] (2) Preparation of polymer

[0116] Same as Example 1, the polymerization results are shown in Table 1.

[0117] Example 6

[0118] (1) Preparation of catalyst components

[0119] Add 4.0 g of magnesium chloride, 90 ml of toluene, 3.0 ml of ethylene oxide, and 9 ml of tripropyl phosphate to the reactor and react for 3 hours at a temperature of 60 ° C. Then add 4 g of phthalic anhydride and continue to react for 3 hours. Cool the system to -30 ° C, slowly add 70 ml of titanium tetrachloride, then gradually increase the temperature to 10 ° C, then add 3 ml of methyl acetate, 6 ml of butanol, and 30 ml of a mixed solution of monochlorobenzene, keep the temperature constant for 2 hours, gradually increase the temperature to 90 ° C, and keep the temperature constant for 2 hours. Add 1 ml of 2,2-dimethyl-1,3-diethoxy-propane and 1 ml of dimethyl phenyl ether, and continue to keep the temperature constant for 3 hours. Stop stirring, let it stand, and wash twice with an inert diluent of toluene. Add 80 ml of hexane to the reactor, cool it to 0 ° C, slowly add 10 ml of a 0.9M monochlorodiethylaluminum heptane solution, react for 1 hour, and heat it to 50 ° C for 1 hour. Stop stirring, let it stand, the suspension will quickly separate into layers, remove the upper clear liquid, wash it with inert diluent toluene and organic solvent hexane for many times, and then dry it to obtain a solid catalyst component with good fluidity.

[0120] (2) Preparation of polymer

[0121] Same as Example 1, the polymerization results are shown in Table 1.

[0122] Example 7

[0123] (1) Preparation of catalyst components

[0124] Add 4.0g magnesium chloride, 60ml toluene, 3.0ml epichlorohydrin, and 9ml tri-n-butyl phosphate to the reactor and react for 2 hours at 70°C. Then add 1g of phthalic anhydride and continue to react for 1 hour. Cool the system to -20°C, slowly drop 70ml of titanium tetrachloride, then add 3ml of ethyl acetate, 3ml of ethanol, and 50% of 20ml of a mixed solution of monochlorobenzene, keep the temperature constant for 1 hour, gradually increase the temperature to 10°C, then add the remaining mixed solution, keep the temperature constant for 1 hour, gradually increase the temperature to 85°C, and keep the temperature constant for 1 hour. Add 1ml of dimethyl phenyl ether and continue to keep the temperature constant for 1 hour. Stop stirring, let it stand, and wash twice with an inert diluent of toluene. Add 60ml of hexane to the reactor, cool to -10°C, slowly add 10ml of a 0.9M monochlorodiethylaluminum heptane solution, react for 1 hour, and heat to 50°C to react for 1 hour. Stop stirring, let it stand, the suspension will quickly separate into layers, remove the upper clear liquid, wash it with inert diluent toluene and organic solvent hexane for many times, and then dry it to obtain a solid catalyst component with good fluidity.

[0125] (2) Preparation of polymer

[0126] Same as Example 1, except that the organoaluminum compound D is triisobutylaluminum. The polymerization results are shown in Table 1.

[0127] Example 8

[0128] (1) Preparation of catalyst components

[0129] Add 4.0 g of magnesium chloride, 100 ml of xylene, 5.0 ml of epichlorohydrin, and 15 ml of tri-n-butyl phosphate to the reactor and react for 3 hours at 80 ° C. Then add 5 g of phthalic anhydride and continue to react for 1 hour. Cool the system to -20 ° C, slowly drop 90 ml of tetraethoxytitanium, then add 3 ml of ethyl acetate, 3 ml of butanol, 1 ml of ethanol, and 50% of 20 ml of dichloromethane mixed solution, keep constant temperature for 1 hour, gradually increase the temperature to 10 ° C, then add the remaining mixed solution, keep constant temperature for 1 hour, gradually increase the temperature to 85 ° C, and keep constant temperature for 1 hour. Add 1 ml of dimethyl phenyl ether and continue to keep constant temperature for 1 hour. Stop stirring, let stand, and wash twice with inert diluent xylene. Add 60 ml of hexane to the reactor, cool to -10 ° C, slowly add 15 ml of 0.9 M triisobutylaluminum heptane solution, react for 1 hour, and heat to 50 ° C to react for 1 hour. Stop stirring, let it stand, the suspension will quickly separate into layers, remove the upper clear liquid, wash it with inert diluent xylene and organic solvent hexane for several times, and then dry it to obtain a solid catalyst component with good fluidity.

[0130] (2) Preparation of polymer

[0131] Same as Example 1, except that the organoaluminum compound D is triisobutylaluminum. The polymerization results are shown in Table 1.

[0132] Example 9

[0133] (1) Preparation of catalyst components

[0134] Add 4.8g of magnesium chloride, 120ml of toluene, 5.0ml of epichlorohydrin, and 18ml of tri-n-butyl phosphate into the reactor and react for 4 hours at 50°C. Then add 3g of phthalic anhydride and continue to react for 1 hour. Cool the system to -30°C, slowly drop 70ml of titanium tetrachloride, then add 3ml of ethyl acetate, 2ml of butanol, 1ml of isooctyl alcohol, and 50% of 20ml of dichlorobenzene mixed solution, keep constant temperature for 1 hour, gradually increase the temperature to 10°C, then add the remaining mixed solution, keep constant temperature for 1 hour, gradually increase the temperature to 85°C, and keep constant temperature for 1 hour. Add 2ml of 1-ethoxy-3-methoxy-propane and 1ml of dimethyl ether, and continue to keep constant temperature for 2 hours. Stop stirring, let stand, and wash twice with inert diluent toluene. Add 80 ml of hexane to the reactor, cool it to -10°C, slowly add 20 ml of 0.9M diethylaluminum monochloride heptane solution, react for 1 hour, heat it to 50°C and react for 2 hours. Stop stirring, let it stand, the suspension will quickly separate, remove the supernatant, wash it with inert diluent toluene and organic solvent hexane several times, and then dry it to obtain a solid catalyst component with good fluidity.

[0135] (2) Preparation of polymer

[0136] Same as Example 1, the polymerization results are shown in Table 1.

[0137] Example 10

[0138] (1) Preparation of catalyst components

[0139] 4.8 g of magnesium chloride, 150 ml of toluene, 6.0 ml of epichlorohydrin, and 18 ml of tri-n-butyl phosphate were added to the reactor and reacted for 3 hours at 60 ° C. Then 4 g of phthalic anhydride was added and the reaction continued for 2 hours. The system was cooled to -30 ° C, 70 ml of titanium tetrachloride was slowly added dropwise, followed by 3 ml of ethyl acetate, 2 ml of butanol, 1 ml of isooctyl alcohol, and 50% of 20 ml of a mixed solution of dichlorobenzene. The mixture was kept at a constant temperature for 1 hour, and the temperature was gradually raised to 10 ° C. Then the remaining mixed solution was added, the temperature was kept at a constant temperature for 1 hour, and the temperature was gradually raised to 85 ° C, and the temperature was kept at a constant temperature for 1 hour. 2 ml of 1-ethoxy-3-methoxy-propane and 1 ml of dimethyl ether were added, and the temperature was continued for 2 hours. Stop stirring, let it stand, and wash twice with an inert diluent of toluene. Add 80 ml of hexane to the reactor, cool it to -10°C, slowly add 20 ml of 0.9M sesquiethylaluminum heptane solution, react for 1 hour, heat it to 50°C and react for 2 hours. Stop stirring, let it stand, the suspension will quickly separate, remove the supernatant, wash it with inert diluent toluene and organic solvent hexane several times, and then dry it to obtain a solid catalyst component with good fluidity.

[0140] (2) Preparation of polymer

[0141] Same as Example 1, the polymerization results are shown in Table 1.

[0142] Embodiment 11

[0143] (1) Preparation of catalyst components

[0144] Add 4.8g of magnesium chloride, 120ml of toluene, 6.0ml of epichlorohydrin, and 18ml of tri-n-butyl phosphate into the reactor and react for 3 hours at 60°C. Then add 3g of phthalic anhydride and continue to react for 2 hours. Cool the system to -20°C, slowly drop 70ml of titanium tetrachloride, then add 5ml of ethyl acetate, 2ml of ethanol, 1ml of isooctyl alcohol, and 30ml of 40% of a mixed solution of dichlorobenzene, keep the temperature constant for 1 hour, gradually increase the temperature to 10°C, then add the remaining mixed solution, keep the temperature constant for 1 hour, gradually increase the temperature to 85°C, and keep the temperature constant for 1 hour. Add 2ml of 2,2-dimethyl-1,3-dimethoxy-propane and 1ml of o-phenylenedimethyl ether, and continue to keep the temperature constant for 2 hours. Stop stirring, let stand, and wash twice with an inert diluent of toluene. Add 80 ml of hexane to the reactor, cool it to -10°C, slowly add 20 ml of 0.9M diethylaluminum chloride heptane solution, react for 2 hours, heat it to 50°C and react for 2 hours. Stop stirring, let it stand, the suspension will quickly separate, remove the supernatant, wash it with inert diluent toluene and organic solvent hexane several times, and then dry it to obtain a solid catalyst component with good fluidity.

[0145] (2) Preparation of polymer

[0146] Same as Example 1, the polymerization results are shown in Table 1.

[0147] Example 12

[0148] (1) Preparation of catalyst components

[0149] Add 4.8g of magnesium chloride, 150ml of toluene, 4.0ml of epichlorohydrin, and 15ml of tri-n-butyl phosphate into the reactor and react for 2 hours at 60°C. Then add 5g of phthalic anhydride and continue to react for 2 hours. Cool the system to -20°C, slowly drop 90ml of titanium tetrachloride, then add 5ml of ethyl acetate, 2ml of ethanol, 1ml of propanol, and 40% of 20ml of dichlorobenzene mixed solution, keep constant temperature for 1 hour, gradually increase the temperature to 10°C, then add the remaining mixed solution, keep constant temperature for 1 hour, gradually increase the temperature to 85°C, and keep constant temperature for 1 hour. Add 2ml of 1-ethoxy-3-methoxy-propane and 1ml of diethyl ether, and continue to keep constant temperature for 2 hours. Stop stirring, let stand, and wash twice with inert diluent toluene. Add 80 ml of hexane to the reactor, cool it to -10°C, slowly add 20 ml of 0.9M diethylaluminum chloride heptane solution, react for 2 hours, heat it to 50°C and react for 2 hours. Stop stirring, let it stand, the suspension will quickly separate, remove the supernatant, wash it with inert diluent toluene and organic solvent hexane several times, and then dry it to obtain a solid catalyst component with good fluidity.

[0150] (2) Preparation of polymer

[0151] Same as Example 1, the polymerization results are shown in Table 1.

[0152] Comparative Example 1

[0153] (1) Preparation of catalyst components

[0154] Add 4.0 g of magnesium chloride, 60 ml of toluene, 3.0 ml of epichlorohydrin, and 9 ml of tri-n-butyl phosphate to the reactor and react for 2 hours at 70 ° C. Then add 2 g of phthalic anhydride and continue to react for 1 hour. Cool the system to -20 ° C, slowly add 70 ml of titanium tetrachloride, then add 3 ml of ethyl acetate and 3 ml of ethanol in turn, keep the temperature constant for 1 hour, gradually increase the temperature to 85 ° C, and keep the temperature constant for 1 hour. Add 1 ml of 2,2-dimethyl-1,3-diethoxy-propane and continue to keep the temperature constant for 1 hour. Stop stirring, let it stand, and wash twice with inert diluent toluene. Add 60 ml of hexane to the reactor, cool to 0 ° C, slowly add 10 ml of 0.9M monochlorodiethylaluminum heptane solution, react for 0.5 hours, and heat to 50 ° C for 1 hour. Stop stirring, let it stand, the suspension will quickly separate into layers, remove the upper clear liquid, wash it with inert diluent toluene and organic solvent hexane for many times, and then dry it to obtain a solid catalyst component with good fluidity.

[0155] (2) Preparation of polymer

[0156] Same as Example 1, the polymerization results are shown in Table 1.

[0157] Comparative Example 2

[0158] (1) Preparation of catalyst components

[0159] Add 4.0 g of magnesium chloride, 60 ml of toluene, 3.0 ml of epichlorohydrin, and 9 ml of tri-n-butyl phosphate to the reactor and react for 2 hours at a temperature of 70 ° C. Then add 2 g of phthalic anhydride and continue to react for 1 hour. Cool the system to -20 ° C, slowly add 70 ml of titanium tetrachloride, then add 3 ml of ethyl acetate, 3 ml of ethanol, and 20 ml of monochlorobenzene in sequence, keep the temperature constant for 1 hour, gradually increase the temperature to 85 ° C, and keep the temperature constant for 1 hour. Add 1 ml of 2,2-dimethyl-1,3-diethoxy-propane and continue to keep the temperature constant for 1 hour. Stop stirring, let it stand, and wash twice with inert diluent toluene. Add 60 ml of hexane to the reactor, cool to 0 ° C, slowly add 10 ml of 0.9M monochlorodiethylaluminum heptane solution, react for 0.5 hours, and heat to 50 ° C for 1 hour. Stop stirring, let it stand, the suspension will quickly separate into layers, remove the upper clear liquid, wash it with inert diluent toluene and organic solvent hexane for many times, and then dry it to obtain a solid catalyst component with good fluidity.

[0160] (2) Preparation of polymer

[0161] Same as Example 1, the polymerization results are shown in Table 1.

[0162] Comparative Example 3

[0163] (1) Preparation of catalyst components

[0164] Add 4.0 g of magnesium chloride, 60 ml of toluene, 3.0 ml of epichlorohydrin, and 9 ml of tri-n-butyl phosphate to the reactor and react for 2 hours at a temperature of 70 ° C. Then add 2 g of phthalic anhydride and continue to react for 1 hour. Cool the system to -20 ° C, slowly add 70 ml of titanium tetrachloride, then add 1 ml of ethyl acetate and 1 ml of ethanol in sequence, keep the temperature constant for 1 hour, gradually increase the temperature to 10 ° C, then add 2 ml of ethyl acetate and 2 ml of ethanol in sequence, keep the temperature constant for 1 hour, gradually increase the temperature to 85 ° C, and keep the temperature constant for 1 hour. Add 1 ml of 2,2-dimethyl-1,3-diethoxy-propane and continue to keep the temperature constant for 1 hour. Stop stirring, let it stand, and wash twice with inert diluent toluene. Add 60 ml of hexane to the reactor, cool to 0 ° C, slowly add 10 ml of 0.9M monochlorodiethylaluminum heptane solution, react for 0.5 hours, and heat to 50 ° C for 1 hour. Stop stirring, let it stand, the suspension will quickly separate into layers, remove the upper clear liquid, wash it with inert diluent toluene and organic solvent hexane for many times, and then dry it to obtain a solid catalyst component with good fluidity.

[0165] (2) Preparation of polymer

[0166] Same as Example 1, the polymerization results are shown in Table 1.

[0167] Comparative Example 4

[0168] (1) Preparation of catalyst

[0169] 4.0 g of magnesium chloride, 60 ml of toluene, 3.0 ml of epichlorohydrin, and 9 ml of tri-n-butyl phosphate were added to the reactor and reacted for 2 hours at a temperature of 70 ° C. Then 2 g of phthalic anhydride was added and the reaction continued for 1 hour. The system was cooled to -20 ° C, 70 ml of titanium tetrachloride was slowly added dropwise, followed by 3 ml of ethyl acetate, 3 ml of ethanol, and 20 ml of monochlorobenzene. The temperature was kept constant for 1 hour, and the temperature was gradually increased to 85 ° C and kept constant for 1 hour. 1 ml of 2,2-dimethyl-1,3-diethoxy-propane was added and the temperature was kept constant for 1 hour. Stop stirring, let it stand, the suspension quickly separated, the upper clear liquid was removed, and it was washed with an inert diluent of toluene and an organic solvent of hexane for several times and then dried to obtain a solid catalyst component with good fluidity.

[0170] (2) Preparation of polymer

[0171] Same as Example 1, the polymerization results are shown in Table 1.

[0172] The polymerization results of Examples 1 to 12 and Comparative Examples 1 to 4 were analyzed, and the specific analysis data are shown in Table 1.

[0173] Table 1

[0174]

[0175] It can be seen from Table 1 that compared with the catalysts prepared in Comparative Examples 1 to 4, when the catalysts prepared in Examples 1 to 12 are used for polymerization, the particle size distribution of the obtained polymer is more concentrated, the particle size distribution of the special / ultra-high molecular weight polyethylene is between 75-500 μm, the mass fraction is ≥99%, the powder particle span is ≤0.8, the branching degree of the polymer is ≤0.5 SCB / 1000C, the sphericity of the polymer is significantly increased, and it has good low entanglement performance.

Claims

1. A catalyst component for olefin polymerization, comprising a reaction product of raw materials including the following components: a magnesium complex, a precipitation aid, a titanium-containing compound, an acetate compound, an organic alcohol compound, an organic aluminum compound N and an electron donor compound; wherein the electron donor compound comprises an electron donor compound a and / or an electron donor compound b; The general formula of the electron donor compound a is as follows: The R1 and R2 are independently methyl or ethyl, and the R3 and R4 are independently hydrogen or methyl; and / or, The general formula of the electron donor compound b is as follows: R5 and R6 are independently methyl or ethyl; R7, R8, R9, R 10 The same or different, independently selected from hydrogen, halogen, C1~C 10 Straight chain alkyl, C1~C 10 Branched alkyl, C1~C 10 A type of alkoxy group.

2. The catalyst component for olefin polymerization according to claim 1, characterized in that The components are calculated per mole of magnesium in the magnesium complex: And the molar amounts of electron donor a and electron donor b are not 0 at the same time.

3. The catalyst component for olefin polymerization according to claim 1, characterized in that The magnesium complex is a product obtained by dissolving a magnesium halide compound in a solvent system including an organic epoxy compound and an organic phosphorus compound; Calculated per mole of magnesium, The organic epoxide added is 0.01 to 1 mole, preferably 0.03 to 0.5 mole; The organic phosphide added is 0.01 to 1 mole, preferably 0.01 to 0.3 mole.

4. The catalyst component for olefin polymerization according to claim 3, characterized in that The magnesium halide compound is one or a combination of magnesium halide, a complex of magnesium halide and water, alcohol or electron donor Y, phenoxymagnesium chloride, isopropoxymagnesium chloride, and butoxymagnesium chloride; preferably, The magnesium halide is one or a combination of magnesium dichloride, magnesium dibromide, magnesium difluoride and magnesium diiodide; and / or, The complex of magnesium halide and alcohol or electron donor Y is a complex of magnesium halide and methanol, ethanol, propanol, butanol, pentanol, hexanol, isooctyl alcohol, ammonia compounds, hydroxylamine compounds, ether compounds, and ester compounds.

5. The catalyst component for olefin polymerization according to claim 3, characterized in that The organic epoxy compound contains C2~C 18 One or a combination of aliphatic olefins, dienes, halogenated aliphatic olefins, oxides, glycidyl ethers, and internal ethers of halogenated dienes; Preferably, the organic epoxy compound is one or a combination of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, and butyl glycidyl ether.

6. The catalyst component for olefin polymerization according to claim 3, characterized in that The organic phosphorus compound is one or a combination of a hydrocarbon ester of orthophosphoric acid or phosphorous acid, or a halogenated hydrocarbon ester of orthophosphoric acid or phosphorous acid; Preferably, the organophosphorus compound is one or a combination of 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, tri-n-octyl phosphate, triisooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, tri-tert-butyl phosphite, tri-n-pentyl phosphite, triisopentyl phosphite, tri-n-hexyl phosphite, triisohexyl phosphite, tri-n-heptyl phosphite, triisoheptyl phosphite, tri-n-octyl phosphite, triisooctyl phosphite, triphenyl phosphite, and di-n-butyl phosphite.

7. The catalyst component for olefin polymerization according to claim 1, characterized in that The precipitation aid is one or a combination of organic acid, organic acid anhydride, organic ether and organic ketone; Preferably, the precipitation aid is a C2-C 20 One or a combination of organic acids, organic anhydrides, organic ethers, and organic ketones; More preferably, the precipitation aid is one or a combination of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether, and pentyl ether.

8. The catalyst component for olefin polymerization according to claim 1, characterized in that The general formula of the titanium-containing compound is Ti(OR 4 ) e X 1 f ; The R 4 Contains C1~C 10 Aliphatic hydrocarbon or C6~C 14 Aromatic hydrocarbon groups; The X 1 is a halogen; preferably one of fluorine, chlorine, bromine and iodine; The e is an integer of 0 to 2, the f is an integer of 1 to 4, and e+f=3 or 4.

9. The catalyst component for olefin polymerization according to claim 8, characterized in that The titanium-containing compound is one or a combination of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium trichloride, tetraethoxytitanium, triethoxytitanium monochloride, diethoxytitanium dichloride and triethoxytitanium trichloride.

10. The catalyst component for olefin polymerization according to claim 1, characterized in that The general formula of the acetate compound is CH3COOR 3 , the R 3 Contains C1~C 10 Alkyl, C2~C 10 Alkenyl, C3~C 10 Cycloalkyl, C2~C 10 Alkynyl, C6~C 10 A kind of aromatic hydrocarbon group; Preferably, R 3 It is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-octyl, cyclopropyl, methylcyclopropyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl and xylyl.

11. The catalyst component for olefin polymerization according to claim 1, characterized in that The general formula of the organic alcohol compound is R 5 OH, the R 5 Contains C1~C 10 The alkyl group; Preferably, the R 5 It is one of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl and isooctyl.

12. The catalyst component for olefin polymerization according to claim 1, characterized in that In the electron donor compound b, R7, R8, R9, R 10 is one of fluorine, chlorine, bromine, iodine, a C1-C6 straight-chain alkyl group, a C1-C6 branched-chain alkyl group, and a C1-C6 alkoxy group; Preferably, the electron donor compound b is one of o-phenylenedimethyl ether, o-phenylenediethyl ether, and 1-ethoxy-2-methoxybenzene.

13. The catalyst component for olefin polymerization according to claim 1, characterized in that When the electron donor compound is a mixture of electron donor compound a and electron donor compound b, the molar ratio of the electron donor compound a to the electron donor compound b is 0.01-100; preferably 0.05-20; more preferably 0.1-20.

14. The catalyst component for olefin polymerization according to claim 1, characterized in that The general formula of the organoaluminum compound N is AlR 6 n X 2 3-n ; wherein said R 6 is hydrogen, contains C1~C 20 One or a combination of hydrocarbon groups; the X 2 is a halogen; said n is an integer of 0≤n≤3; preferably, The organoaluminum compound N is one or a combination of triethylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, sesquiethylaluminum, isobutylaluminum dichloride, triisobutylaluminum, diisopropylaluminum monochloride, methyl-n-propylaluminum monochloride, and diphenylaluminum monochloride.

15. The method for preparing a catalyst component for olefin polymerization according to any one of claims 1 to 14, characterized in that: The method comprises the following steps: Step 1, dissolving the magnesium halide compound in the organic epoxy compound, the organic phosphorus compound and the inert diluent A to react to form a solution system containing a magnesium complex; Step 2, adding a precipitation aid to the solution system obtained in step 1 to continue the reaction; Step 3: then lower the temperature of the reaction system in step 2, add the titanium-containing compound and continue the reaction; Step 4: subsequently adding a mixed solution of an inert diluent B containing the acetate compound and the organic alcohol compound to the reaction system of step 3 at one time or in steps to continue the reaction; Step 5, adding the electron donor compound to the reaction system of step 4 to continue the reaction; Step 6: Wash the mixture obtained in step 5 with an inert diluent A, and then add the organoaluminum compound N to continue the reaction to obtain the catalyst component.

16. The method for preparing a catalyst component for olefin polymerization according to claim 15, characterized in that: In the step 1, the reaction conditions for preparing the magnesium-containing complex are: temperature of 40 to 80° C., preferably 50 to 70° C.; time of 1 to 5 hours, preferably 1 to 3 hours; and / or, In the step 2, the reaction conditions for adding the precipitation aid are: temperature of 40 to 80° C., preferably 50 to 70° C.; time of 0.5 to 3 h; and / or, In step 3, the reaction conditions for adding the titanium-containing compound are: temperature of -60 to -30°C; time of 0.5 to 3 hours; and / or, In step 5, the reaction conditions for adding the electron donor are: temperature of 70 to 95° C., preferably 80 to 90° C.; time of 0.5 to 3 h; preferably 1 to 2 h; and / or, In step 6, the reaction conditions for adding the organoaluminum compound N are: temperature of -10 to 100°C, preferably 0 to 20°C; time of 0.5 to 3 hours; preferably 1 to 2 hours; and / or, In step 6, after the reaction of the organoaluminum compound N is completed, the reaction system is allowed to stand, unreacted substances and solvent are removed, and a solid catalyst component is obtained.

17. The method for preparing a catalyst component for olefin polymerization according to claim 15, characterized in that: In the step 4, the mixed solution of the acetate compound and the organic alcohol compound in an inert diluent B is added in whole or in batches to the reaction system in the step 3; The reaction conditions for all the additions are: temperature of -60 to 30°C, preferably -20 to 20°C; time of 0.5 to 3h, preferably 1 to 2h; The reaction conditions for the batch addition are: the inert diluent mixed solution of the acetate compound and the organic alcohol compound is added in at least two batches; preferably: After the first batch is added, the reaction is carried out at a constant temperature for 0.5 to 1 hour, and then the temperature is gradually raised to 0 to 30°C, and then the remaining mixed solution is added, and the reaction is continued at a constant temperature for 0.5 to 1 hour, and then the temperature is gradually raised to 60 to 100°C, and the reaction is continued at a constant temperature for 1 to 3 hours; the heating rate of the system is preferably 0.2 to 2°C / min.

18. The catalyst component for olefin polymerization according to claim 15, characterized in that Calculated per mole of magnesium, In the step 1, the amount of the inert diluent A is 0.01 to 5 moles, preferably 0.4 to 2 moles; In the step 4, the amount of the inert diluent B is 0.001 to 2 moles, preferably 0.05 to 0.5 moles.

19. The catalyst component for olefin polymerization according to claim 15, wherein the inert diluent A is one or a combination of aromatic hydrocarbon compounds and alkane compounds; preferably, the aromatic hydrocarbon compounds are one or a combination of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and its derivatives; and / or, The alkane compounds include C3~C 20 At least one of a straight-chain alkane, a branched-chain alkane or a cycloalkane having 10 carbon atoms.

20. The catalyst component for olefin polymerization according to claim 15, wherein the inert diluent B is one or a combination of halogenated aromatic hydrocarbon compounds and halogenated alkane compounds; preferably, the halogenated aromatic hydrocarbon compounds are aromatic hydrocarbons containing C6 - C8 and their derivatives; more preferably monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and its derivatives, monobromobenzene, dibromobenzene, tribromobenzene, monobromotoluene and its derivatives; and / or, The halogenated alkane compound contains C3~C 20 One or a combination of straight-chain halogenated alkanes, branched halogenated alkanes, and halogenated cycloalkanes; more preferably one or a combination of dichloromethane, chloroform, tetrachloromethane, ethyl bromide, and ethyl chloride.

21. A catalyst for olefin polymerization, characterized in that: The catalyst comprises: Component 1, the catalyst component for olefin polymerization according to any one of claims 1 - 14 or the catalyst component prepared by the method according to any one of claims 15 - 20; Component 2, an organoaluminum compound D; Wherein, the general formula of the organoaluminum compound D is AlR 7 d X 3 3-d ; The R 7 is hydrogen, contains C1~C 20 One or a combination of hydrocarbon groups; The X 3 is a halogen; preferably one of fluorine, chlorine and bromine; d is an integer where 0 < d ≤ 3.

22. The catalyst for olefin polymerization according to claim 21, characterized in that The molar ratio of titanium atoms in Component 1 to aluminum atoms in Component 2 is 0.1:1 to 20:1; preferably 0.5:1 to 10:1; more preferably 0.5:1 to 5:

1.

23. The catalyst for olefin polymerization according to claim 21, wherein the organoaluminum compound D is one or a combination of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum, diisobutylaluminum, monochlorodiethylaluminum, sesquialuminum ethoxide, dichloroethylaluminum.

24. Use of the catalyst for olefin polymerization according to any one of claims 21 to 23, characterized in that: The catalyst is used for olefin polymerization reaction; Preferably, the catalyst is used for the preparation of special / ultra - high molecular weight polyolefins by olefin polymerization reaction; More preferably, the molecular weight of the special / ultra - high molecular weight polyolefin is greater than 500,000.

25. Use of the catalyst for olefin polymerization according to claim 24, characterized in that: In the olefin polymerization reaction, the general formula of at least one olefin in the raw material olefins is CH2=CHR, where R is hydrogen or an alkyl group with C1 - C6; Preferably, the raw material olefin is a homopolymerization system of ethylene; or, the raw material olefin is a copolymerization system of ethylene and / or α - olefin with other comonomers; more preferably, the comonomers are one or a combination of propylene, butene, pentene, hexene, octene, 4 - methyl - 1 - pentene.

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