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

Abstract

The invention discloses a catalyst component for olefin polymerization, a catalyst as well as a preparation method and application of the catalyst, and relates to the technical field of olefin polymerization catalysts. The catalyst component comprises a reaction product of the following components: a solid catalyst component F, a second alcohol compound, a second organic epoxy compound, a second titanium compound, an electron donor a and / or an electron donor b, and an organic aluminum compound; the molar ratio of the solid catalyst component F to the second alcohol compound to the second organic epoxy compound to the second titanium compound to the electron donor a and / or the electron donor b to the organic aluminum compound is 1: (0.05-20): (0.01-50): (0.5-50): (0.01-100): (0.001-10.0), preferably 1: (0.1-1.0): (0.1-10): (2.0-30.0): (0.02-10): (0.005-2). Under the specific composition, under the synergistic cooperation of all the components, especially by adopting the specific preparation method, the organic aluminum compound is added after two times of titanium loading, the catalyst has high catalyst activity and bulk density, and the obtained polymer has the advantages of controllable molecular weight, narrow distribution Mw / Mn < = 7, sphericity degree SPHT > = 0.75, and swelling time < = 40 min.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of olefin polymerization catalysts, and further relates to a catalyst component for olefin polymerization, a catalyst, and a preparation method and application thereof. BACKGROUND

[0002] Ultra high molecular weight polyethylene (UHMWPE) is a special polyethylene variety with a molecular weight greater than 1.5 million. Most of the commercial UHMWPE is currently prepared by Ziegler-Natta catalyst (Z-N catalyst), which has unparalleled wear resistance, impact resistance, self-lubrication, corrosion resistance, low temperature resistance, hygiene, non-toxicity, non-adhesion, non-water absorption, small density, and other comprehensive properties compared with ordinary polyethylene and other engineering plastics. Very high molecular weight polyethylene (VHMWPE) refers to polyethylene with a molecular weight between 300,000 and 1.5 million. The product has excellent mechanical properties, high impact strength, and good wear resistance. Compared with UHMWPE, VHMWPE has better processing performance and can be used in application fields with better performance and lower cost than ordinary polyethylene. Its downstream applications usually include pressed plates, extruded profiles, pipes, battery separators, sintered filter materials, and modified extruded UHMWPE granules. VHMWPE is mainly used for pipe and modified injection molding applications in extrusion molding processing. A new use of VHMWPE is for wet lithium-ion battery separators, especially those produced by the wet biaxial stretching method, which have high longitudinal and transverse strength due to biaxial stretching.

[0003] Due to the difficulty in processing UHMWPE, its large-scale application is hindered. Two key requirements for high-end products are: 1. Suitable molecular weight and narrow molecular weight distribution according to the application. 2. Low hexane extractable content and ash content. When used in lithium battery separators or artificial joints, it must have low ash content to improve the anti-breakdown capacity of the product or reduce the impact on the human body. 3. Good swelling performance. When producing lithium battery separators using a wet process, the base material needs to be swelled before film formation. Good swelling performance can reduce the requirements on equipment, shorten the processing time, and help to increase the tensile strength of the separator and optimize the extrusion processing performance of the separator. Most of the widely used high-end special / ultra high molecular weight polyethylene products are from abroad. With the continuous advancement of the aging process in China, the increasing demand for health and the improvement of payment ability, as well as the development of the lithium-ion battery industry, domestic special / ultra high molecular weight polyethylene powder manufacturers still have room for improvement.

[0004] The present inventors have found that when the polymer particles are uniform, the content of hexane extractables is low and the sphericity is high, the processing of the ultra-high molecular weight polyethylene by using the plunger extrusion, the mold pressing, the dry / wet method bidirectional stretching method is easier and the quality is higher. Especially in the production of lithium battery diaphragm by using the wet process, the polymer is uniformly swollen, the balance time is short, the solvent exudation amount is low, the production efficiency and the product quality of the diaphragm can be effectively improved. Therefore, it is necessary to provide a catalyst for producing the ultra-high molecular weight polyethylene with appropriate particle size, uniform distribution, narrow molecular weight distribution, good swelling performance and high sphericity. SUMMARY

[0005] In order to solve the problems in the prior art, the present application provides a catalyst component for olefin polymerization, a catalyst and a preparation method and application thereof. After the electron donor a and the electron donor b are introduced into the Z-N catalyst, the active center for generating the low molecular weight PE component can be reduced, thereby improving the molecular weight of the polymerization product, and the addition amount can be adjusted to control the molecular weight of the polymer. The present inventors have found that by using the specific method in the present application to prepare the spherical or spherical-like fixed catalyst intermediate, and by using the specific method in the present application to treat the fixed catalyst intermediate, and by using the step of treating the fixed catalyst intermediate with the organic aluminum compound, the swelling performance of the catalyst can be unexpectedly and significantly improved, the catalyst has high activity, and the obtained polymer has high bulk density, narrow particle size distribution, narrow molecular weight distribution and controllable number average molecular weight.

[0006] One of the objects of the present application is to provide a catalyst component for olefin polymerization.

[0007] The catalyst component for olefin polymerization according to the present application comprises the reaction product of the following components:

[0008] The solid catalyst component F, the second alcohol compound, the second organic epoxy compound, the second titanium compound, the electron donor a and / or the electron donor b, and the organic aluminum compound;

[0009] The molar ratio of the solid catalyst component F, the second alcohol compound, the second organic epoxy compound, the second titanium compound, the electron donor a and / or the electron donor b, and the organic aluminum compound is 1:(0.05-20):(0.01-50):(0.5-50):(0.01-100):(0.001-10.0), preferably 1:(0.1-1.0):(0.1-10):(2.0-30.0):(0.02-10):(0.005-2).

[0010] The addition of the organoaluminum compound helps to improve the catalytic activity, so that the polymer prepared by the catalyst component of the application has a narrow particle size distribution, a high molecular weight, and excellent swelling performance, which helps to process the subsequent ultra-high molecular weight polyethylene product.

[0011] The inventors of the present application have found that, by preparing the solid catalyst component F in the specific method of the present application, and then treating the solid catalyst component F by the etching method described above, the polymerization activity of the catalyst corresponding to the catalyst component can be unexpectedly and significantly improved, and the powder particles with high bulk density can be obtained by polymerization. Under preferred conditions, the catalyst can also polymerize to obtain polyethylene powder with high bulk density, good sphericity, narrow particle size distribution, and good swelling performance.

[0012] In a preferred embodiment of the present application, the solid catalyst component F is prepared by the following method:

[0013] After the first reaction of the magnesium complex with the organic acid anhydride compound, the second reaction of the magnesium complex with the first titanium compound, the first alcohol compound, and the acetate compound is carried out to obtain the solid catalyst component F;

[0014] The molar ratio of the magnesium complex, the organic acid anhydride compound, the first titanium compound, the first alcohol compound, and the acetate compound is 1:(0.01-10):(5-1000):(0.01-20):(0.01-10), preferably 1:(0.01-1):(10-200):(0.1-5):(0.02-2), and more preferably the molar ratio of the magnesium complex to the first titanium compound is 1:(5-50).

[0015] The solid catalyst component F is prepared by further reacting the magnesium complex with the organic acid anhydride compound, the first titanium compound, the first alcohol compound, and the acetate compound, which can convert the magnesium complex in a dissolved state without catalytic function into a solid with catalytic function.

[0016] In a more preferred embodiment of the present application, the solid catalyst component F is prepared by the following method:

[0017] (a) dissolving the magnesium halide in a solvent system containing the first organic epoxy compound and the organic phosphorus compound to obtain a magnesium complex;

[0018] (b) reacting the magnesium complex with the organic acid anhydride compound to obtain a reaction mixture;

[0019] (c) contacting the reaction mixture obtained in step (b) with the first titanium compound to obtain a reaction mixture;

[0020] (d) reacting the reaction mixture in step (c) with the first alcohol compound to obtain the solid catalyst component F; wherein the acetic acid ester compound is added in one or more of the optional step (a), step (b), step (c), step (d). In this preferred embodiment, the reaction product containing the solid catalyst component F obtained in this preferred way (i.e. the catalyst component in the present application) corresponds to a catalyst with higher polymerization activity, which can be used to polymerize polyethylene powder with high bulk density, good sphericity, narrow particle size distribution and good swelling performance.

[0021] In the above technical solution, "adding the acetic acid ester compound in one or more of the optional step (a), step (b), step (c), step (d)" means that the acetic acid ester compound can be added in one of the steps (a), (b), (c), (d), or can be added in two, three or four of the above four steps, all of which can achieve the present application.

[0022] In a further more preferred embodiment of the present application, the solid catalyst component F is prepared by the following method: dissolving the magnesium halide in a solvent system containing the first organic epoxy compound and the organic phosphorus compound to obtain a magnesium complex; reacting the magnesium complex with the organic acid anhydride compound, then contacting the reaction mixture with the first titanium compound, and then reacting with the acetic acid ester compound and the first alcohol compound to obtain a spherical or spherical-like solid catalyst component F. When the organic acid anhydride compound, the acetic acid ester compound, the alcohol electron donor, the electron donor a and / or the electron donor b are introduced into the N series polyolefin catalyst preparation system as a complex electron donor according to the more preferred specific method steps of the present application, and in particular when the specific preparation method of the present application is used, unexpectedly, the reaction product containing the solid catalyst component F obtained in this more preferred way (i.e. the catalyst component in the present application) corresponds to a catalyst with higher polymerization activity, which can be used to polymerize polyethylene powder with high bulk density, good sphericity, narrow particle size distribution and good swelling performance.

[0023] In a preferred embodiment of the present application:

[0024] The reaction temperature of the first reaction is 50-70℃, and / or the reaction time is 0.5-2 hours; and / or,

[0025] The temperature of the system after the first reaction is reduced to -60℃ to 20℃, and then contacted with the first titanium compound, the first alcohol compound and the acetic acid ester compound; and / or,

[0026] The reaction temperature of the second reaction is 75-100°C, and / or the temperature increasing rate is 0.2-2°C / min, and / or the reaction time is 1-4h.

[0027] In a preferred embodiment of the present application, the magnesium complex is prepared by the following method:

[0028] The magnesium complex is prepared by dissolving magnesium halide in a solvent system containing a first organic epoxy compound, an organic phosphorus compound, optionally an acetate compound, and optionally an inert diluent;

[0029] When the acetate compound and the inert diluent are contained, the molar ratio of the magnesium halide, the first organic epoxy compound, the organic phosphorus compound, the acetate compound, and the inert diluent is 1:(0.2-10):(0.1-10):(0.01-1):(5-50), preferably 1:(0.5-2):(0.5-2):(0.05-0.20):(10-30).

[0030] In a preferred embodiment of the present application, the amount of the first organic epoxide compound is 0.2 to 10 moles, for example 0.2, 0.5, 1, 3, 6, 9, 10 moles, and any two values or any range of any two values, per mole of magnesium halide; the amount of the organic phosphorus compound is 0.1 to 10 moles, for example 0.1, 0.5, 1, 3, 6, 9, 10 moles, and any two values or any range of any two values; the amount of the organic acid anhydride compound is 0.01 to 10 moles, for example 0.01, 0.03, 0.05, 0.1, 0.3, 0.6, 0.9, 1, 5, 10 moles, and any two values or any range of any two values; the amount of the first titanium compound is 5 to 1000 moles, for example 5, 10, 50, 100, 200, 400, 600, 800, 1000 moles, and any two values or any range of any two values; the amount of the acetate compound is 0.01 to 10 moles, for example 0.01, 0.1, 1, 5, 10 moles, and any two values or any range of any two values; the amount of the first alcohol compound is 0.01 to 20 moles, for example 0.01, 0.05, 1.0, 2.0, 5, 10, 20 moles, and any two values or any range of any two values; the amount of the second alcohol compound is 0.05 to 20 moles, for example 0.05, 0.1, 0.5, 1, 5, 10, 15, 20 moles, and any two values or any range of any two values; the amount of the second organic epoxide compound is 0.01 to 50 moles, for example 0.01, 0.1, 1, 5, 10, 20, 50 moles, and any two values or any range of any two values; the amount of the second titanium compound is 0.5 to 50 moles, for example 0.5, 1, 5, 10, 20, 50 moles, and any two values or any range of any two values; the amount of the organic aluminum compound is 0.001 to 10 moles, for example 0.001, 0.01, 0.1, 1, 2, 5, 10; and the molar amounts of electron donor a and electron donor b are not both zero, the amount of the electron donor a and / or the electron donor b is 0.01 to 100 moles, for example 0.01, 0.1, 0.5, 1, 5, 10, 20, 50, 100 moles, and any two values or any range of any two values.

[0031] In a more preferred embodiment of the present application, the amount of the first organic epoxy compound is 0.5-2.0 moles, the amount of the organic phosphorus compound is 0.5-2.0 moles, the amount of the organic acid anhydride compound is 0.01-1 mole, the amount of the first titanium compound is 10-200 moles, the amount of the acetic acid ester compound is 0.02-2 moles, the amount of the first alcohol compound is 0.1-5 moles, the amount of the second alcohol compound is 0.1-1.0 moles, the amount of the second organic epoxy compound is 0.1-10 moles, the amount of the second titanium compound is 2.0-30.0 moles, the amount of the organic aluminum compound is 0.005-2.0 moles, and the amount of the electron donor a and / or the electron donor b is 0.02-10 moles, relative to the magnesium halide in terms of moles of magnesium.

[0032] The inventors of the present application have unexpectedly found that, according to the preparation method of the present application, under the more preferred ratio conditions, a solid catalyst component F with better spherical or quasi-spherical particle morphology can be obtained, and by treating the solid catalyst component F according to the method described in the present application, a catalyst corresponding to the solid catalyst component with better performance can be obtained, and more unexpectedly, the catalyst can be used to polymerize to obtain spherical powder particles, and in addition, the obtained spherical powder particles have the characteristics of high bulk density, good sphericity, narrow particle size distribution, and good swelling performance. The more preferred ratio is: the amount of the first organic epoxy compound is 0.5-1.5 moles, the amount of the organic phosphorus compound is 0.5-1.5 moles, the amount of the organic acid anhydride compound is 0.1-0.3 moles, the amount of the first titanium compound is 10-20 moles, the amount of the acetic acid ester compound is 0.05-0.20 moles, the amount of the first alcohol compound is 0.1-1.0 moles, the amount of the second alcohol compound is 0.1-1.0 moles, the amount of the second organic epoxy compound is 0.1-4 moles, the amount of the second titanium compound is 2.0-10.0 moles, the amount of the organic aluminum compound is 0.05-2.0 moles, and the amount of the electron donor a and / or the electron donor b is 0.1-5 moles, relative to the magnesium halide in terms of moles of magnesium.

[0033] In a preferred embodiment of the present application:

[0034] The magnesium halide is a dihalogenated magnesium or a complex formed by the dihalogenated magnesium and at least one of water, alcohol or an electron donor; preferably, the dihalogenated magnesium is at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, magnesium diiodide; and / or, the alcohol is at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, isooctanol; and / or, the electron donor is at least one of ammonia, hydroxylamine, ether, ester; and / or,

[0035] The first and second organic epoxy compounds can be the same or different, and are each independently selected from at least one of oxides of olefin compounds, glycidyl ethers, and internal ethers; preferably, the olefin compounds are at least one of C2-C18 aliphatic olefins, aliphatic diolefins, halogenated aliphatic olefins, halogenated aliphatic diolefins; more preferably, the first and second organic epoxy compounds are each independently selected from at least one of oxymethylenes, oxymethylpropanes, oxymethylbutanes, butadiene oxides, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, butyl glycidyl ether; and / or,

[0036] The organic phosphorus compound is a hydrocarbyl ester or a halogenated hydrocarbyl ester of a phosphoric acid compound; preferably, the phosphoric acid compound is orthophosphoric acid or phosphorous acid; more preferably, the organic phosphorus compound is at least one of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, tri-i-propyl phosphate, tri-n-butyl phosphate, tri-i-butyl phosphate, tri-t-butyl phosphate, tri-n-pentyl phosphate, tri-i-pentyl phosphate, tri-n-hexyl phosphate, tri-i-hexyl phosphate, tri-n-heptyl phosphate, tri-i-heptyl phosphate, tri-n-octyl phosphate, tri-i-octyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, tri-i-propyl phosphite, tri-n-butyl phosphite, tri-i-butyl phosphite, tri-t-butyl phosphite, tri-n-pentyl phosphite, tri-i-pentyl phosphite, tri-n-hexyl phosphite, tri-i-hexyl phosphite, tri-n-heptyl phosphite, tri-i-heptyl phosphite, tri-n-octyl phosphite, tri-i-octyl phosphite, triphenyl phosphite, di-n-butyl phosphite; and / or,

[0037] The dissolution temperature is 50-70℃, and / or the dissolution time is 1-3 hours.

[0038] In a preferred embodiment of the present application:

[0039] The structure of the organic acid anhydride compound is:

[0040]

[0041] wherein R5' and R6' can be the same or different, and are each independently one of hydrogen, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl, C6-C10 aromatic hydrocarbon; preferably, the organic acid anhydride compound is at least one of acetic anhydride, propionic anhydride, butyric anhydride, acrylic anhydride, phthalic anhydride, butenyl anhydride, maleic anhydride; and / or,

[0042] The first and second titanium compounds can be the same or different, and are each independently selected from Ti(OR8) a X bwherein R8 is a C1-C10 aliphatic or aromatic hydrocarbon group, X is a halogen, preferably fluorine, chlorine or bromine, a is 0, 1 or 2, and b is any integer from 1 to 4; preferably, the sum of a and b is 3 or 4; more preferably, the first and second titanium compounds are independently selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraethoxide, titanium chloride triethoxide, titanium trichloride, titanium dichloride diethoxide, titanium trichloride monoethoxide; and / or,

[0043] The first and second alcohol compounds can be the same or different, and are independently a C1-C18 aliphatic or aromatic alcohol; preferably, the first and second alcohol compounds are independently at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, hexanol, cyclohexanol, octanol, isooctanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, isohexylene glycol; more preferably, the first alcohol compound is a C4-C18 aliphatic or aromatic alcohol, preferably at least one of butanol, isobutanol, t-butanol, hexanol, cyclohexanol, octanol, isooctanol, benzyl alcohol, phenethyl alcohol, butylene glycol, hexylene glycol, isohexylene glycol.

[0044] In one preferred embodiment of the present application:

[0045] The acetic ester compound has a structure of CH3COOR7, wherein R7 is a C1-C10 alkyl, C2-C10 alkenyl, C3-C10 cycloalkyl, C2-C10 alkynyl or C6-C10 aromatic hydrocarbon group; preferably, R7 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl or n-hexyl; more preferably, the acetic ester compound is at least one of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, n-octyl acetate.

[0046] In one preferred embodiment of the present application:

[0047] The electron donor a and / or electron donor b is a diether electron donor; preferably,

[0048] The electron donor a has a structure of:

[0049]

[0050] wherein R1 and R2 can be the same or different, and are each independently a methyl group or an ethyl group, and R3 and R4 can be the same or different, and are each independently hydrogen or a methyl group; preferably, the electron donor a is at least one 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; and / or,

[0051] The electron donor b has the following structural formula:

[0052]

[0053] wherein R5 and R6 can be the same or different, and are each independently a methyl group or an ethyl group, and R7, R8, R9 and R 10 may be the same or different, and are each independently hydrogen, halogen, a C1-C10 linear alkyl group, a C1-C10 branched alkyl group or a C1-C10 alkoxy group; preferably, the R7, R8, R9 and R 10 are each independently hydrogen, fluorine, chlorine, bromine, iodine, a C1-C6 linear alkyl group, a C1-C6 branched alkyl group or a C1-C6 alkoxy group; more preferably, the electron donor b is at least one of o-dioxane, o-diethyl ether and 1-ethoxy-2-methoxybenzene; and / or,

[0054] The organic aluminum compound is AlR 6 n X 2 3-n wherein R 6 is hydrogen or a C1-C20 hydrocarbon group, X 2 is halogen, and 0≤n≤3; preferably, the organic aluminum compound is at least one of triethylaluminum, monochlorodiethylaluminum, dichloro-monoethylaluminum, hemiethylaluminum, dichloroisobutylaluminum, triisobutylaluminum, monochlorodiisopropylaluminum, monochloromethyl-n-propylaluminum, monochlorodiethylaluminum, preferably at least one of monochlorodiethylaluminum, dichloro-monoethylaluminum and triethylaluminum.

[0055] The second object of the present application is to provide a preparation method of a catalyst component for olefin polymerization.

[0056] The preparation method of the catalyst component for olefin polymerization comprises:

[0057] After the solid catalyst component F is dispersed in an inert solvent, the second alcohol compound, the second organic epoxide compound and the second titanium compound are subjected to a first contact reaction, and then the electron donor a and / or the electron donor b are subjected to a second contact reaction, and finally the organic aluminum compound is used for treatment to obtain the catalyst component.

[0058] Specifically, the following method can be used:

[0059] (1) Preparation of the solid catalyst component F: a reaction product of a magnesium complex, an organic acid anhydride compound, an acetic acid ester compound, a first alcohol compound, and a first titanium compound; wherein the magnesium complex is a complex formed by dissolving a magnesium halide in a solvent system containing a first organic epoxy compound and an organic phosphorus compound;

[0060] (2) Contacting the spherical or spherical-like solid catalyst component F with a second alcohol compound and a second organic epoxy compound to obtain a reaction mixture;

[0061] (3) Obtaining a solid intermediate from the reaction mixture obtained in step (2) and contacting it with a second titanium compound to obtain a reaction mixture;

[0062] (4) Contacting the reaction mixture obtained in step (3) with an electron donor a and / or an electron donor b, and an organic aluminum compound to obtain the catalyst component.

[0063] In a preferred embodiment of the present application, step (1) above is carried out according to the following method:

[0064] (a) Dissolving a magnesium halide in a solvent system containing a first organic epoxy compound and an organic phosphorus compound to obtain a magnesium complex;

[0065] (b) Reacting the magnesium complex with an organic acid anhydride compound to obtain a reaction mixture;

[0066] (c) Contacting the reaction mixture obtained in step (b) with a first titanium compound to obtain a reaction mixture;

[0067] (d) Reacting the reaction mixture in step (c) with a first alcohol compound to obtain the solid catalyst component F; wherein an acetic acid ester compound is added in one or more of the optional steps (a), (b), (c), and (d).

[0068] In a further more preferred embodiment of the present application, the method for preparing the catalyst component comprises the following steps:

[0069] S1. Dissolving a magnesium halide in a solvent system containing a first organic epoxy compound and an organic phosphorus compound, and forming a homogeneous solution;

[0070] S2. Reacting the solution obtained in step S1 with an organic acid anhydride compound, then contacting it with a first titanium compound, and then contacting it with an acetic acid ester compound and a first alcohol compound, and then raising the temperature to precipitate solid particles;

[0071] S3, removing unreacted substances and solvent from the mixture obtained in step S2, washing to obtain the spherical or spherical-like solid catalyst component F;

[0072] S4, dispersing the spherical or spherical-like solid catalyst component F in an inert solvent and forming a suspension;

[0073] S5, contacting the suspension obtained in S4 with a second alcohol compound, a second organic epoxide compound, and a second titanium compound and reacting;

[0074] S6, contacting the suspension obtained in S5 with an electron donor a and / or an electron donor b and reacting;

[0075] S7, washing the reaction mixture obtained in S6 with an inert solvent and treating with an organic aluminum compound;

[0076] S8, removing unreacted substances and solvent from the mixture obtained in step S7, washing to obtain the catalyst component.

[0077] According to the present application, low temperature refers to a temperature range of -60°C to -10°C.

[0078] According to the present application, high temperature refers to a temperature range of 60°C or higher, preferably 75°C to 100°C.

[0079] In a preferred embodiment of the present application, in S1, the dissolution temperature is 50-70°C and the time is 1-3 hours.

[0080] In a preferred embodiment of the present application, in S2, the reaction temperature of the solution with the organic acid anhydride compound is the same as or different from the temperature in step S1, preferably 50-70°C, and the reaction time is 0.5-2 hours, after which the temperature of the reaction system is lowered to -60°C to 20°C, and then contacted with the first titanium compound, the acetate compound and the first alcohol compound; then gradually increasing the temperature, preferably at a rate of 0.2-2°C / min, to 75°C-100°C, and then reacting for 1-4h.

[0081] In a preferred embodiment of the present application, in S5, the temperature of the system is first lowered to -60°C to 20°C, and then the second alcohol compound, the second organic epoxide compound, and the second titanium compound are added for reaction, and the reaction time is 0.5-2 hours.

[0082] In a preferred embodiment of the present application, in step S6, the system is first gradually increased in temperature, preferably at a rate of 0.2-2°C / min, to 75°C-100°C, and then reacted for 1-4h, and then the electron donor a and / or the electron donor b are added for contact reaction.

[0083] In a preferred embodiment of the present application, in step S7, the system is first cooled to a temperature of -20 to 20°C, then the organic aluminum compound is added for treatment, and then the system is gradually heated, preferably at a heating rate of 0.2 to 2°C / min, to a temperature of 40 to 80°C, and then reacted for 1 to 4 hours.

[0084] In a preferred embodiment of the present application, the inert diluent is selected from the group consisting of aromatic compounds and / or alkanes, and preferably is at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene, and / or at least one of straight-chain alkanes, branched alkanes, and cyclic alkanes having 3 to 20 carbon atoms, preferably at least one of isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, and kerosene.

[0085] The inert diluent and the inert diluent can be the same or different, and each is independently selected from aromatic compounds and / or alkanes; preferably, the aromatic compound is at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene; and / or, the alkane is at least one of straight-chain alkanes, branched alkanes, and cyclic alkanes having 3 to 20 carbon atoms, preferably at least one of isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, and kerosene; and / or,

[0086] The molar ratio of the solid catalyst component F to the inert diluent is 1:(5-50); preferably 1:(10-30); and / or,

[0087] After the solid catalyst component F is dispersed in the inert diluent, the system is cooled to a temperature of -60 to 20°C, and then contacted with the second alcohol compound, the second organic epoxide compound, and the second titanium compound; and / or,

[0088] The reaction temperature of the first contact reaction is -60 to 20°C, and / or the reaction time is 0.5 to 2 hours; and / or,

[0089] The reaction temperature of the second contact reaction is 75 to 100°C, and / or the heating rate is 0.2 to 2°C / min, and / or the reaction time is 1 to 4 hours; and / or,

[0090] After the second contact reaction, the system is cooled to a temperature of -20 to 20°C, and then contacted with the organic aluminum compound; and / or,

[0091] The treatment temperature is 40 to 80°C, and / or the heating rate is 0.2 to 2°C / min, and / or the treatment time is 1 to 4 hours.

[0092] A third object of the present application is to provide a catalyst for olefin polymerization.

[0093] The catalyst for olefin polymerization of the present application comprises the following components:

[0094] The catalyst component as described in one of the objects of the present application or the catalyst component prepared by the preparation method as described in the second object of the present application, an organic aluminum compound;

[0095] Preferably, the structure of the organic aluminum compound is AlR' d X' 3-d wherein R' is hydrogen or a Cl-C20 hydrocarbon group, X' is a halogen atom, preferably fluorine, chlorine or bromine, 0 < d < 3; and / or,

[0096] The molar ratio of aluminum in the organic aluminum compound to titanium in the catalyst component is (5-500):1, preferably (20-200):1, more preferably (50-100):1, such as 50, 60, 70, 80, 90, 100, and any two values or any interval of any two values to 1, most preferably (60-90):1.

[0097] In a preferred embodiment of the present application, R' is hydrogen or an alkyl group, aralkyl group or aryl group having 1-20 carbon atoms; preferably, the organic aluminum compound is at least one of Al(CH3)3, Al(CH2CH3)3, Al(i-Bu)3, AlH(CH2CH3)2, AlH(i-Bu)2, AlCl(CH2CH3)2, Al2Cl3(CH2CH3)3, AlCl(CH2CH3)2, AlCl2(CH2CH3), preferably at least one of Al(CH2CH3)3, Al(i-Bu)3.

[0098] The fourth object of the present application is to provide a use of the catalyst as described in the third object of the present application in the preparation of polyolefin by polymerization of olefin.

[0099] The fourth object of the present application is to provide a use of the catalyst as described in the third object of the present application in the preparation of polyolefin by polymerization of olefin.

[0100] Preferably,

[0101] The olefin is CH2=CHR, wherein R is hydrogen or a C1-C6 alkyl group; more preferably, the olefin is at least one of ethylene, propylene, butylene; and / or,

[0102] The polyolefin is a very high molecular weight polyolefin or an ultrahigh molecular weight polyolefin, more preferably, the polyolefin is a very high molecular weight polyethylene or an ultrahigh molecular weight polyethylene, further preferably, the very high molecular weight polyethylene or the ultrahigh molecular weight polyethylene has a number average molecular weight greater than 1 million, more preferably, the very high molecular weight polyethylene or the ultrahigh molecular weight polyethylene is a spherical polyethylene powder having a high sphericity; and / or,

[0103] The reaction temperature of the polymerization reaction is 40-100°C, preferably 60-85°C, more preferably 60-70°C, and / or the reaction time is 1-10h, preferably 2-4h, and / or the reaction pressure is 0.3-2Mpa, preferably 0.35-0.6Mpa.

[0104] The catalyst of the present application can be used for homopolymerization of ethylene, and also for copolymerization of ethylene with alpha-olefins, and the comonomer can be propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene.

[0105] The polymerization in the present application can be slurry polymerization, or gas phase polymerization.

[0106] In a preferred embodiment of the present application, the slurry polymerization medium comprises: isobutane, hexane, heptane, cyclohexane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, xylene and other saturated aliphatic hydrocarbons or aromatic hydrocarbons and other inert solvents.

[0107] In a preferred embodiment of the present application, the activity of the catalyst in ethylene slurry homopolymerization is greater than 20000gPE / g Cat.

[0108] After the catalyst of the present application is subjected to ethylene slurry polymerization / copolymerization, a special / ultra-high molecular weight polyethylene powder with a viscosity average molecular weight greater than 1 million, a narrow polymer molecular weight distribution Mw / Mn≤7, a sphericity SPHT≥0.75 and a swelling time ≤40min can be obtained.

[0109] Compared with the prior art, the present application has the following advantages:

[0110] According to the above technical solution, the catalyst component of the present application comprises the reaction product of the following components: a magnesium complex, an organic acid anhydride compound, an acetic ester compound, an alcohol compound, a titanium-containing compound, an organic aluminum compound, an electron donor a and / or an electron donor b; the magnesium complex is a complex formed by dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organic phosphorus compound. Under the specific composition of the present application, under the synergistic cooperation of each component, especially by using a specific preparation method, by adding an organic aluminum compound after two titanium loadings, the catalyst has high catalyst activity and bulk density, and the obtained polymer has controllable molecular weight, narrow distribution Mw / Mn≤7, sphericity SPHT≥0.75 and swelling time ≤40min. DETAILED DESCRIPTION

[0111] The present application will be described in detail below in conjunction with specific examples. It is necessary to point out here that the following examples are only used to further illustrate the present application and cannot be understood as limiting the protection scope of the present application. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present application still fall within the protection scope of the present application.

[0112] The raw materials used in the examples and comparative examples of the present application are all commercially available products.

[0113] The test methods used in the examples and comparative examples of the present application are as follows:

[0114] 1. Polymer bulk density was measured by ASTM D1895 Plastic apparent density, volume factor and pourability test method.

[0115] 2. Polymer molecular weight and molecular weight distribution was measured by Polymer Laboratories PL-GPC220. Eluent: Trichlorobenzene (0.1% antioxidant by mass). Calibration sample: Polystyrene. Flow rate: 1.0 ml / min. Test temperature: 135°C.

[0116] 3. Sphericity was measured by Camsizer particle size analyzer of Retsch GmbH, Germany.

[0117] 4. Polymerization activity was calculated by the mass of polymer obtained divided by the amount of catalyst added.

[0118] 5. Swelling experiment: A certain amount of white oil was added to a swelling kettle, stirred and heated to 170°C, then a polymer powder with a mass of 1 / 4 of the white oil was added until complete swelling at constant temperature, and the uniformity and white oil seepage were observed after cooling.

[0119] 6. Catalyst particle size distribution (span value) was measured by Malvern laser particle size analyzer.

[0120] The following examples are more detailed descriptions of the present application, but the present application is not limited to these examples.

[0121] Example 1

[0122] (1) Preparation of catalyst component

[0123] Into a reactor, 4.8 g of magnesium chloride, 100 ml of toluene, 5.0 ml of epichlorohydrin, 12 ml of tri-n-butyl phosphate were added, and the mixture was reacted at 65°C for 2 hours. Then, 1.1 g of phthalic anhydride was added, and the mixture was reacted at the same temperature for 1 hour. The mixture was cooled to -30°C, and 70 ml of titanium tetrachloride was added dropwise. Then, 3 ml of ethyl acetate and 6 ml of ethanol were added, and the mixture was gradually heated to 85°C at a rate of 0.5°C / min. The mixture was reacted at the same temperature for 1 hour. The mixture was cooled to 50°C, and washed twice with toluene. Then, 90 ml of toluene was added to dilute the mixture, and the mixture was cooled to -20°C. Then, 2 ml of butanol, 2 ml of epichlorohydrin, and 20 ml of titanium tetrachloride were added in this order dropwise. The mixture was reacted at the same temperature for 30 min, and then gradually heated to 85°C at a rate of 0.4°C / min. The mixture was reacted at the same temperature for 1 hour, and then 1 ml of 2,2-dimethyl-1,3-diethoxypropane was added. The mixture was reacted at the same temperature for 1 hour. The stirring was stopped, and the mixture was allowed to stand. The mixture was washed twice with toluene. Then, 60 ml of hexane was added to the reactor, and the mixture was cooled to 0°C. Then, 10 ml of 0.9 M diethylaluminum chloride solution in heptane was added dropwise. The mixture was reacted at 50°C for 1 hour. The stirring was stopped, and the mixture was allowed to stand. The upper layer was removed, and the mixture was washed with toluene and hexane. The solid catalyst component was obtained.

[0124] (2) Polymerization reaction

[0125] A 2 L stainless steel reactor was sufficiently substituted with high-purity nitrogen, and then 1 L of hexane and 1.0 ml of 1 M triethylaluminum were added. Then, the solid catalyst component prepared in the above-mentioned method (0.6 mg of titanium) was added, and the mixture was heated to 60°C. Then, the total pressure in the reactor was adjusted to 0.35 MPa (gauge pressure) by introducing ethylene. The mixture was polymerized at 70°C for 2 hours. The polymerization results are shown in Table 1.

[0126] Example 2

[0127] (1) Preparation of catalyst component

[0128] To a reaction vessel was added 4.8 g of magnesium dibromide, 100 ml of toluene, 5.0 ml of glycidyl methacrylate, 12 ml of tri-n-butyl phosphate, and the mixture was heated to 65°C and stirred for 2 hours. Then, 1.1 g of phthalic anhydride was added and the mixture was heated at 65°C for 1 hour. The mixture was cooled to -10°C and 70 ml of titanium tetrachloride was added dropwise. Then, 3 ml of ethyl acetate and 6 ml of ethanol were added and the mixture was heated to 85°C at a rate of 0.5°C / min and stirred at 85°C for 1 hour. The mixture was cooled to 50°C and washed twice with toluene. Then, 90 ml of toluene was added and the mixture was cooled to -20°C. Then, 1 ml of butanol, 1 ml of ethanol, 2 ml of epichlorohydrin, and 20 ml of titanium tetrachloride were added and the mixture was stirred at -20°C for 30 minutes. The mixture was heated to 85°C at a rate of 0.4°C / min and stirred at 85°C for 1 hour. Then, 1 ml of 2,2-dimethyl-1,3-dimethoxypropane was added and the mixture was stirred at 85°C for 1 hour. The stirring was stopped and the mixture was allowed to stand. The mixture was washed twice with toluene. Then, 60 ml of hexane was added to the reaction vessel and the mixture was cooled to 0°C. Then, 10 ml of 0.9 M diethylaluminum chloride solution in heptane was added dropwise and the mixture was stirred at 0°C for 0.5 hour. The mixture was heated to 50°C at a rate of 0.4°C / min and stirred at 50°C for 1 hour. The stirring was stopped and the mixture was allowed to stand. The supernatant was removed and the residue was washed with toluene and hexane to obtain a solid catalyst component having good fluidity.

[0129] (2) Polymerization: Same as in Example 1. The results are shown in Table 1.

[0130] Example 3

[0131] (1) Preparation of Catalyst Component

[0132] Into a reactor, 4.8 g of magnesium chloride, 100 ml of toluene, 2.5 ml of epichlorohydrin, 12 ml of triisopropyl phosphate were added, and the mixture was reacted at 65°C for 2 hours. Then, 1.1 g of phthalic anhydride was added, and the mixture was further reacted at the same temperature for 1 hour. The system was cooled to -30°C, and 70 ml of titanium tetrachloride was added dropwise. Then, 3 ml of n-butyl acetate and 6 ml of ethanol were added, and the mixture was gradually heated to 85°C at a rate of 0.4°C / min. The mixture was reacted at the same temperature for 1 hour. The system was cooled to 50°C, and washed twice with inert solvent toluene. Then, 90 ml of toluene was added to dilute the system, and the mixture was cooled to -20°C. Then, 1 ml of butanol, 2 ml of isooctanol, 2 ml of propylene oxide and 20 ml of titanium tetrachloride were added successively dropwise, and the mixture was reacted at the same temperature for 30 min. The mixture was gradually heated to 85°C at a rate of 0.6°C / min, and reacted at the same temperature for 1 hour. Then, 1 ml of 2,2-dimethyl-1,3-diethoxypropane was added, and the mixture was further reacted at the same temperature for 1 hour. The stirring was stopped, and the mixture was allowed to stand. The mixture was washed twice with inert solvent toluene. Then, 60 ml of hexane was added to the reactor, and the mixture was cooled to 0°C. Then, 10 ml of 0.9M diethylaluminum chloride in heptane was added dropwise, and the mixture was reacted for 0.5 hour. The mixture was heated to 50°C at a rate of 0.4°C / min, and reacted at the same temperature for 1 hour. The stirring was stopped, and the mixture was allowed to stand. The suspension was quickly separated into two layers, and the supernatant was removed. The mixture was washed with inert solvent toluene and organic solvent hexane, and dried to obtain a solid catalyst component having good fluidity.

[0133] (2) Polymerization: Same as in Example 1. The polymerization results are shown in Table 1.

[0134] Example 4

[0135] (1) Preparation of catalyst component

[0136] Into a reactor, 4.8 g of magnesium chloride, 100 ml of toluene, 5.0 ml of epichlorohydrin, 12 ml of triisopropyl phosphate were added, and the mixture was reacted at 65°C for 2 hours. Then, 1.1 g of phthalic anhydride was added, and the mixture was further reacted at the same temperature for 1 hour. The system was cooled to -30°C, and 70 ml of tetraethoxytitanium was added dropwise. Then, 3 ml of n-butyl acetate and 6 ml of ethanol were added, and the mixture was gradually heated to 85°C at a rate of 0.4°C / min. The mixture was reacted at the same temperature for 1 hour. The system was cooled to 50°C, and washed twice with inert solvent toluene. Then, 90 ml of toluene was added to dilute the system, and the mixture was cooled to -20°C. Then, 1 ml of butanol, 2 ml of isooctanol, 2 ml of propylene oxide and 20 ml of tetraethoxytitanium were added successively dropwise, and the mixture was reacted at the same temperature for 30 min. The mixture was gradually heated to 85°C at a rate of 0.7°C / min, and reacted at the same temperature for 1 hour. Then, 1 ml of 1-ethoxy-2-methoxybenzene was added, and the mixture was further reacted at the same temperature for 1 hour. The stirring was stopped, and the mixture was allowed to stand. The suspension was quickly separated into two layers, and the supernatant was removed. The obtained solid catalyst component was washed with inert solvent toluene and organic solvent hexane, and dried to obtain a solid catalyst component having good fluidity.

[0137] (2) Polymerization: Same as in Example 1. The polymerization results are shown in Table 1.

[0138] Example 5

[0139] (1) Preparation of catalyst component

[0140] Into a reactor, 4.8 g of magnesium chloride, 100 ml of toluene, 5.0 ml of epichlorohydrin, 12 ml of tri-n-octyl phosphate were added, and the mixture was reacted at 65°C for 2 hours. Then, 1.1 g of acetic anhydride was added, and the mixture was further reacted at the same temperature for 1 hour. The system was cooled to -30°C, and 70 ml of titanium tetrachloride was added dropwise. Then, 3 ml of n-butyl acetate and 6 ml of hexanediol were added, and the mixture was gradually warmed to 85°C at a rate of 0.4°C / min. The mixture was reacted at the same temperature for 1 hour. The system was cooled to 50°C, and washed twice with inert solvent toluene. Then, 90 ml of toluene was added to dilute the system, and the mixture was cooled to -20°C. Then, 1 ml of butanol, 2 ml of isooctanol, 2 ml of propylene oxide and 20 ml of titanium tetrachloride were added successively dropwise, and the mixture was reacted at the same temperature for 30 min. The mixture was gradually warmed to 85°C at a rate of 0.7°C / min, and reacted at the same temperature for 1 hour. Then, 1 ml of o-dithyl ether was added, and the mixture was further reacted at the same temperature for 1 hour. The stirring was stopped, and the mixture was allowed to stand. The suspension was quickly separated into two layers, and the supernatant was removed. The obtained solid catalyst component was washed several times with inert solvent toluene and organic solvent hexane, and dried to obtain a solid catalyst component having good fluidity.

[0141] (2) Polymerization: Same as in Example 1. The polymerization results are shown in Table 1.

[0142] Example 6

[0143] (1) Preparation of catalyst component

[0144] To a reaction vessel was added 4.8 g magnesium chloride, 100 ml toluene, 5.0 ml epichlorohydrin, 12 ml tri-n-butyl phosphate, and the mixture was heated to 65°C and stirred for 2 hours. Then 1.1 g phthalic anhydride was added and the mixture was heated at 65°C for 1 hour. The mixture was cooled to -20°C and 70 ml titanium tetrachloride was added slowly. Then 3 ml isopropyl acetate and 6 ml ethanol were added and the mixture was heated to 85°C at a rate of 0.5°C / min and held at 85°C for 1 hour. The mixture was cooled to 50°C and washed twice with toluene. Then 90 ml toluene was added and the mixture was cooled to -20°C. Then 2 ml butanol, 2 ml epichlorohydrin, and 20 ml titanium tetrachloride were added and the mixture was held at -20°C for 30 minutes. The mixture was heated to 85°C at a rate of 0.4°C / min and held at 85°C for 1 hour. Then 1 ml 2,2-dimethyl-1,3-diethoxypropane was added and the mixture was held at 85°C for 1 hour. The stirring was stopped and the mixture was allowed to settle. The mixture was washed twice with toluene. Then 60 ml hexane was added to the reactor and the mixture was cooled to 0°C. Then 10 ml of a 0.9 M solution of diethylaluminum chloride in heptane was added slowly and the mixture was held at 0°C for 0.5 hours. The mixture was heated to 50°C at a rate of 0.5°C / min and held at 50°C for 1 hour. The stirring was stopped and the mixture was allowed to settle. The supernatant was removed and the solid was washed with toluene and hexane and dried to give a solid catalyst component having good flow properties.

[0145] (2) Polymerization: Same as Example 1. The polymerization results are shown in Table 1.

[0146] Example 7

[0147] (1) Preparation of Catalyst Component

[0148] Into a reactor, 4.8 g of magnesium chloride, 50 ml of xylene, 2.5 ml of epichlorohydrin, 6 ml of tri-n-octyl phosphate were added, and the mixture was reacted at 65°C for 2 hours. Then, 0.5 g of acetic anhydride was added, and the mixture was further reacted at the same temperature for 1 hour. The system was cooled to -30°C, and 35 ml of titanium tetrachloride was added dropwise. Then, 0.3 ml of n-butyl acetate and 0.5 ml of hexanediol were added, and the mixture was gradually heated to 85°C at a rate of 0.4°C / min. The mixture was reacted at 85°C for 1 hour. The system was cooled to 50°C, and washed twice with inert solvent xylene. Then, 30 ml of xylene was added to dilute the system, and the mixture was cooled to -20°C. Then, 1 ml of butanol, 2 ml of isooctanol, 2 ml of propylene oxide and 15 ml of titanium tetrachloride were added successively dropwise. The mixture was reacted at -20°C for 30 min, and then gradually heated to 85°C at a rate of 0.7°C / min. The mixture was reacted at 85°C for 1 hour. Then, 1 ml of 1-ethoxy-2-methoxybenzene was added, and the mixture was further reacted at the same temperature for 1 hour. The stirring was stopped, and the mixture was allowed to stand. The suspension was quickly separated into two layers, and the supernatant was removed. The mixture was washed with inert solvent xylene and organic solvent hexane, and then dried to obtain a solid catalyst component having good fluidity.

[0149] (2) Polymerization: Same as in Example 1. The polymerization results are shown in Table 1.

[0150] Example 8

[0151] (1) Preparation of catalyst component

[0152] To a reaction vessel was added 4.8 g magnesium chloride, 100 ml toluene, 5.0 ml epichlorohydrin, 12 ml tri-n-butyl phosphate, and the mixture was heated to 65°C and stirred for 2 hours. 1.1 g phthalic anhydride was added and the mixture was heated at 65°C for 1 hour. The mixture was cooled to -30°C and 70 ml titanium tetrachloride was added slowly. The mixture was then heated to 85°C at a rate of 0.5°C / minute and stirred for 1 hour. The mixture was cooled to 0°C and 10 ml of a 0.9 M solution of diethylaluminum chloride in heptane was added slowly. The mixture was heated to 50°C at a rate of 0.5°C / minute and stirred for 1 hour. The mixture was allowed to settle and the supernatant was decanted. The solid was washed with toluene and hexane. The solid was dried under vacuum to give a solid catalyst component having good flow properties.

[0153] Comparative Example 1

[0154] (1) Preparation of Catalyst Component

[0155] To a reaction vessel was added 4.8 g magnesium chloride, 100 ml toluene, 5.0 ml epichlorohydrin, 12 ml tri-n-butyl phosphate, and the mixture was heated to 65°C and stirred for 2 hours. 1.1 g phthalic anhydride was added and the mixture was heated at 65°C for 1 hour. The mixture was cooled to -30°C and 70 ml titanium tetrachloride was added slowly. The mixture was then heated to 85°C at a rate of 0.5°C / minute and stirred for 1 hour. The mixture was cooled to 0°C and 10 ml of a 0.9 M solution of diethylaluminum chloride in heptane was added slowly. The mixture was heated to 50°C at a rate of 0.5°C / minute and stirred for 1 hour. The mixture was allowed to settle and the supernatant was decanted. The solid was washed with toluene and hexane. The solid was dried under vacuum to give a solid catalyst component having good flow properties.

[0156] (2) Polymerization: Same as Example 1. The results are shown in Table 1.

[0157] Comparative Example 2

[0158] (1) Preparation of the catalyst component

[0159] To a reaction vessel were added 4.8 g of magnesium dichloride, 100 ml of toluene, 5.0 ml of glycidyl methacrylate, 12 ml of tri-n-butyl phosphate, and the mixture was reacted at 65°C for 2 hours. Then, 1.1 g of phthalic anhydride was added and the mixture was further reacted at the same temperature for 1 hour. The system was cooled to -10°C, and 70 ml of titanium tetrachloride was added dropwise. Then, 3 ml of ethyl acetate and 6 ml of ethanol were added, and the mixture was gradually heated to 85°C at a rate of 0.5°C / min. After 1 hour of reaction at the same temperature, 1 ml of 2,2-dimethyl-1,3-dimethoxypropane was added, and the mixture was further reacted at the same temperature for 1 hour. The stirring was stopped, and the mixture was allowed to stand. The solid catalyst component was washed with toluene, and then 60 ml of hexane was added to the reactor. The mixture was cooled to 0°C, and 10 ml of 0.9 M diethylaluminum chloride solution in heptane was added dropwise. The mixture was reacted at 50°C for 1 hour at a rate of 0.4°C / min. The stirring was stopped, and the mixture was allowed to stand. The upper layer was removed, and the solid catalyst component was washed with toluene and hexane. The solid catalyst component was obtained as a solid having good flowability.

[0160] (2) Polymerization: Same as Example 1. The polymerization results are shown in Table 1.

[0161] Comparative Example 3

[0162] (1) Preparation of the catalyst component

[0163] To a reaction vessel were added 4.8 g of magnesium dichloride, 100 ml of toluene, 5.0 ml of glycidyl methacrylate, 12 ml of tri-n-butyl phosphate, and the mixture was reacted at 65°C for 2 hours. Then, 1.1 g of phthalic anhydride was added and the mixture was further reacted at the same temperature for 1 hour. The system was cooled to -10°C, and 70 ml of titanium tetrachloride was added dropwise. Then, 3 ml of ethyl acetate and 6 ml of ethanol were added, and the mixture was gradually heated to 85°C at a rate of 0.5°C / min. After 1 hour of reaction at the same temperature, 1 ml of 2,2-dimethyl-1,3-dimethoxypropane was added, and the mixture was further reacted at the same temperature for 1 hour. The stirring was stopped, and the mixture was allowed to stand. The solid catalyst component was washed with toluene, and then 60 ml of hexane was added to the reactor. The mixture was cooled to 0°C, and 10 ml of 0.9 M diethylaluminum chloride solution in heptane was added dropwise. The mixture was reacted at 50°C for 1 hour at a rate of 0.4°C / min. The stirring was stopped, and the mixture was allowed to stand. The upper layer was removed, and the solid catalyst component was washed with toluene and hexane. The solid catalyst component was obtained as a solid having good flowability.

[0164] (2) Polymerization: Same as Example 1. The polymerization results are shown in Table 1.

[0165] Comparative Example 4

[0166] (1) Preparation of the catalyst component

[0167] Into a reactor, 4.8 g of magnesium chloride, 100 ml of toluene, 5.0 ml of epichlorohydrin, 12 ml of triisopropyl phosphate were added, and the mixture was reacted at 65°C for 2 hours. Then, 1.1 g of phthalic anhydride was added, and the mixture was further reacted at the same temperature for 1 hour. The system was cooled to -30°C, and 70 ml of tetraethoxy titanium was added dropwise. Then, 3 ml of n-butyl acetate and 6 ml of ethanol were added, and the mixture was gradually warmed to 85°C at a rate of 0.4°C / min. After the mixture was reacted at the same temperature for 1 hour, 1 ml of 1-ethoxy-2-methoxybenzene was added, and the mixture was further reacted at the same temperature for 1 hour. The stirring was stopped, and the mixture was allowed to stand. The supernatant was removed, and the solid was washed with toluene and hexane. The solid catalyst component having good fluidity was obtained.

[0168] (2) Polymerization: Same as Example 1. The polymerization results are shown in Table 1.

[0169] Comparative Example 5

[0170] (1) Preparation of catalyst component

[0171] Into a reactor, 4.8 g of magnesium chloride, 100 ml of toluene, 5.0 ml of epichlorohydrin, 12 ml of triisopropyl phosphate were added, and the mixture was reacted at 65°C for 2 hours. Then, 1.1 g of phthalic anhydride was added, and the mixture was further reacted at the same temperature for 1 hour. The system was cooled to -30°C, and 70 ml of tetraethoxy titanium was added dropwise. Then, 3 ml of n-butyl acetate and 6 ml of ethanol were added, and the mixture was gradually warmed to 85°C at a rate of 0.4°C / min. After the mixture was reacted at the same temperature for 1 hour, 1 ml of 1-ethoxy-2-methoxybenzene was added, and the mixture was further reacted at the same temperature for 1 hour. The stirring was stopped, and the mixture was allowed to stand. The supernatant was removed, and the solid was washed with toluene and hexane. The solid catalyst component having good fluidity was obtained.

[0172] (2) Polymerization: Same as Example 1. The polymerization results are shown in Table 1.

[0173] Table 1

[0174]

[0175] From Table 1, under the specific composition of the present application, under the synergistic cooperation of each component, especially using the specific preparation method, by adding the organoaluminum compound after two times of titanium loading, the catalyst has high catalyst activity and bulk density, and the obtained polymer has controllable molecular weight, narrow distribution Mw / Mn≤7, spherical degree SPHT≥0.75, and swelling time ≤40 min. The catalysts in Comparative Examples 1-4 are not treated by the method of the present application and two times of titanium loading, the particle size distribution (span value) is wide, the spherical degree is slightly poor, resulting in long swelling time. The addition of alcohol compound (ethanol) in the early stage in Comparative Example 5 does not form a dissolution and precipitation system, and the addition of ethanol in the early stage has a great influence on the activity of the catalyst, but affects the particle type of the catalyst, so the spherical degree is not high.

[0176] It should be noted that the above-described embodiments are only used to explain the present application and do not constitute any limitation on the present application. The present application is described by referring to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than limiting words. The present application can be modified as specified within the scope of the claims of the present application, and the present application can be revised within the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and embodiments, it does not mean that the present application is limited to the specific examples disclosed therein, on the contrary, the present application can be extended to all other methods and applications having the same function.

[0177] All publications, patent applications, patents and other references mentioned in this specification are hereby incorporated by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the definition in this specification prevails.

[0178] When the specification derives a material, substance, method, step, device or component, etc. with the word head "known to those skilled in the art", "prior art" or similar words, the object derived by the word head covers those commonly used in the art at the time of the present application, but also includes those which are not commonly used at present, but will be recognized as suitable for similar purposes in the art.

[0179] The endpoints of the ranges and any values disclosed in this application document are not limited to the precise values stated. The ranges and values should be interpreted as being approximate. Values that are near to the endpoints of the ranges and values are hereby incorporated into the specification as if explicitly written herein. In the following, the individual technical solutions can be combined with each other in principle to obtain new technical solutions, which should also be regarded as specifically disclosed herein.

[0180] In the context of the present specification, unless explicitly stated otherwise, any reference to any item or matter not mentioned is to be taken directly from those known in the art without any need for any change.

[0181] Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, whereby the resulting technical solution or technical idea is to be considered as part of the original disclosure or original teaching of the present application and should not be considered as new matter not disclosed or anticipated herein, unless the combination is considered to be clearly unreasonable by the person skilled in the art.

Claims

1. A catalyst component for the polymerization of olefins, said catalyst component comprising the reaction product of the following components: a solid catalyst component F, a second alcoholic compound, a second organic epoxide compound, a second titanium compound, an electron donor a and / or an electron donor b, an organic aluminum compound; the molar ratio of the solid catalyst component F, the second alcoholic compound, the second organic epoxide compound, the second titanium compound, the electron donor a and / or the electron donor b, the organic aluminum compound is 1 : (0.05-20) : (0.01-50) : (0.5-50) : (0.01-100) : (0.001-10.0), preferably 1 : (0.1-1.0) : (0.1-10) : (2.0-30.0) : (0.02-10) : (0.005-2).

2. The catalyst component of claim 1, characterized in that the solid catalyst component F is prepared by the following process: a first reaction of a magnesium complex with an organic acid anhydride compound, followed by a second reaction with a first titanium compound, a first alcoholic compound and an acetate compound, to produce the solid catalyst component F; the molar ratio of the magnesium complex, the organic acid anhydride compound, the first titanium compound, the first alcoholic compound and the acetate compound is 1 : (0.01-10) : (5-1000) : (0.01-20) : (0.01-10), preferably 1 : (0.01-1) : (10-200) : (0.1-5) : (0.02-2).

3. The catalyst component according to claim 2, wherein: the reaction temperature of the first reaction is 50-70°C, and / or the reaction time is 0.5-2 hours; and / or the temperature of the system after the first reaction is reduced to -60°C to 20°C, before being contacted with the first titanium compound, the first alcoholic compound and the acetate compound; and / or the reaction temperature of the second reaction is 75-100°C, and / or the temperature increase rate is 0.2-2°C / min, and / or the reaction time is 1-4 hours.

4. The catalyst component of claim 2, characterized by the magnesium complex is prepared by the following process: dissolving a magnesium halide in a solvent system containing a first organic epoxide compound, an organic phosphorus compound, optionally an acetate compound and optionally an inert diluent, to produce the magnesium complex; when containing an acetate compound and an inert diluent, the molar ratio of the magnesium halide, the first organic epoxide compound, the organic phosphorus compound, the acetate compound and the inert diluent is 1 : (0.2-10) : (0.1-10) : (0.01-1) : (5-50), preferably 1 : (0.5-2) : (0.5-2) : (0.05-0.20) : (10-30).

5. The catalyst component according to claim 4, wherein: the magnesium halide is a magnesium dihalide or a complex of a magnesium dihalide with at least one of water, an alcohol or an electron donor; preferably, the magnesium dihalide is at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, magnesium diiodide; and / or, the alcohol is at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, iso-octanol; and / or, the electron donor is at least one of ammonia, hydroxylamine, an ether, an ester; and / or, the first and second organic epoxy compounds can be the same or different and are each independently selected from at least one of an oxide of an olefinic compound, a glycidyl ether and an internal ether; preferably, the olefinic compound is at least one of a C2-C18 aliphatic olefin, an aliphatic diene, a halogenated aliphatic olefin, a halogenated aliphatic diene; more preferably, the first and second organic epoxy compounds are each independently selected from at least one of oxirane, oxetane, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, butyl glycidyl ether; and / or, the organic phosphorus compound is a hydrocarbyl ester or a halogenated hydrocarbyl ester of a phosphoric acid compound; preferably, the phosphoric acid compound is orthophosphoric acid or phosphorous acid; more preferably, the organic phosphorus compound is at least one of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, tri-i-propyl phosphate, tri-n-butyl phosphate, tri-i-butyl phosphate, tri-t-butyl phosphate, tri-n-pentyl phosphate, tri-i-pentyl phosphate, tri-n-hexyl phosphate, tri-i-hexyl phosphate, tri-n-heptyl phosphate, tri-i-heptyl phosphate, tri-n-octyl phosphate, tri-i-octyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, tri-i-propyl phosphite, tri-n-butyl phosphite, tri-i-butyl phosphite, tri-t-butyl phosphite, tri-n-pentyl phosphite, tri-i-pentyl phosphite, tri-n-hexyl phosphite, tri-i-hexyl phosphite, tri-n-heptyl phosphite, tri-i-heptyl phosphite, tri-n-octyl phosphite, tri-i-octyl phosphite, triphenyl phosphite, di-n-butyl phosphite; and / or, the dissolution temperature is 50-70°C and / or the dissolution time is 1-3 hours.

6. The catalyst component according to claim 2, wherein: the structure of the organic anhydride compound is: wherein R5’ and R6’ can be the same or different and are each independently one of hydrogen, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C3-C10 cycloalkyl group, a C6-C10 aromatic hydrocarbon group; preferably, the organic anhydride compound is at least one of acetic anhydride, propionic anhydride, butyric anhydride, acrylic anhydride, phthalic anhydride, butenyl anhydride, maleic anhydride; and / or, the dissolution temperature is 50-70°C and / or the dissolution time is 1-3 hours. The first and second titanium compounds can be the same or different and are each independently selected from Ti(OR8)4-aXa a X b wherein R8is a C1-C10 aliphatic or aromatic hydrocarbon group, X is a halogen, preferably fluorine, chlorine or bromine, a is 0, 1 or 2, and b is any integer from 1 to 4; preferably, the sum of a and b is 3 or 4; more preferably, the first and second titanium compounds are each independently selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraethoxide, titanium chloride triethoxide, titanium trichloride, titanium dichloride diethoxide, and titanium trichloride monoethoxide; and / or, The first and second alcohol compounds can be the same or different, and are each independently a C1-C18 aliphatic alcohol or aromatic alcohol; preferably, the first and second alcohol compounds are each independently at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, hexanol, cyclohexanol, octanol, isooctanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, isohexylene glycol.

7. The catalyst component according to any one of claims 2-4, wherein: The acetic ester compound has a structural formula of CH3COOR7, wherein R7 is a C1-C10 alkyl group, a C2-C10 alkenyl group, a C3-C10 cycloalkyl group, a C2-C10 alkynyl group, or a C6-C10 aromatic hydrocarbon group; preferably, R7 is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group, or a n-hexyl group; more preferably, the acetic ester compound is at least one of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, n-octyl acetate.

8. The catalyst component according to claim 1, wherein: The electron donor a and / or the electron donor b is a diether electron donor; preferably, The electron donor a has a structural formula of: wherein R1 and R2 can be the same or different, and are each independently a methyl group or an ethyl group, and R3 and R4 can be the same or different, and are each independently hydrogen or a methyl group; preferably, the electron donor a is at least one 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; and / or, The electron donor b has a structural formula of: wherein R5and R6may be the same or different, each independently a methyl or ethyl group, R7, R8, R9and R 10 may be the same or different, each independently hydrogen, halogen, C1-C10 linear alkyl, C1-C10 branched alkyl or C1-C10 alkoxy; preferably, said R7, R8, R9and R 10 each independently hydrogen, fluorine, chlorine, bromine, iodine, C1-C6 linear alkyl, C1-C6 branched alkyl or C1-C6 alkoxy; more preferably, said electron donor b is at least one of o-dianisole, o-diethyl ether and 1-ethoxy-2-methoxybenzene; and / or, The organic aluminum compound is wherein R 6 is hydrogen or a C1-C20 hydrocarbon group, X 2 is halogen, 0 The organic aluminum compound is at least one of triethylaluminum, monochlorodiethylaluminum, dichloro-monoethylaluminum, hemiethylaluminum, di-chloroisobutylaluminum, triisobutylaluminum, monochlorodiisopropylaluminum, monochloromethyl-n-propylaluminum, monochlorodiphenylaluminum, di-chlorodiethylaluminum, preferably at least one of monochlorodiethylaluminum, dichloro-monoethylaluminum, triethylaluminum.

9. A method for preparing the catalyst component for olefin polymerization according to any one of claims 1-8, the method comprising: After dispersing the solid catalyst component F in an inert solvent, the first contact reaction is performed with a second alcohol compound, a second organic epoxide compound, and a second titanium compound, and then the second contact reaction is performed with the electron donor a and / or the electron donor b, and finally the catalyst component is prepared after treatment with an organic aluminum compound.

10. The method for preparing according to claim 9, wherein: The inert solvent and the inert diluent can be the same or different, and are each independently selected from aromatic compounds and / or alkanes; preferably, the aromatic compound is at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene; and / or, the alkane is at least one of a straight-chain alkane, a branched-chain alkane, a cycloalkane having 3-20 carbon atoms; and / or, The molar ratio of the solid catalyst component F and the inert solvent is 1:(5-50); preferably, 1:(10-30); and / or, The molar ratio of the solid catalyst component F and the inert solvent is 1:(5-50); preferably, 1:(10-30); and / or, After the solid catalyst component F is dispersed in the inert solvent, the temperature of the system is lowered to -60℃ to 20℃, and then the second alcohol compound, the second organic epoxide compound, and the second titanium compound are contacted therewith; and / or, The reaction temperature of the first contact reaction is -60℃ to 20℃, and / or, the reaction time is 0.5 to 2 hours; and / or, The reaction temperature of the second contact reaction is 75 to 100℃, and / or, the heating rate is 0.2 to 2℃ / min, and / or, the reaction time is 1 to 4 hours; and / or, After the second contact reaction, the temperature of the system is lowered to -20℃ to 20℃, and then the organic aluminum compound is contacted therewith; and / or, The treatment temperature is 40 to 80℃, and / or, the heating rate is 0.2 to 2℃ / min, and / or, the treatment time is 1 to 4 hours.

11. A catalyst for the polymerization of olefins, comprising the following components: The catalyst component as claimed in any one of claims 1 to 8 or prepared by the preparation method as claimed in claim 9 or 10, and an organic aluminum compound; Preferably, the structural formula of the organoaluminum compound is AlR’ d X’ 3-d , where R’ is hydrogen or a C1-C20 hydrocarbon group, X’ is a halogen atom, preferably fluorine, chlorine or bromine, and 0 < d ≤ 3; and / or, The molar ratio of aluminum in the organic aluminum compound to titanium in the catalyst component is (5-500):1, preferably (20-200):

1.

12. Use of the catalyst as claimed in claim 11 in the preparation of polyolefins by the polymerization of olefins, Preferably, The olefin is CH2=CHR, wherein R is hydrogen or C1-C6 alkyl; more preferably, the olefin is at least one of ethylene, propylene, and butylene; and / or, The polyolefin is a very high molecular weight polyolefin or an ultra high molecular weight polyolefin, more preferably, the polyolefin is a very high molecular weight polyethylene or an ultra high molecular weight polyethylene; and / or, The reaction temperature of the polymerization reaction is 40 to 100℃, and / or, the reaction time is 1 to 10 hours, and / or, the reaction pressure is 0.3 to 2 Mpa.

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