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

Abstract

The invention discloses a catalyst component for olefin polymerization, a catalyst, a preparation method and application, and relates to the technical field of olefin polymerization catalysts. The catalyst component comprises reaction products of the following components: a magnesium-containing compound solution, an organic anhydride compound, a titanium compound, an acetate compound, a first alcohol compound and an aromatic ester compound, in the catalyst component, the molar ratio of the magnesium element to the organic anhydride compound to the titanium compound to the acetate compound to the first alcohol compound to the aromatic ester compound is 1: (0.01-1): (2-30): (0.01-10.0): (0.05-10.0): (0.01-5.0). The catalyst component prepared by the preparation method provided by the invention is concentrated in particle size distribution, the catalyst containing the catalyst component has higher polymerization activity, the hydrogen regulation sensitivity under the condition of high hydrogen-ethyl ratio is greatly improved, the hydrogen regulation sensitivity under the condition of low hydrogen-ethyl ratio is moderate, and the catalyst component is suitable for industrial production. The catalyst can catalyze ethylene polymerization to obtain powder particles with high bulk density, the content of fine powder with the size smaller than 75 microns in the polymerized powder is greatly reduced, and almost no fine powder exists.

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, a preparation method and application thereof. BACKGROUND

[0002] At present, Ziegler-Natta type olefin polymerization catalysts still dominate the industrial production of polyolefins. In the slurry polymerization process of ethylene, the Ziegler-Natta catalysts are required to have high polymerization activity, the powder prepared by the catalysts is required to have high bulk density, and the product resin is required to have excellent performance.

[0003] In the process of ethylene polymerization, a catalyst with excellent hydrogen regulation performance can perform chain transfer reaction at a lower hydrogen / ethylene ratio, thereby achieving the expected molecular weight of the resin, and the use of a smaller amount of hydrogen also reduces the suppression of polymerization activity. Developing a catalyst with high hydrogen regulation sensitivity can not only reduce the hydrogen consumption of the polymerization device, but also improve the polymerization activity to some extent. However, during the production of multi-modal grades such as PE100 grade pipe resin grades and multi-modal membrane material grades, the hydrogen regulation sensitivity is too high under the condition of low hydrogen / ethylene ratio, and problems such as "pockmarks" and "crystal points" often occur, which seriously affects the quality of the product. Therefore, it is very important to develop a catalyst with hydrogen regulation sensitivity under high hydrogen / ethylene ratio and moderate hydrogen regulation performance under low hydrogen / ethylene ratio.

[0004] In some slurry polymerization processes, the polymer / hexane slurry is separated by centrifugation, and the hexane carrying amount of the high bulk density powder is lower, which is beneficial to reduce the energy consumption of powder drying and improve the load of the drying unit, thereby increasing the load of the polymerization reaction unit. In addition, due to excellent flow performance, high bulk density powder is beneficial to the efficient operation of the powder conveying unit of the industrial device, thereby enabling the industrial device to achieve higher production load. Therefore, it is very important to develop a catalyst for preparing high bulk density powder.

[0005] To balance the high activity, excellent hydrogen response and high bulk density of the prepared polymer powder, researchers have made a lot of exploration and research. There are patents reported, for example, in Chinese patent CN1086191C, which uses magnesium chloride as the carrier and titanium tetrachloride as the active component. The preparation method of the catalyst is as follows: first, dissolve MgCl2 in a solvent system to form a uniform transparent solution, then react with TiCl4 at low temperature, and precipitate the solid catalyst by slowly heating. When the prepared catalyst component is used for ethylene polymerization, the catalyst has high catalytic activity, and the catalyst particle morphology is also improved to a certain extent. However, due to the unsatisfactory polymer particle morphology, especially the unsatisfactory flowability of the prepared polymer powder, it is difficult to fully meet the needs of industrial production when producing some resins with high requirements for polymer powder particle morphology and powder flowability, and the hydrogen response is not good, and the hydrogen consumption of the polymerization device is high.

[0006] Therefore, it is necessary to develop a polyethylene catalyst which can prepare high activity and high hydrogen response sensitivity and moderate low hydrogen response sensitivity, and the catalyst can polymerize to obtain high bulk density of powder particles, and the prepared polymer powder should have good flowability. SUMMARY

[0007] In order to solve the problems existing in the prior art, the present application provides a catalyst component for olefin polymerization, a catalyst and a preparation method and application. The catalyst component and the catalyst containing the catalyst component have high polymerization activity and hydrogen response sensitivity, can catalyze ethylene polymerization to obtain high bulk density of powder particles, and the content of fine powder with a size of less than 75 μm is greatly reduced, and there is almost no fine powder.

[0008] One of the purposes of the present application is to provide a catalyst component for olefin polymerization.

[0009] The catalyst component for olefin polymerization according to the present application is characterized in that the catalyst component comprises the reaction product of the following components:

[0010] The magnesium-containing complex solution, the organic acid anhydride compound, the titanium compound, the acetic ester compound, the first alcohol compound and the aromatic ester compound;

[0011] The molar ratio of magnesium element, organic acid anhydride compound, titanium compound, acetic ester compound, first alcohol compound and aromatic ester compound in the catalyst component is 1:(0.01-1):(2-30):(0.01-10.0):(0.05-10.0):(0.01-5.0).

[0012] In a preferred embodiment of the present application:

[0013] The molar ratio of the magnesium element, the organic acid anhydride compound, the titanium compound, the first alcohol compound, and the aromatic ester compound in the catalyst component is 1 : (0.02-0.5) : (5-25) : (0.02-5.0) : (0.1-5.0) 1 : (0.1-3.0).

[0014] In a preferred embodiment of the present application, the magnesium-containing complex solution is prepared from raw materials comprising:

[0015] The magnesium element in the magnesium halide, the organic phosphorus compound, the organic epoxy compound, and the inert diluent;

[0016] The molar ratio of the magnesium element in the magnesium halide, the organic phosphorus compound, the organic epoxy compound, and the inert diluent is 1 : (0.1-3.0) : (0.1-3.0) : (1-50), preferably 1 : (0.5-1.5) : (0.5-1.5) : (5-20).

[0017] In a preferred embodiment of the present application:

[0018] The magnesium halide is a dihalogenated magnesium and / or a complex formed by the dihalogenated magnesium and at least one of water, a second alcohol compound, and an electron donor; preferably, the dihalogenated magnesium is at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, and magnesium diiodide, and / or the second alcohol compound is at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, and isooctanol, and / or the electron donor is at least one of ammonia, hydroxylamine, an ether, and an ester; and / or,

[0019] 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, preferably at least one of triethyl phosphate, tri-n-butyl phosphate, tri-i-butyl phosphate, tri-i-octyl phosphate, triphenyl phosphate, triethyl phosphite, tri-n-butyl phosphite, tri-i-butyl phosphite, and di-n-butyl phosphite; and / or,

[0020] The organic epoxide compound is at least one of aliphatic olefin, aliphatic diene, halogenated aliphatic olefin, halogenated aliphatic diene, oxide, glycidyl ether, internal ether; preferably, the number of carbon atoms of the organic epoxide compound is 2-8; more preferably, the organic epoxide compound is at least one of oxirane, oxetane, butylene oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran, further preferably at least one of oxirane, oxetane, epichlorohydrin, tetrahydrofuran; and / or,

[0021] The inert diluent is at least one of C6-C10 alkane and derivatives thereof and / or C6-C8 aromatic hydrocarbon and derivatives thereof, preferably at least one of hexane, heptane, octane, decane, benzene, toluene, xylene.

[0022] In a preferred embodiment of the present application:

[0023] The structure of the organic acid anhydride compound is shown in formula (I):

[0024]

[0025] In formula (I), R1 and R2 can be the same or different, and are independently selected from hydrogen, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl or C6-C10 aromatic hydrocarbon group; and / or, R1 and R2 can be arbitrarily annulated; 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,

[0026] The chemical formula of the titanium compound is TiX n (OR) 4-n wherein X is halogen, R is C1-C14 aliphatic hydrocarbon group or C6-C14 aromatic hydrocarbon group, and n is any integer from 0 to 4; preferably, the titanium compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetraethoxide, titanium tetrabutoxide, chlorotriethoxy titanium, dichlorodiethoxy titanium, chloroethoxy titanium, more preferably at least one of titanium tetrachloride, titanium tetraethoxide, titanium tetrabutoxide; and / or,

[0027] 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; and / or,

[0028] the first alcohol compound is at least one of C1-C12 aliphatic alcohol and its derived substituted alcohol, and / or C7-C12 aromatic alcohol and its derived substituted alcohol, preferably at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, benzyl alcohol, phenethyl alcohol, more preferably at least one of ethanol, isopropanol, butanol, 2-ethylhexanol, benzyl alcohol, phenethyl alcohol; and / or.

[0029] the aromatic ester compound is of the formula C5H5[(CH2) n COOR9], wherein R9 is C1-C10 aliphatic hydrocarbon group or C1-C10 aromatic hydrocarbon group, and n is any integer from 0 to 9; preferably, the aromatic ester compound is at least one of methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, octyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, hexyl phenylacetate, octyl phenylacetate.

[0030] The second object of the present application is to provide a preparation method of the catalyst component for olefin polymerization as described in the first object of the present application.

[0031] The preparation method of the catalyst component for olefin polymerization of the present application comprises:

[0032] S1: dissolving the magnesium halide in the organic phosphorus compound, the organic epoxy compound and the inert diluent, and reacting at elevated temperature to obtain the magnesium-containing complex solution;

[0033] S2: mixing the magnesium-containing complex solution with the organic acid anhydride compound, and reacting at elevated temperature to obtain a first mixture, and then cooling down;

[0034] S3: reacting the first mixture with the titanium compound to obtain a second mixture;

[0035] S4: reacting the second mixture with the first alcohol compound at elevated temperature to obtain a reaction mother liquor and a precipitate;

[0036] S5: aging treatment, filtering, washing, and precipitating the reaction mother liquor and the precipitate to obtain the catalyst component;

[0037] At least one of steps S3, S4, and S5 adds the aromatic ester compound, preferably, steps S4 and / or S5 add the aromatic ester compound.

[0038] At least one of steps S1, S2, S3, S4, and S5 adds the acetic ester compound, preferably, step S4 adds the acetic ester compound.

[0039] At least one of steps S3, S4, and S5 adds the aromatic ester compound, which means that the aromatic ester compound can be added in one of steps S3, S4, and S5, or the aromatic ester compound can be added in two or three of steps S3, S4, and S5, and all of the above can achieve the present application. At least one of steps S1, S2, S3, S4, and S5 adds the acetic ester compound, which means that the acetic ester compound can be added in one of steps S1, S2, S3, S4, and S5, or the acetic ester compound can be added in two, three, four, or five of steps S1, S2, S3, S4, and S5, and all of the above can achieve the present application.

[0040] In a preferred embodiment of the present application, step S4 adds the acetic ester compound and / or steps S4 and / or S5 add the aromatic ester compound.

[0041] For example, step S5 adds the aromatic ester compound, which can be implemented as follows:

[0042] S1: dissolving a magnesium halide in a solvent system containing an organic phosphorus compound, an organic epoxy compound, and an inert diluent to form a uniform solution to obtain a magnesium-containing composite solution;

[0043] S2: mixing the magnesium-containing composite solution with an organic acid anhydride compound, heating to react, obtaining a first mixture, and cooling;

[0044] S3: contacting the first mixture with a titanium compound under the temperature condition after cooling to obtain a second mixture;

[0045] S4: reacting the second mixture with an acetic ester compound and a first alcohol compound under the temperature condition after cooling, heating to a preset temperature, and reacting to make the second mixture precipitate spherical or spherical-like solid particles to obtain a reaction mother liquor and a precipitate;

[0046] S5: continue the constant temperature, and age the reaction mother liquor and the precipitate; and, add the aromatic ester compound to the reaction mother liquor and the solid particles in the aging stage to react.

[0047] S6: remove the unreacted substance and the solvent in the catalyst component obtained in step S5 through filtration and washing to obtain a catalyst component for olefin polymerization.

[0048] For example, the addition of the aromatic ester compound in step S4 can be carried out according to the following scheme:

[0049] S1: dissolve the magnesium halide in a solvent system containing the organophosphorus compound, the organoepoxy compound and the inert diluent to form a uniform solution to prepare a magnesium-containing complex solution;

[0050] S2: mix the magnesium-containing complex solution with the organic acid anhydride compound, and react at a high temperature to obtain a first mixture, and then cool down;

[0051] S3: contact the first mixture with the titanium compound at the temperature after cooling to obtain a second mixture;

[0052] S4: react the second mixture with the acetic ester compound, the first alcohol compound and the aromatic ester compound at the temperature after cooling, and then heat and keep the temperature to make the spherical or spherical-like solid particles precipitate in the second mixture to obtain a reaction mother liquor and a precipitate;

[0053] S5: continue the constant temperature, and age the reaction mother liquor and the precipitate;

[0054] S6: remove the unreacted substance and the solvent in the catalyst component obtained in step S5 through filtration and washing to obtain a catalyst component for olefin polymerization.

[0055] In a preferred embodiment of the present application:

[0056] In step S1: the reaction temperature of the reaction at a high temperature is 30-120°C, preferably 40-80°C, and / or the reaction time is 0.1-15 hours, preferably 1-3 hours; and / or,

[0057] In step S2: the reaction temperature of the reaction at a high temperature is 30-120°C, preferably 40-80°C, and / or; the reaction time is 0.1-15 hours, preferably 0.2-3 hours; and / or, the temperature after cooling is -60-0°C, preferably -50--20°C; and / or,

[0058] In step S3: the reaction temperature is -60-0°C, preferably -50--20°C; and / or,

[0059] In step S4, the reaction temperature of the temperature-raising reaction is 40-120 DEG C, preferably 80-100 DEG C, and / or the reaction time is 0.1-15 hours, preferably 0.5-10 hours, and / or the temperature-raising rate is 0.01-5.0 DEG C / min, preferably 0.1-2.0 DEG C / min; and / or,

[0060] In step S5, the temperature of the aging treatment is 40-120 DEG C, preferably 80-100 DEG C, and / or the aging treatment time is 0.01-10 hours, preferably 0.1-5 hours.

[0061] The above reaction temperature and reaction time can be selected by those skilled in the art according to actual needs.

[0062] It is found through research that, by using the special method of adding aromatic ester compounds, the ability of chain transfer reaction to hydrogen can be greatly improved under the condition of high hydrogen concentration, and the melt index of high hydrogen ethylene is high, and under the condition of low hydrogen concentration, the reaction ability of chain transfer to hydrogen is moderate, and the hydrogen regulation performance is also moderate under the condition of low hydrogen ethylene.

[0063] A third object of the present application is to provide a catalyst for olefin polymerization.

[0064] The catalyst for olefin polymerization comprises:

[0065] The organic aluminum compound and the catalyst component according to the first object of the present application or the catalyst component prepared by the method according to the second object of the present application;

[0066] The molar ratio of titanium element in the catalyst component to aluminum element in the organic aluminum compound is 1:(20-200), preferably 1:(50-100).

[0067] In a preferred embodiment of the present application:

[0068] The chemical formula 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, and d is any integer from 0 to 3; 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), more preferably Al(CH2CH3)3 and / or Al(i-Bu)3.

[0069] The organic aluminum compound acts as a cocatalyst in the polymerization process together with the catalyst component, and plays a role in polymerization catalysis; the organic aluminum compound is only added as a cocatalyst in the polymerization, and the organic aluminum compound is not used in the catalyst component, and the organic aluminum compound is not introduced into the catalyst component, so as to prevent the organic aluminum compound from competing with the catalyst component or directly reacting with the catalyst component, and the influence of the organic aluminum compound on the number and distribution of active centers in the catalyst component can be effectively avoided.

[0070] The fourth object of the present application is to provide an application of the catalyst in olefin polymerization as described in the fifth object of the present application.

[0071] The application of the catalyst in olefin polymerization, preferably,

[0072] The olefin polymerization is ethylene polymerization; more preferably,

[0073] The ethylene polymerization is homopolymerization of ethylene or copolymerization of ethylene and α-olefin; and / or,

[0074] The ethylene polymerization is slurry polymerization or gas phase polymerization; further preferably,

[0075] The slurry polymerization medium comprises saturated aliphatic hydrocarbon and / or aromatic hydrocarbon, preferably at least one of isobutane, n-hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene, more preferably at least one of toluene, n-hexane, cyclohexane.

[0076] It can be known from the above technical solutions that the present application first discovers a catalyst component, the particle size distribution of which is concentrated; the hydrogen regulation sensitivity of the catalyst component under high hydrogen-to-ethylene ratio conditions is greatly improved, and the hydrogen regulation sensitivity under low hydrogen-to-ethylene ratio conditions is moderate; the catalyst with hydrogen regulation sensitivity under high hydrogen-to-ethylene ratio conditions and moderate hydrogen regulation performance under low hydrogen-to-ethylene ratio conditions can greatly reduce the hydrogen consumption in the production of multi-modal polyethylene resin, and due to the insensitivity under low hydrogen-to-ethylene ratio conditions, the occurrence of "pitting" of pipe material and "crystal point" of film material can be avoided in the production of PE100 grade pipe material resin and multi-modal film material resin; the catalyst component can catalyze ethylene polymerization to obtain high bulk density powder particles, and the content of fine powder with a size less than 75 μm in the polymerized powder is extremely small, almost no fine powder. BRIEF DESCRIPTION OF DRAWINGS

[0077] Figure 1 The scanning electron microscope photograph of the catalyst component prepared in Example 1.

[0078] Figure 2 The scanning electron microscope photograph of the catalyst component prepared in Example 2.

[0079] Figure 3A scanning electron microscope picture of the catalyst component prepared in Example 4.

[0080] Figure 4 A scanning electron microscope picture of the catalyst component prepared in Example 5.

[0081] From Figures 1-4 It can be seen that the embodiments of the present application can prepare spherical and / or spheroidal catalyst component particles with very uniform particle morphology. DETAILED DESCRIPTION

[0082] The following detailed description of the application is presented in connection with specific embodiments thereof. It is to be understood that the following is intended only to illustrate the present application and is not intended to limit the scope of the present application. Some non-essential improvements and adjustments to the present application made by those skilled in the art based on the content of the present application are still within the scope of the present application.

[0083] In the following examples and comparative examples of the present application, all raw materials are commercially available unless otherwise specified, and the specific information is shown in Table 1 below.

[0084] Table 1

[0085] Raw materials Source Grade or brand Magnesium chloride Beijing Innochem Company 99% anhydrous magnesium chloride powder Magnesium fluoride Beijing Innochem Company 99.99% magnesium fluoride Magnesium iodide Aladdin Company 98% magnesium iodide hydrate n-Hexane Beijing Innochem Company ≥95% chromatographic grade n-hexane Toluene Beijing Innochem Company ≥99.5% analytical pure toluene Xylene Beijing Innochem Company 99% analytical pure xylene Epichlorohydrin Beijing Innochem Company 99% epichlorohydrin Ethylene oxide Aladdin Company 99.5% ethylene oxide Tetrahydrofuran Beijing Innochem Company ≥99.8% chromatographic grade stabilizer-free tetrahydrofuran Tri-n-butyl phosphate Beijing Innochem Company ≥99% tri-n-butyl phosphate Tri-iso-butyl phosphate Aladdin Company 98% tri-iso-butyl phosphate Triethyl phosphate Beijing Innochem Company 99+% triethyl phosphate Ethanol Beijing Innochem Company 99.7% analytical pure anhydrous ethanol Butanol Beijing Innochem Company 99.5% n-butanol 2-Ethylhexanol Beijing Innochem Company 99% analytical pure iso-octanol Titanium tetrachloride Beijing Innochem Company 99% analytical pure titanium tetrachloride Titanium tetraethoxide Beijing Innochem Company 98% titanium tetraethoxide Titanium tetrabutoxide Beijing Innochem Company ≥99% titanium tetrabutoxide Phthalic anhydride Beijing Innochem Company ≥99% phthalic anhydride Acetic anhydride Shanghai Macklin Company ≥99% acetic anhydride Acrylic anhydride Beijing Innochem Company 97% acrylic anhydride Ethyl acetate Beijing Innochem Company 99% ethyl acetate Methyl acetate Beijing Innochem Company 99% methyl acetate n-Propyl acetate Beijing Innochem Company 99+% n-propyl acetate Ethyl benzoate Beijing Innochem Company 99+% ethyl benzoate Methyl benzoate Beijing Innochem Company 99% methyl benzoate n-Propyl benzoate Beijing Innochem Company 99% n-propyl benzoate

[0086] Example 1

[0087] (1) Preparation of the catalyst component

[0088] In a reactor which was sufficiently replaced by high-purity nitrogen, 4.8 g of magnesium chloride (50.4 mmol), 82 mL of toluene, 12.0 mL of tri-n-butyl phosphate, and 4.3 mL of epichlorohydrin were sequentially added, and the molar ratio of magnesium chloride, tri-n-butyl phosphate, epichlorohydrin, and toluene was 1:0.9:1.1:15.3. The temperature was raised to 70°C under stirring at 450 rpm, and the temperature was kept constant for 1.7 h to obtain a magnesium-containing complex solution. Then, 1.8 g of phthalic anhydride was added, and the reaction was continued for 0.7 h. Subsequently, the temperature was cooled to -40°C, and 67 mL of titanium tetrachloride, 1.2 mL of ethyl acetate, and 2 mL of ethanol were sequentially added dropwise. Then, the temperature was gradually raised to 90°C at a rate of 0.5°C / min, and the temperature was kept constant for 1 h to obtain a reaction mother liquor and a precipitate. The molar ratio of magnesium element, phthalic anhydride, titanium tetrachloride, ethyl acetate, and ethanol in the reaction mother liquor and the precipitate was 1:0.2:12.1:0.2:0.7. Subsequently, 3.2 mL of ethyl benzoate was added at 90°C, and the temperature was kept constant for 1 h. The molar ratio of magnesium element and ethyl benzoate in the system was 1:0.5. Then, the stirring was stopped, and the suspension was quickly separated into two layers. The upper clear liquid was removed, and the solid was washed twice with toluene and four times with hexane. The solid catalyst component was obtained by blowing dry with high-purity nitrogen. The performance parameters of the solid catalyst component are shown in Table 2.

[0089] (2) Slurry polymerization

[0090] Homopolymerization with low hydrogen / ethylene ratio: A 2 L stainless steel reactor was purged with high purity nitrogen, then 1 L hexane and 1.0 mL of triethylaluminum (1 mmol) with a concentration of 1 mol / L were added, followed by the addition of the catalyst component prepared above (containing 0.01 mmol Ti), and the temperature was raised to 70°C. Hydrogen was introduced to make the pressure in the reactor 0.28 MPa (gauge pressure), and then ethylene was introduced to make the total pressure in the reactor 0.73 MPa. Polymerization was carried out at 80°C for 2 hours. The polymerization results are shown in Tables 3 and 4.

[0091] Homopolymerization with low hydrogen / ethylene ratio: A 2 L stainless steel reactor was purged with high purity nitrogen, then 1 L hexane and 1.0 mL of triethylaluminum (1 mmol) with a concentration of 1 mol / L were added, followed by the addition of the catalyst component prepared above (containing 0.01 mmol Ti), and the temperature was raised to 70°C. Hydrogen was introduced to make the pressure in the reactor 0.28 MPa (gauge pressure), and then ethylene was introduced to make the total pressure in the reactor 0.73 MPa. Polymerization was carried out at 80°C for 2 hours. The polymerization results are shown in Tables 3 and 4.

[0092] Homopolymerization with low hydrogen / ethylene ratio: A 2 L stainless steel reactor was purged with high purity nitrogen, then 1 L hexane and 1.0 mL of triethylaluminum (1 mmol) with a concentration of 1 mol / L were added, followed by the addition of the catalyst component prepared above (containing 0.01 mmol Ti), and the temperature was raised to 70°C. Hydrogen was introduced to make the pressure in the reactor 0.28 MPa (gauge pressure), and then ethylene was introduced to make the total pressure in the reactor 0.73 MPa. Polymerization was carried out at 80°C for 2 hours. The polymerization results are shown in Tables 3 and 4.

[0093] The pressure in the reactor in the above polymerization reactions is gauge pressure.

[0094] Example 2

[0095] (1) Preparation of the catalyst component

[0096] In a reactor purged with high purity nitrogen, 4.8 g of magnesium chloride (50.4 mmol), 75 mL of toluene, 11.7 mL of tri-n-butyl phosphate, and 3.8 mL of epichlorohydrin were added successively, the molar ratio of magnesium chloride, tri-n-butyl phosphate, epichlorohydrin, and toluene being 1:0.9:1.0:14.0, and the reactor was warmed to 66°C with stirring at 300 rpm, and reacted for 1.4 h at constant temperature. A solution of magnesium complex was obtained. Then, 1.2 g of phthalic anhydride was added, and the reaction was continued for 0.4 h. Subsequently, the reactor was cooled to -35°C, and 59 mL of titanium tetrachloride, 1.5 mL of ethyl acetate, and 6 mL of butanol were added dropwise successively. The reactor was then warmed to 85°C at a rate of 0.9°C / min, and reacted for 1.2 h at constant temperature. The molar ratio of magnesium, phthalic anhydride, titanium tetrachloride, ethyl acetate, and butanol in the reaction mother liquor and the precipitate was 1:0.2:10.7:0.2:1.3. Subsequently, 3.6 mL of ethyl benzoate was added at 85°C, and the reaction was continued for 1.2 h at constant temperature. The molar ratio of magnesium to ethyl benzoate in the system was 1:0.5. Then, the stirring was stopped, and the suspension was allowed to separate into two layers. The supernatant was removed, and the precipitate was washed with toluene twice and hexane four times. The product was dried under high purity nitrogen to give a solid catalyst component having good fluidity. The performance parameters of the catalyst component are shown in Table 2.

[0097] (2) Slurry polymerization: The same procedure as in Example 1 was repeated using the catalyst component described above. The polymerization results are shown in Tables 3 and 4.

[0098] Example 3

[0099] (1) Preparation of catalyst component

[0100] In a reactor purged with high purity nitrogen, 3.1 g of magnesium fluoride (50.4 mmol), 33.0 mL of hexane, 7.0 mL of triisobutyl phosphate, and 1.8 mL of propylene oxide were added successively, the molar ratio of magnesium fluoride, triisobutyl phosphate, propylene oxide, and hexane was 1:0.5:0.5:5, the stirring speed was 400 rpm, the temperature was raised to 45°C, and the reaction was carried out for 6 h at this temperature. Then the temperature was lowered to 30°C, 0.1 mL of acetic anhydride was added, and the reaction was carried out for another 2 h. Then the temperature was lowered to -40°C, 52.8 mL of tetraethoxytitanium, 0.1 mL of methyl acetate, and 0.8 mL of 2-ethylhexanol were added successively, the temperature was raised to 50°C at a rate of 0.02°C / min, and the reaction was carried out for 10 h at this temperature. The molar ratio of magnesium element, acetic anhydride, tetraethoxytitanium, methyl acetate, and 2-ethylhexanol in the reaction mother liquor and the precipitate was 1:0.02:5:0.02:0.1. Then 0.6 mL of methyl benzoate was added at 50°C, and the reaction was carried out for another 5 min. The molar ratio of magnesium element to methyl benzoate in the system was 1:0.1. Then the stirring was stopped, and the suspension was separated into two layers. The upper clear liquid was removed, washed with toluene twice and hexane four times, and dried by blowing high purity nitrogen. A solid catalyst component with good fluidity was obtained, and its performance parameters are shown in Table 2.

[0101] (2) Slurry polymerization: the same as in Example 1, the above catalyst component was used, and the polymerization results are shown in Tables 3 and 4.

[0102] Example 4

[0103] (1) Preparation of the catalyst component

[0104] In a reactor purged with high purity nitrogen, 4.8 g of magnesium chloride (50.4 mmol), 89 mL of toluene, 13.1 mL of tri-n-butyl phosphate, and 3.7 mL of epichlorohydrin were added successively in the molar ratio of 1:1.0:0.9:16.6, and the mixture was stirred at 350 rpm and heated to 62°C. After 2 hours of constant temperature reaction, a magnesium complex solution was obtained. Then, 1.0 g of phthalic anhydride was added, and the reaction was continued for 0.5 h. Subsequently, the mixture was cooled to -32°C, and 69 mL of titanium tetrachloride, 1.8 mL of ethyl acetate, 1.5 mL of ethanol, and 4 mL of butanol were added dropwise successively. Thereafter, the mixture was gradually heated to 93°C at a rate of 0.6°C / min, and constant temperature reaction was performed for 0.9 h. Thus, a reaction mother liquor and a precipitate were obtained, and the molar ratio of magnesium, phthalic anhydride, titanium tetrachloride, ethyl acetate, ethanol, and butanol in the mixture was 1:0.1:12.5:0.2:0.5:0.9. Subsequently, 4.0 mL of ethyl benzoate was added at 93°C, and the mixture was further reacted at constant temperature for 0.9 h. The molar ratio of magnesium to ethyl benzoate in the system was 1:0.6. Then, 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 residue was washed with toluene twice and hexane four times, and dried under high purity nitrogen stream. Thus, a solid catalyst component having good fluidity was obtained. The performance parameters of the catalyst component are shown in Table 2.

[0105] (2) Slurry polymerization: The same procedure as in Example 1 was repeated using the above catalyst component. The polymerization results are shown in Tables 3 and 4.

[0106] Example 5

[0107] (1) Preparation of catalyst component

[0108] In a reactor purged with high purity nitrogen, 4.8 g of magnesium chloride (50.4 mmol), 103 mL of toluene, 15.8 mL of tri-n-butyl phosphate, and 3.5 mL of epichlorohydrin were added successively, the molar ratio of magnesium chloride, tri-n-butyl phosphate, epichlorohydrin, and toluene being 1:1.2:0.9:19.2, and the stirring speed was 350 rpm. The temperature was raised to 53°C, and the reaction was carried out at this temperature for 1.5 h. Then, 1.7 g of phthalic anhydride was added, and the reaction was carried out for another 0.5 h. Subsequently, the temperature was lowered to -37°C, and 58 mL of titanium tetrachloride and 0.7 mL of ethyl acetate were added dropwise successively. Then, the temperature was raised to 87°C at a rate of 0.3°C / min, and the reaction was carried out at this temperature for 1.5 h. The molar ratio of magnesium, phthalic anhydride, titanium tetrachloride, ethyl acetate, and ethanol in the reaction mother liquor and the precipitate was 1:0.2:10.5:0.1:2.7. Subsequently, 2.0 mL of ethyl benzoate was added at 87°C, and the reaction was carried out at this temperature for another 1.5 h. The molar ratio of magnesium and ethyl benzoate in the system was 1:0.3. Then, the stirring was stopped, and the suspension was allowed to separate. The supernatant was removed, and the precipitate was washed with toluene twice and with hexane four times. The product was dried under high purity nitrogen to give a solid catalyst component with good fluidity. The performance parameters of the catalyst component are shown in Table 2.

[0109] (2) Slurry polymerization: The same procedure as in Example 1 was used, except that the catalyst component described above was used. The polymerization results are shown in Tables 3 and 4.

[0110] Example 6

[0111] (1) Preparation of catalyst component

[0112] In a reactor purged with high purity nitrogen, 4.8 g of magnesium chloride (50.4 mmol), 85 mL of toluene, 11.0 mL of tri-n-butyl phosphate, and 3.1 mL of epichlorohydrin were added successively in the molar ratio of 1:0.8:0.8:15.9, and the mixture was stirred at 400 rpm and heated to 76°C. After 1.8 hours of reaction at constant temperature, a magnesium complex solution was obtained. Then, 1.6 g of phthalic anhydride was added, and the reaction was continued for 0.8 hours. After cooling to -43°C, 55 mL of titanium tetrachloride, 2.0 mL of ethyl acetate, and 1.8 mL of butanol were added dropwise successively, and the mixture was heated to 95°C at a rate of 0.7°C / min. After 0.6 hours of reaction at constant temperature, a reaction mother liquor and a precipitate were obtained, and the molar ratio of magnesium, phthalic anhydride, titanium tetrachloride, ethyl acetate, and butanol in the mixture was 1:0.2:10.0:0.3:0.4. Then, 2.7 mL of ethyl benzoate was added at 95°C, and the mixture was kept at constant temperature for 0.6 hours. The molar ratio of magnesium to ethyl benzoate in the system was 1:0.4. Then, the stirring was stopped, and the suspension was separated into two layers. The upper layer was removed, and the solid was washed with toluene twice and hexane four times. After drying under high purity nitrogen, a solid catalyst component with good fluidity was obtained. The performance parameters of the component are shown in Table 2.

[0113] (2) Slurry polymerization: The same as in Example 1, using the above catalyst component, and the polymerization results are shown in Tables 3 and 4.

[0114] Example 7

[0115] (1) Preparation of a catalyst component

[0116] In a reactor purged with high purity nitrogen, 14.0 g of magnesium iodide (50.4 mmol), 247.6 mL of xylene, 21.4 mL of triethyl phosphate, 10.3 mL of tetrahydrofuran were added successively, the molar ratio of magnesium iodide, triethyl phosphate, tetrahydrofuran and xylene was 1:2.5:2.5:40, the reactor was heated to 90°C with stirring at 300 rpm, and the temperature was kept constant for 1.2 hours to obtain a magnesium complex solution. Then 4.6 mL of acrylic anhydride was added, and the reaction was continued for 0.2 h, and then the temperature was cooled to 0°C. After the temperature was reached, 430.7 mL of tetrabutyl titanate, 46.4 mL of n-propyl acetate, 18.0 mL of ethanol, and 9.2 mL of butanol were added successively, and then the temperature was gradually increased to 110°C at a rate of 4.0°C / min, and the temperature was kept constant for 0.2 h to obtain a reaction mother liquor and a precipitate, wherein the molar ratio of magnesium, acrylic anhydride, tetrabutyl titanate, n-propyl acetate, ethanol and butanol was 1:0.8:25:8.0:6.0:2.0. Then 32.7 mL of n-propyl benzoate was added at 110°C, and the temperature was kept constant for 1 h, the molar ratio of magnesium and n-propyl benzoate in the system was 1:4.0. Then the stirring was stopped, and the suspension was quickly separated into two layers. The upper clear liquid was removed, washed with toluene twice, washed with hexane four times, and dried with high purity nitrogen to obtain a solid catalyst component with good flowability, and the performance parameters are shown in Table 2.

[0117] (2) Slurry polymerization reaction: the same as in Example 1, using the above catalyst component, the polymerization results are shown in Tables 3 and 4.

[0118] Example 8

[0119] (1) Preparation of catalyst component: the same as in Example 1.

[0120] (2) Slurry polymerization reaction

[0121] Low hydrogen ethylene homopolymerization: a 2L stainless steel reactor was purged with high purity nitrogen, 1L of cyclohexane and 1.0 mL of triisobutylaluminum (1 mmol) with a concentration of 1 mol / L were added, and then the catalyst component prepared by the above method (containing 0.005 mmol of Ti) was added, the temperature was increased to 70°C, hydrogen was introduced to make the pressure in the reactor 0.28 MPa (gauge pressure), and then ethylene was introduced to make the total pressure in the reactor 0.73 MPa, and the polymerization was carried out at 80°C for 2 hours, and the polymerization results are shown in Tables 3 and 4.

[0122] Homopolymerization of ethylene: A 2 L stainless steel reactor was purged with high purity nitrogen and charged with 1 L of heptane and 1.0 mL of 1 mol / L diethylaluminum chloride (1 mmol) and 0.05 mmol of the catalyst component prepared as described above. The reactor was heated to 75°C and pressurized to 0.58 MPa (gauge pressure) with hydrogen and then pressurized to 0.73 MPa with ethylene. The polymerization was carried out at 85°C for 2 hours. The results are shown in Tables 3 and 4.

[0123] The pressure in the reactor in the above polymerization is gauge pressure.

[0124] Comparative Example 1

[0125] (1) Preparation of the catalyst component

[0126] A reactor was purged with high purity nitrogen and charged with 4.8 g of magnesium chloride (50.4 mmol), 82 mL of toluene, 12.0 mL of tri-n-butyl phosphate, and 4.3 mL of epichlorohydrin. The molar ratio of magnesium chloride, tri-n-butyl phosphate, epichlorohydrin, and toluene was 1:0.9:1.1:15.3. The reactor was heated to 70°C with stirring at 450 rpm and held at that temperature for 1.7 hours to obtain a solution of the magnesium-containing complex. Then, 1.8 g of phthalic anhydride was added and the reaction was continued for 0.7 hours. The reactor was then cooled to -40°C and 67 mL of titanium tetrachloride, 1.2 mL of ethyl acetate, and 2 mL of ethanol were added dropwise. The reactor was then heated to 90°C at a rate of 0.5°C / min and held at that temperature for 1 hour to obtain a reaction mother liquor and a precipitate. The molar ratio of magnesium, phthalic anhydride, titanium tetrachloride, ethyl acetate, and ethanol in the precipitate was 1:0.2:12.1:0.2:0.7. The stirring was then stopped and the reactor was allowed to stand. The supernatant was removed and the precipitate was washed with toluene twice and hexane four times. The precipitate was then dried with high purity nitrogen to obtain a solid catalyst component having good flowability. The performance parameters of the catalyst component are shown in Table 2.

[0127] (2) Slurry polymerization: The same procedure as in Example 1 was used with the catalyst component described above. The results are shown in Tables 3 and 4.

[0128] Comparative Example 2

[0129] (1) Preparation of the catalyst component

[0130] In a reactor purged with high purity nitrogen, 4.8 g magnesium chloride (50.4 mmol), 75 mL toluene, 11.7 mL tri-n-butyl phosphate, 3.8 mL epichlorohydrin were added successively, the molar ratio of magnesium chloride, tri-n-butyl phosphate, epichlorohydrin and toluene was 1:0.9:1.0:14.0, the temperature was increased to 66°C with stirring at 300 rpm, and the temperature was kept constant for 1.4 h to obtain a magnesium complex solution. Then 1.2 g phthalic anhydride was added, and the reaction was continued for 0.4 h. Then the temperature was decreased to -35°C, and 59 mL titanium tetrachloride, 1.5 mL ethyl acetate, and 6 mL butanol were added successively dropwise. Then the temperature was increased to 85°C at a rate of 0.9°C / min, and the temperature was kept constant for 1.2 h to obtain a reaction mother liquor and a precipitate, the molar ratio of magnesium element, phthalic anhydride, titanium tetrachloride, ethyl acetate and butanol in the precipitate being 1:0.2:10.7:0.2:1.3. Then the stirring was stopped, and the suspension was separated into two layers. The upper clear solution was removed, and the solid was washed with toluene twice and hexane four times. The solid was dried under high purity nitrogen to obtain a solid catalyst component with good fluidity. The performance parameters of the catalyst component are shown in Table 2.

[0131] (2) Slurry polymerization: Same as Example 1, using the catalyst component described above, the polymerization results are shown in Tables 3 and 4.

[0132] Comparative Example 3

[0133] (1) Preparation of catalyst component

[0134] In a reactor purged with high purity nitrogen, 4.8 g magnesium chloride (50.4 mmol), 89 mL toluene, 13.1 mL tri-n-butyl phosphate, 3.7 mL epichlorohydrin were added successively, the molar ratio of magnesium chloride, tri-n-butyl phosphate, epichlorohydrin and toluene was 1:1.0:0.9:16.6, the temperature was increased to 62°C with stirring at 350 rpm, and the temperature was kept constant for 2 h to obtain a magnesium complex solution. Then 1.0 g phthalic anhydride was added, and the reaction was continued for 0.5 h. Then the temperature was decreased to -32°C, and 69 mL titanium tetrachloride, 1.8 mL ethyl acetate, 1.5 mL ethanol, and 4 mL butanol were added successively dropwise. Then the temperature was increased to 93°C at a rate of 0.6°C / min, and the temperature was kept constant for 0.9 h to obtain a reaction mother liquor and a precipitate, the molar ratio of magnesium element, phthalic anhydride, titanium tetrachloride, ethyl acetate, ethanol and butanol in the precipitate being 1:0.1:12.5:0.2:0.5:0.9. Then the stirring was stopped, and the suspension was separated into two layers. The upper clear solution was removed, and the solid was washed with toluene twice and hexane four times. The solid was dried under high purity nitrogen to obtain a solid catalyst component with good fluidity. The performance parameters of the catalyst component are shown in Table 2.

[0135] (2) Slurry polymerization: Same as Example 1, using the catalyst component described above, the polymerization results are shown in Tables 3 and 4.

[0136] Comparative Example 4

[0137] (1) Preparation of catalyst component

[0138] Into a reactor purged with high purity nitrogen, 4.8 g of magnesium chloride (50.4 mmol), 103 mL of toluene, 15.8 mL of tri-n-butyl phosphate, and 3.5 mL of epichlorohydrin were added successively in the molar ratio of 1:1.2:0.9, and the mixture was stirred at 350 rpm and heated to 53°C. After 1.5 hours of constant temperature reaction, 1.7 g of phthalic anhydride was added, and the reaction was continued for 0.5 hours. Then, the mixture was cooled to -37°C, and 58 mL of titanium tetrachloride, 0.7 mL of ethyl acetate, and 8.0 mL of ethanol were added successively dropwise. Thereafter, the mixture was gradually heated to 87°C at a rate of 0.3°C / min, and the constant temperature reaction was performed for 1.5 hours. The reaction mother liquor and precipitate were obtained, and the molar ratio of magnesium element, phthalic anhydride, titanium tetrachloride, ethyl acetate, and ethanol was 1:0.2:10.5:0.1:2.7. Then, the stirring was stopped, and the suspension was quickly separated into two layers. The upper clear solution was removed, and the obtained solid catalyst component was washed twice with toluene and four times with hexane, and then dried under high purity nitrogen to obtain a solid catalyst component having good fluidity. The performance parameters of the catalyst component are shown in Table 2.

[0139] (2) Slurry polymerization reaction: The same as in Example 1, using the above catalyst component, and the polymerization results are shown in Tables 3 and 4.

[0140] Comparative Example 5

[0141] (1) Preparation of catalyst component

[0142] Into a reactor purged with high purity nitrogen, 4.8 g of magnesium chloride (50.4 mmol), 85 mL of toluene, 11.0 mL of tri-n-butyl phosphate, and 3.1 mL of epichlorohydrin were added successively in the molar ratio of 1:0.8:0.8, and the mixture was stirred at 400 rpm and heated to 76°C. After 1.8 hours of constant temperature reaction, 1.6 g of phthalic anhydride was added, and the reaction was continued for 0.8 hours. Then, the mixture was cooled to -43°C, and 55 mL of titanium tetrachloride, 2.0 mL of ethyl acetate, and 1.8 mL of butanol were added successively dropwise. Thereafter, the mixture was gradually heated to 95°C at a rate of 0.7°C / min, and the constant temperature reaction was performed for 0.6 hours. The reaction mother liquor and precipitate were obtained, and the molar ratio of magnesium element, phthalic anhydride, titanium tetrachloride, ethyl acetate, and butanol was 1:0.2:10.0:0.3:0.4. Then, the stirring was stopped, and the suspension was quickly separated into two layers. The upper clear solution was removed, and the obtained solid catalyst component was washed twice with toluene and four times with hexane, and then dried under high purity nitrogen to obtain a solid catalyst component having good fluidity. The performance parameters of the catalyst component are shown in Table 2.

[0143] (2) Slurry polymerization: same as example 1, using the catalyst component described above, the polymerization results are shown in table 3 and table 4.

[0144] The following tests were performed on the catalyst components prepared in step (1) of the above examples and comparative examples:

[0145] 1. Relative weight percentage of titanium element in the catalyst component: determined by spectrophotometry.

[0146] 2. Particle size distribution of the catalyst component: determined by Malvern laser particle size analyzer.

[0147] The specific test results are shown in table 2 below.

[0148] Table 2

[0149] Number Ti (wt%) Average particle size D50 (μm) Particle size distribution span Example 1 3.4 4.8 1.02 Example 2 3.3 4.0 1.05 Example 3 4.1 3.6 1.34 Example 4 3.5 6.6 1.07 Example 5 3.6 4.1 1.03 Example 6 3.2 4.3 1.04 Example 7 2.9 8.7 1.29 Comparative Example 1 3.3 4.8 1.03 Comparative Example 2 3.2 4.0 1.04 Comparative Example 3 3.4 6.6 1.08 Comparative Example 4 3.5 4.1 1.05 Comparative Example 5 3.1 4.3 1.06

[0150] As shown in table 2, the span value of the particle size distribution of the catalyst component prepared in the examples of the present application can reach a value close to that of the comparative examples, and the particle size distribution is narrow.

[0151] The following tests were performed on the polymers obtained after slurry polymerization in step (2) of the above examples and comparative examples:

[0152] 1. Bulk density of polymer powder: determined by ASTM D1895-1996 (2003) Test Method for Plastic Volume Resistivity, Bulk Factor, and Pourability.

[0153] 2. Determination of polymer powder melt index (MFR): determined according to GB / T 3682.1-2018, load 2.16 kg, 190°C.

[0154] 3. Determination of polymer powder particle size distribution: sieving determination by German Retsch sieve shaker.

[0155] 4. Determination of polymerization activity: the ratio of the mass of the powder obtained after the polymerization reaction to the mass of the catalyst component is recorded as the polymerization activity of the catalyst.

[0156] The specific test results are shown in table 3 and table 4.

[0157] Table 3

[0158]

[0159] As shown by the results in Table 3, compared with the catalyst of the comparative example, the catalyst of the inventive example has a great increase in the polymerization activity and melt index under the condition of high hydrogen / ethylene ratio, indicating that the hydrogen regulation sensitivity under the condition of high hydrogen / ethylene ratio is greatly improved, and the melt index under the condition of low hydrogen / ethylene ratio does not change significantly, indicating that the hydrogen regulation sensitivity under the condition of low hydrogen / ethylene ratio is moderate. The catalyst with high hydrogen regulation sensitivity under the condition of high hydrogen / ethylene ratio and moderate hydrogen regulation sensitivity under the condition of low hydrogen / ethylene ratio can greatly reduce the hydrogen consumption in the production of multimodal polyethylene resin, and can avoid the occurrence of "pitting" of pipe material and "crystallization point" of film material in the production of PE100 grade pipe material resin and multimodal film material resin. The catalyst of the inventive example has a high bulk density of the prepared powder, and the bulk density of the powder under the condition of low hydrogen / ethylene ratio can be ≥0.36 g / mL.

[0160] Table 4

[0161]

[0162] As shown by the results in Table 4, the polymerization powder prepared by the catalyst of the inventive example has a great decrease in the content of fine powder with a size of less than 75 μm, and almost no fine powder.

[0163] As can be known from the above conclusion, the present application first discloses a catalyst component. The catalyst component has a concentrated particle size distribution; the hydrogen regulation sensitivity of the catalyst component under the condition of high hydrogen / ethylene ratio is greatly improved, and the hydrogen regulation sensitivity under the condition of low hydrogen / ethylene ratio is moderate. The catalyst with high hydrogen regulation sensitivity under the condition of high hydrogen / ethylene ratio and moderate hydrogen regulation sensitivity under the condition of low hydrogen / ethylene ratio can greatly reduce the hydrogen consumption in the production of multimodal polyethylene resin, and can avoid the occurrence of "pitting" of pipe material and "crystallization point" of film material in the production of PE100 grade pipe material resin and multimodal film material resin. The catalyst component can catalyze the polymerization of ethylene to obtain powder particles with high bulk density, and the content of fine powder with a size of less than 75 μm in the polymerization powder is greatly reduced, and almost no fine powder is present.

[0164] Obviously, the above-mentioned embodiments of the present application are only examples for clearly illustrating the present application, and are not intended to limit the embodiments of the present application. For those skilled in the art, other different forms of changes or modifications can be made on the basis of the above description, and it is impossible to enumerate all the embodiments here. Any obvious changes or modifications derived from the technical solutions of the present application still fall within the protection scope of the present application

[0165] It should be noted that the above-mentioned examples serve only to illustrate the application and are not to be construed as limiting the application in any way. The application has been described in great detail in the foregoing disclosure with reference to certain embodiments. It should be understood that the words which have been used are words of description and illustration, and are not to be construed as limiting the application in any way. Modifications and alterations of the application will occur to those skilled in the art upon reading the preceding disclosure and it is intended to include all such modifications and alterations insofar as they come within the scope of the claims. Although the application has been described in connection with specific embodiments thereof, it will be understood that the application is not limited to the specific embodiments disclosed, but rather, it will be understood to be broadly within the appended claims, as well as within the further scope of equivalents thereof.

[0166] All publications, patents, patent applications and other references mentioned in this specification are herein incorporated by reference. Unless otherwise defined, all technical and scientific terms used in this specification are to be taken as commonly understood terms within the skill of the art. In the case of conflict between the present specification and the definitions of terms, the present specification controls.

[0167] When the specification states a genus of elements with disclosure of examples, it is intended to convey that the genus can be limited to the disclosed examples, unless otherwise indicated. When the specification states a genus of elements without disclosure of examples, it is intended to convey that the genus can include any member of the genus regardless of whether or not the member is known or listed elsewhere.

[0168] The endpoints of the ranges and any values described in this application document are not to be understood as being limited to the exact values recited as the exact dimensions are not critical unless expressly stated otherwise. Any numerical range recited is intended to include all sub-ranges subsumed therein. For ranges including numeric values that are not divisible by one, the range is intended to include one half of the lower value and half, rounded up, of the higher value. For ranges including numeric values that are divisible by one, the range is intended to include the lower value and the higher value. Any reference to priority documents, including priority documents that are not available in the United States, is not intended to constitute a admission that the priority documents are prior art with respect to the present application.

[0169] In the context of the present specification, except in the event of a specific definition, any use of an article in the singular or plural can be modified in meaning and scope by the context in which it is used. In the context of the present specification, the word "comprising" does not exclude the presence of unrecited elements or limitations; the word "a" or "an" preceding an element does not exclude the presence of a plurality of such elements; and a statement that one or more thing is "based on" one or more thing does not preclude additional non-recited thing based on which the one or more thing is based.

[0170] Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are all considered to be part of the original disclosure or original description of the present application, and should not be considered to be new content that has not been disclosed or anticipated herein, unless the combination is deemed to be obviously unreasonable by those skilled in the art.

Claims

1. A catalyst component for the polymerization of olefins, characterized by The catalyst component comprises a reaction product of the following components: a magnesium-containing complex solution, an organic acid anhydride compound, a titanium compound, an acetate compound, a first alcohol compound, and an aromatic ester compound; The molar ratio of the magnesium element, the organic acid anhydride compound, the titanium compound, the acetate compound, the first alcohol compound, and the aromatic ester compound in the catalyst component is 1: (0.01-1): (2-30): (0.01-10.0): (0.05-10.0): (0.01-5.0).

2. The catalyst component according to claim 1, wherein: The molar ratio of the magnesium element, the organic acid anhydride compound, the titanium compound, the acetate compound, the first alcohol compound, and the aromatic ester compound in the catalyst component is 1: (0.02-0.5): (5-25): (0.02-5.0): (0.1-5.0): (0.1-3.0).

3. The catalyst component of claim 1, characterized by The magnesium-containing complex solution is prepared from raw materials comprising: a magnesium halide, an organic phosphorus compound, an organic epoxy compound, and an inert diluent; The molar ratio of the magnesium element, the organic phosphorus compound, the organic epoxy compound, and the inert diluent in the magnesium halide is 1: (0.1-3.0): (0.1-3.0): (1-50), preferably 1: (0.5-1.5): (0.5-1.5): (5-20).

4. The catalyst component according to claim 3, wherein: The magnesium halide is a magnesium dihalide and / or a complex of the magnesium dihalide with at least one of water, a second alcohol compound, an electron donor; preferably, the magnesium dihalide is at least one of magnesium dichloride, magnesium dibromide, magnesium difluoride, magnesium diiodide, and / or the second alcohol compound 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 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, preferably at least one of triethyl phosphate, tri-n-butyl phosphate, tri-i-butyl phosphate, tri-i-octyl phosphate, triphenyl phosphate, triethyl phosphite, tri-n-butyl phosphite, tri-i-butyl phosphite, di-n-butyl phosphite; and / or, The organic epoxide compound is at least one of aliphatic olefin, aliphatic diene, halogenated aliphatic olefin, halogenated aliphatic diene, oxide, glycidyl ether, internal ether; preferably, the number of carbon atoms of the organic epoxide compound is 2-8; more preferably, the organic epoxide compound is at least one of oxirane, oxetane, butyloxirane, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran, further preferably at least one of oxirane, oxetane, epichlorohydrin, tetrahydrofuran; and / or, The inert diluent is at least one of C6-C10 alkane and derivatives thereof and / or C6-C8 aromatic hydrocarbon and derivatives thereof, preferably at least one of hexane, heptane, octane, decane, benzene, toluene, xylene.

5. The catalyst component according to claim 1 or 2, wherein: The structure of the organic anhydride compound is shown in formula (I): In formula (I), R1 and R2 can be the same or different, and are independently selected from hydrogen, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl or C6-C10 aromatic hydrocarbon group; and / or, R1 and R2 can be arbitrarily ringed; 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 chemical formula of the titanium compound is TiX n (OR) 4-n wherein X is halogen, R is a C1-C14 aliphatic hydrocarbon group or a C6-C14 aromatic hydrocarbon group, and n is any integer from 0 to 4; preferably, the titanium compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetraethoxide, titanium tetrabutoxide, titanium chloride triethoxide, titanium dichloride diethoxide, titanium chloride monoethoxide, more preferably at least one of titanium tetrachloride, titanium tetraethoxide, titanium tetrabutoxide; and / or, The chemical formula of the acetic ester compound is CH3COOR7, wherein R7 is C1-C10 alkyl, C2-C10 alkenyl, C3-C10 cycloalkyl, C2-C10 alkynyl or C6-C10 aromatic hydrocarbon group, preferably 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; and / or, The first alcohol compound is C1-C12 aliphatic alcohol and its derivative substituted alcohol and / or C7-C12 aromatic alcohol and its derivative substituted alcohol, preferably at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, benzyl alcohol, phenethyl alcohol, more preferably at least one of ethanol, isopropanol, butanol, 2-ethylhexanol, benzyl alcohol, phenethyl alcohol; and / or, The chemical formula of the aromatic ester compound is C5H5[(CH2) n COOR9], wherein R9 is a C1-C10 aliphatic hydrocarbon group or a C1-C10 aromatic hydrocarbon group, and n is any integer from 0 to 9; preferably, the aromatic ester compound is at least one of methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, octyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, hexyl phenylacetate, and octyl phenylacetate.

6. A preparation method of the catalyst component for olefin polymerization according to any one of claims 1-5, the method comprising: S1: dissolving the magnesium halide in the organic phosphorus compound, organic epoxide compound and inert diluent, and reacting at elevated temperature to obtain the magnesium-containing complex solution; S2: mixing the magnesium-containing complex solution with the organic anhydride compound, reacting at elevated temperature to obtain a first mixture, and then cooling; S3: reacting the first mixture with the titanium compound to obtain a second mixture; and S4: mixing the second mixture with the first alcohol compound to obtain the catalyst component. S4: reacting the second mixture with the first alcohol compound to obtain a reaction mother liquor and a precipitate; S5: aging the reaction mother liquor and the precipitate, and filtering, washing, and precipitating to obtain the catalyst component; Preferably, the aromatic ester compound is added in at least one of steps S3, S4, and S5, and more preferably, the aromatic ester compound is added in steps S4 and / or S5. Preferably, the acetic ester compound is added in at least one of steps S1, S2, S3, S4, and S5, and more preferably, the acetic ester compound is added in step S4.

7. The method of claim 6, wherein: In step S1, the reaction temperature of the warming reaction is 30-120°C, preferably 40-80°C, and / or the reaction time is 0.1-15 hours, preferably 1-3 hours; and / or In step S2, the reaction temperature of the warming reaction is 30-120°C, preferably 40-80°C, and / or the reaction time is 0.1-15 hours, preferably 0.2-3 hours; and / or the temperature after the cooling is -60-0°C, preferably -50--20°C; and / or In step S3, the reaction temperature is -60-0°C, preferably -50--20°C; and / or In step S4, the reaction temperature of the warming reaction is 40-120°C, preferably 80-100°C, and / or the reaction time is 0.1-15 hours, preferably 0.5-10 hours, and / or the warming rate is 0.01-5.0°C / min, preferably 0.1-2.0°C / min; and / or In step S5, the temperature of the aging treatment is 40-120°C, preferably 80-100°C, and / or the aging treatment time is 0.01-10 hours, preferably 0.1-5 hours.

8. A catalyst for the polymerization of olefins, characterized in that The catalyst comprises: an organic aluminum compound and the catalyst component of claims 1-5 or the catalyst component prepared by the method of claims 6 or 7; The molar ratio of titanium in the catalyst component to aluminum in the organic aluminum compound is 1:(20-200), preferably 1:(50-100).

9. The catalyst of claim 8, wherein: The organic aluminum compound has the chemical formula AlR' d X' 3-d wherein R' is hydrogen or a Cl-C20 hydrocarbon group, X' is a halogen atom, and d is any integer from 0 to 3; 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)3, more preferably Al(CH2CH3)3 and / or Al(i-Bu)3.

10. Use of the catalyst of claims 8 and 9 in olefin polymerization, preferably, the olefin polymerization is ethylene polymerization; more preferably, the ethylene polymerization is homopolymerization of ethylene or copolymerization of ethylene and an α-olefin; and / or the ethylene polymerization is slurry polymerization or gas phase polymerization; further preferably, the slurry polymerization medium comprises at least one of saturated aliphatic hydrocarbons and / or aromatic hydrocarbons, preferably isobutane, n-hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene, more preferably at least one of toluene, n-hexane, and cyclohexane.

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