A catalyst component for ethylene polymerization, preparation method thereof, catalyst and application thereof

Abstract

The present invention belongs to the field of catalyst technology and discloses a catalyst component for ethylene polymerization, its preparation method, catalyst, and application. The catalyst component comprises the reaction product of the following components: 1) a spherical or quasi-spherical solid catalyst component B; 2) an alcohol compound; 3) a second organic epoxy compound; and 4) a second titanium compound. The spherical or quasi-spherical solid catalyst component B comprises the reaction product of a magnesium complex, an organic anhydride compound, an acetate compound, and the first titanium compound. The catalyst exhibits high polymerization activity and hydrogen modulation sensitivity for ethylene polymerization.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysts, and in particular relates to a catalyst component for ethylene polymerization, a method for preparing the catalyst component, a catalyst comprising the catalyst component, and applications of the catalyst component and the catalyst. Background Art

[0002] Ziegler-Natta-type olefin polymerization catalyst particles possess the unique ability to replicate their morphology in the polyolefin powder particles they produce. For example, spherical / ellipsoidal catalyst particles typically produce spherical / ellipsoidal powder particles, and high-porosity catalyst particles typically produce high-porosity powder particles. Because spherical / ellipsoidal polyolefin powder particles have excellent flowability and high bulk density, a simple method for producing these powder particles would have promising industrial prospects.

[0003] Dissolution-precipitation catalysts offer a shorter preparation process and greater control over catalyst particle shape, making them a preferred choice. The N-series polyolefin catalysts from the Beijing Research Institute of Chemical Industry are typical examples of dissolution-precipitation catalysts. These catalyst particles are non-spherical, typically with a particle size less than 50 μm. The powder particles obtained from ethylene polymerization are also non-spherical. Precise control over the precipitation and formation of catalyst particles is essential for producing narrowly distributed, spherical / ellipsoidal N-type polyolefin catalyst particles.

[0004] For example, patent document CN201410531766.2 introduces organic anhydrides, acetates, and cyclic ketones as composite electron donors, resulting in the first preparation of spherical / ellipsoidal polyethylene catalyst particles. These catalysts can be subjected to ethylene slurry polymerization / copolymerization to produce spherical / ellipsoidal powder particles. However, the polymerization activity and hydrogen sensitivity of these spherical / ellipsoidal polyethylene catalysts are relatively low, failing to meet the requirements of some industrial slurry polyethylene production plants for high-activity and high hydrogen sensitivity catalysts.

[0005] Therefore, it is necessary to prepare a spherical / ellipsoidal polyethylene catalyst with high activity and high hydrogen adjustment sensitivity, and the catalyst can be polymerized to obtain spherical / ellipsoidal powder particles. Summary of the Invention

[0006] In response to the above situation, the inventors of the present invention have discovered that treating a spherical / quasi-spherical solid catalyst component with an alcohol compound, an organic epoxy compound, and a titanium compound can significantly improve the catalyst's polymerization activity and hydrogen sensitivity, resulting in spherical / ellipsoidal powder particles. Based on this, the present invention provides a catalyst component for ethylene polymerization, a preparation method, a catalyst, and its use.

[0007] A first aspect of the present invention provides a catalyst component for ethylene polymerization, the catalyst component comprising the reaction product of:

[0008] 1) Spherical or quasi-spherical solid catalyst component B;

[0009] 2) alcohol compounds;

[0010] 3) a second organic epoxy compound;

[0011] 4) a second titanium compound;

[0012] The spherical or quasi-spherical solid catalyst component B comprises a reaction product of a magnesium complex, an organic acid anhydride compound, an acetate compound and a first titanium compound.

[0013] The second aspect of the present invention provides a method for preparing the above-mentioned catalyst component for ethylene polymerization, which is selected from the following method 1 or method 2, wherein:

[0014] Method 1 includes the following steps:

[0015] (1) dispersing a spherical or quasi-spherical solid catalyst component B in an inert solvent to form a suspension;

[0016] (2) contacting the suspension obtained in step (1) with an alcohol compound and a second organic epoxy compound;

[0017] (3) removing unreacted materials and solvent from the mixture obtained in step (2), washing the mixture, and preparing a suspension containing a solid intermediate;

[0018] (4) contacting the suspension obtained in step (3) with an alcohol compound and a second titanium compound to react;

[0019] (5) removing unreacted substances and solvent from the mixture obtained in step (4), washing the mixture, and obtaining the catalyst component;

[0020] Method 2 includes the following steps:

[0021] 1) dispersing a spherical or quasi-spherical solid catalyst component B in an inert solvent to form a suspension;

[0022] 2) contacting the suspension obtained in step 1) with an alcohol compound and a second organic epoxy compound for reaction;

[0023] 3) contacting the suspension obtained in step 2) with a second titanium compound to react;

[0024] 4) removing unreacted substances and solvent from the mixture obtained in step 3), and washing the mixture to obtain the catalyst component.

[0025] A third aspect of the present invention provides a catalyst for ethylene polymerization, the catalyst comprising the following components:

[0026] M) the above-mentioned catalyst component or the catalyst component prepared by the above-mentioned preparation method;

[0027] N) general formula is AlR' d X' 3-d An organoaluminum compound, wherein R' is hydrogen or C1-C 20 Hydrocarbyl group, X' is a halogen atom, preferably fluorine, chlorine or bromine, 0<d≤3.

[0028] The fourth aspect of the present invention provides the use of the above-mentioned catalyst component, the catalyst component prepared by the above-mentioned preparation method, or the above-mentioned catalyst in ethylene polymerization.

[0029] The catalyst of the present invention exhibits high polymerization activity and hydrogen sensitivity for ethylene polymerization. Under polymerization conditions of 0.28 MPa hydrogen partial pressure, 0.45 MPa ethylene partial pressure, 80°C temperature, and 2 hours, the polymerization activity exceeds 25,000 gPE / gCat. Under polymerization conditions of 0.58 MPa hydrogen partial pressure, 0.15 MPa ethylene partial pressure, 85°C temperature, and 2 hours, the melt index exceeds 380 g / 10 minutes. The resulting polyethylene powder is spherical or ellipsoidal in shape.

[0030] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is an electron microscope photograph of the spherical or quasi-spherical solid catalyst component B1.

[0032] Figure 2 This is an electron microscope photograph of catalyst component 1.

[0033] Figure 3 This is an electron microscope photograph of the polymer obtained by low hydrogen-to-ethyl ratio polymerization in Example 1.

[0034] Figure 4 This is an electron microscope photograph of the polymer obtained by low hydrogen-to-ethyl ratio polymerization in Example 1.

[0035] Figure 5 This is an electron microscope photograph of catalyst component 2.

[0036] Figure 6 This is an electron microscope photograph of the polymer obtained by low hydrogen-to-ethyl ratio polymerization in Example 2.

[0037] Figure 7 This is an electron microscope photograph of the polymer obtained by low hydrogen-to-ethyl ratio polymerization in Example 2.

[0038] Figure 8 This is an electron microscope photograph of the polymer obtained by high hydrogen-to-ethyl ratio polymerization in Example 2.

[0039] Figure 9 This is an electron microscope photograph of the polymer obtained by high hydrogen-to-ethyl ratio polymerization in Example 2.

[0040] Figure 10 This is an electron microscope photograph of catalyst component D2.

[0041] Figure 11 This is an electron microscope photograph of the polymer prepared by low hydrogen-to-ethyl ratio polymerization in comparative example 2.

[0042] Figure 12 This is an electron microscope photograph of the polymer prepared by low hydrogen-to-ethyl ratio polymerization in comparative example 2. DETAILED DESCRIPTION

[0043] The following is a detailed description of the specific embodiments of the present invention. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention.

[0044] According to a first aspect of the present invention, there is provided a catalyst component for ethylene polymerization, the catalyst component comprising the reaction product of:

[0045] 1) Spherical or quasi-spherical solid catalyst component B;

[0046] 2) alcohol compounds;

[0047] 3) a second organic epoxy compound;

[0048] 4) a second titanium compound;

[0049] The spherical or quasi-spherical solid catalyst component B comprises a reaction product of a magnesium complex, an organic acid anhydride compound, an acetate compound and a first titanium compound.

[0050] In the present invention, the magnesium complex is a complex formed by dissolving magnesium halide in a solvent system containing a first organic epoxy compound and an organic phosphorus compound.

[0051] According to the present invention, the magnesium halide may be magnesium dichloride, magnesium dibromide, magnesium difluoride or magnesium diiodide, preferably magnesium dichloride.

[0052] In the present invention, the first organic epoxy compound can be selected from C2-C 18At least one of an oxide, glycidyl ether, and internal ether of an aliphatic olefin, an aliphatic diene, a halogenated aliphatic olefin, or a halogenated aliphatic diene. Specifically, the first organic epoxy compound may be at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, and butyl glycidyl ether.

[0053] In the present invention, the organophosphorus compound can be a hydrocarbon ester or a halogenated hydrocarbon ester of orthophosphoric acid or phosphorous acid, preferably at least one selected from triethyl phosphate, tri-n-butyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite and di-n-butyl phosphite.

[0054] According to the present invention, the structure of the organic anhydride compound is shown in formula (I):

[0055]

[0056] In formula (I), R5 and R6 are the same or different and are independently hydrogen, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C3-C 10 Cycloalkyl or C6-C 10 An aromatic hydrocarbon group, and R5 and R6 may arbitrarily form a ring.

[0057] Preferably, the organic acid anhydride compound is at least one selected from acetic anhydride, propionic anhydride, butyric anhydride, acrylic anhydride, phthalic anhydride, crotonic anhydride and maleic anhydride.

[0058] In the present invention, the general formula of the acetate compound is CH3COOR7, wherein R7 is C1-C 10 Alkyl, C2-C 10 Alkenyl, C3-C 10 Cycloalkyl, C2-C 10 Alkynyl or C6-C 10 R7 is an aromatic hydrocarbon group, preferably, R7 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl or n-hexyl.

[0059] Specifically, the acetate compound can be at least one selected from methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate and n-octyl acetate.

[0060] According to the present invention, the general formula of the first titanium compound is Ti(OR8) a X b , where R8 is C1-C 10wherein the first titanium compound is an aliphatic or aromatic hydrocarbon group, X is a halogen, preferably fluorine, chlorine, or bromine, a is 0, 1, or 2, b is an integer from 1 to 4, and a+b=3 or 4. Specifically, the first titanium compound may be at least one of titanium tetrachloride, titanium tetrabromide, tetraethoxytitanium, triethoxytitanium monochloride, titanium trichloride, diethoxytitanium dichloride, and triethoxytitanium monochloride.

[0061] In the present invention, the preparation method of the spherical or quasi-spherical solid catalyst component B comprises the following steps:

[0062] S1, dissolving magnesium halide in a solvent system containing a first organic epoxy compound and an organic phosphorus compound to form a uniform solution;

[0063] S2, reacting the solution obtained in step S1 with an organic acid anhydride compound and an acetate compound, and then contacting the solution with a first titanium compound, and then heating the solution to precipitate magnesium / titanium-containing solid particles;

[0064] S3, removing unreacted materials and solvent from the mixture obtained in step S2, washing the mixture, and obtaining a solid catalyst component B.

[0065] Preferably, per mole of magnesium halide, the amount of the first organic epoxy compound is 0.2-10 moles; the amount of the organic phosphorus compound is 0.1-10 moles; the amount of the organic anhydride compound is 0.03-1.0 moles; the amount of the acetate compound is 0.01-1 mole; and the amount of the first titanium compound is 0.5-120 moles.

[0066] Preferably, in step S1, the dissolution temperature is 50-70° C. and the dissolution time is 1-3 hours.

[0067] Preferably, in step S2, the reaction temperature of the solution with the organic anhydride compound and the acetate compound is the same as the dissolution temperature, the reaction time is 0.5-2 hours, the temperature of the system after the reaction is reduced to -60°C to -20°C, and then contacted with the first titanium compound; the heating is gradually increased, and the heating rate can be 0.2-2°C / min, and the temperature is increased to 75°C-100°C.

[0068] According to the present invention, the alcohol compound is selected from C1-C 18 The aliphatic alcohol or aromatic alcohol is preferably at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isooctyl alcohol, benzyl alcohol, phenylethyl alcohol, ethylene glycol, propylene glycol, butanediol, hexanediol and isohexanediol.

[0069] In the present invention, the second organic epoxy compound can be selected from C2-C 18The second organic epoxy compound is preferably at least one of an oxide, glycidyl ether, and internal ether of an aliphatic olefin, an aliphatic diene, a halogenated aliphatic olefin, or a halogenated aliphatic diene. The second organic epoxy compound is preferably at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, and butyl glycidyl ether. The second organic epoxy compound in the present invention may be the same as or different from the first organic epoxy compound.

[0070] According to the present invention, the second titanium compound has the general formula Ti(OR8) a X b , where R8 is C1-C 10 wherein X is a halogen, preferably fluorine, chlorine, or bromine; a is 0, 1, or 2; b is an integer from 1 to 4, and a + b = 3 or 4. The second titanium compound is preferably at least one of titanium tetrachloride, titanium tetrabromide, tetraethoxytitanium, triethoxytitanium monochloride, titanium trichloride, diethoxytitanium dichloride, and triethoxytitanium monochloride. The second titanium compound in the present invention may be the same as or different from the first titanium compound.

[0071] Preferably, based on each mole of magnesium in the spherical or quasi-spherical solid catalyst component B, the amount of the alcohol compound is 0.05-2.0 moles; the amount of the second organic epoxy compound is 0.01-0.5 moles; and the amount of the second titanium compound is 0.5-15 moles.

[0072] According to the second aspect of the present invention, the present invention provides a method for preparing the above-mentioned catalyst component for ethylene polymerization, which is selected from the following method 1 or method 2, wherein:

[0073] Method 1 includes the following steps:

[0074] (1) dispersing a spherical or quasi-spherical solid catalyst component B in an inert solvent to form a suspension;

[0075] (2) contacting the suspension obtained in step (1) with an alcohol compound and a second organic epoxy compound;

[0076] (3) removing unreacted materials and solvent from the mixture obtained in step (2), washing the mixture, and preparing a suspension containing a solid intermediate;

[0077] (4) contacting the suspension obtained in step (3) with an alcohol compound and a second titanium compound to react;

[0078] (5) removing unreacted substances and solvent from the mixture obtained in step (4), washing the mixture, and obtaining the catalyst component;

[0079] Preferably, in step (2), the system temperature is first lowered to -60°C to 20°C, and then the alcohol compound and the second organic epoxy compound are added to react for 0.5-2 hours;

[0080] Preferably, in step (4), the system temperature is first lowered to -30°C to 0°C, and then the alcohol compound and the second titanium compound are added, and the temperature is raised to 50-90°C and kept constant for 0.5-2 hours.

[0081] Method 2 includes the following steps:

[0082] 1) dispersing a spherical or quasi-spherical solid catalyst component B in an inert solvent to form a suspension;

[0083] 2) contacting the suspension obtained in step 1) with an alcohol compound and a second organic epoxy compound for reaction;

[0084] 3) contacting the suspension obtained in step 2) with a second titanium compound to react;

[0085] 4) removing unreacted substances and solvent from the mixture obtained in step 3), washing the mixture to obtain the catalyst component;

[0086] Preferably, in step 2), the system temperature is first lowered to -60°C to 20°C, and then the alcohol compound and the second organic epoxy compound are added to react for 0.5-2 hours;

[0087] Preferably, in step 3), the system temperature is first lowered to -30°C to 0°C, and then the second titanium compound is added, and the temperature is raised to 50-90°C and kept constant for 0.5-2 hours.

[0088] In the present invention, the inert solvent can be a saturated aliphatic hydrocarbon or aromatic hydrocarbon such as isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc.

[0089] According to the present invention, "aliphatic hydrocarbon group" refers to a linear or branched hydrocarbon group consisting only of carbon atoms and hydrogen atoms, and specific examples include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, vinyl, 1-propenyl, allyl, ethynyl, 1-propynyl, 2-propynyl, butynyl, etc. "Aromatic hydrocarbon group" refers to a hydrocarbon group having a benzene ring, including aryl, aryl-substituted hydrocarbon group, or hydrocarbon-substituted aryl group, such as phenyl, benzyl, anthracenyl, and naphthyl.

[0090] According to a third aspect of the present invention, the present invention provides a catalyst for ethylene polymerization, the catalyst comprising the following components:

[0091] M) the above-mentioned catalyst component or the catalyst component prepared by the above-mentioned preparation method;

[0092] N) general formula is AlR' d X' 3-d An organoaluminum compound, wherein R' is hydrogen or C1-C 20 Hydrocarbyl group, X' is a halogen atom, preferably fluorine, chlorine or bromine, 0<d≤3.

[0093] In the present invention, the organic aluminum compound can be 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), etc., preferably Al(CH2CH3)3, Al(i-Bu)3.

[0094] According to the present invention, the molar ratio of aluminum in component N) to titanium in component M) may be 5:1-500:1, preferably 20:1-200:1, more preferably 50:1-100:1.

[0095] According to a fourth aspect of the present invention, the present invention provides the above-mentioned catalyst component, the catalyst component prepared by the above-mentioned preparation method or the use of the above-mentioned catalyst in ethylene polymerization.

[0096] The substances and parameters not limited in the present invention can be selected according to the existing technology and belong to the conventional technical means in this field.

[0097] The present invention will be further described below with reference to the following examples, but is not limited to these examples.

[0098] In the following preparation examples, embodiments and comparative examples, the relevant data were obtained according to the following test methods:

[0099] 1. Morphology of spherical or quasi-spherical solid catalyst component B / catalyst component / polymer: measured using a FEI XL-30 / Hitachi S-4800 scanning electron microscope.

[0100] 2. Bulk density of polymers: Determined using the (ASTM D1895) test method for apparent density, bulk factor, and pourability of plastics.

[0101] 3. Particle size distribution of spherical or quasi-spherical solid catalyst component B / catalyst component: measured using a Malvern laser particle size and shape analyzer.

[0102] 4. Relative weight percentage of spherical or quasi-spherical solid catalyst component B / titanium element in the catalyst component: determined by spectrophotometry.

[0103] 5. Melt index of polymer (MI / 2.16 kg): measured according to ASTM D1238-99.

[0104] Preparation Example 1

[0105] 4.8 g of magnesium chloride, 90 mL of toluene, 5.0 mL of epichlorohydrin, and 15.0 mL of tri-n-butyl phosphate were added to a reactor, stirred at 450 rpm and 60°C for 2 hours, 1.1 g of phthalic anhydride and 0.7 mL of ethyl acetate were added, the temperature was kept constant for 1 hour, the temperature was lowered to -40°C, 70 mL of titanium tetrachloride was added dropwise, the temperature was gradually raised to 90°C, and the temperature was kept constant for 1 hour. The mother liquor was filtered off, and the mixture was washed several times with an inert diluent of toluene and an organic solvent of hexane, and then dried to obtain a spherical or quasi-spherical solid catalyst component B1. Its performance parameters are shown in Table 1, and the electron microscope photograph is shown in Table 1. Figure 1 shown.

[0106] Preparation Example 2

[0107] 4.8 g of magnesium chloride, 90 mL of toluene, 5.0 mL of epichlorohydrin, and 11.0 mL of tri-n-butyl phosphate were added to a reactor and allowed to react at 60°C with stirring at 450 rpm for 2 hours. 1.6 g of phthalic anhydride and 0.4 mL of ethyl acetate were then added, and the temperature was maintained constant for 1 hour. The temperature was then lowered to -40°C, and 40 mL of titanium tetrachloride was added dropwise. The temperature was gradually raised to 90°C and maintained constant for 1 hour. The mother liquor was filtered off, and the mixture was washed repeatedly with an inert diluent, toluene, and an organic solvent, hexane, and then dried to obtain a spherical or quasi-spherical solid catalyst component B2. The performance parameters of the catalyst component B2 are shown in Table 1.

[0108] Example 1

[0109] (1) Preparation of catalyst component 1

[0110] Add 6.5g of spherical or quasi-spherical solid catalyst component B1 (containing 0.051mol magnesium) and 85mL of toluene into the reactor, cool the system to -10°C, slowly add 2.0mL of butanol and 1.0mL of epichlorohydrin, and react at a constant temperature for 30min. Filter out the mother liquor and wash once with an inert diluent. Add 80mL of hexane and cool the system to -10°C. Slowly add 1.0mL of butanol and 15mL of titanium tetrachloride, heat to 60°C in 1h, and then keep the temperature constant for 1h. Filter out the mother liquor, wash several times with an inert diluent and then dry. A catalyst component 1 with good fluidity is obtained, and its performance parameters are shown in Table 1. The electron microscope photo is shown in Table 1. Figure 2 shown.

[0111] (2) Polymerization reaction

[0112] Polymerization at a low hydrogen-to-ethylene ratio: A 2-L stainless steel reactor was fully purged with high-purity nitrogen, and then 1 L of hexane and 1.0 mL of 1 M triethylaluminum were added. The catalyst component 1 (containing 0.6 mg of titanium) prepared by the above method was then added. The reaction mixture was heated to 70°C, and hydrogen was introduced to a pressure of 0.28 MPa (gauge pressure). Ethylene was then introduced to a total pressure of 0.73 MPa. Polymerization was carried out at 80°C for 2 hours. The polymerization results are shown in Table 2.

[0113] Polymerization with a high hydrogen-to-ethylene ratio: A 2-liter stainless steel reactor was fully purged with high-purity nitrogen, and then 1 L of hexane and 1.0 mL of 1 M triethylaluminum were added. The catalyst component 1 (containing 1.8 mg of titanium) prepared by the above method was then added. The reaction mixture was heated to 75° C., hydrogen was introduced to a pressure of 0.58 MPa (gauge pressure), and ethylene was introduced to a total pressure of 0.73 MPa. Polymerization was continued at 85° C. for 2 hours. The polymerization results are shown in Table 2. The electron microscope photograph of the polymer obtained by polymerization with a low hydrogen-to-ethylene ratio is shown in Table 2. Figure 3 、 Figure 4 shown.

[0114] Example 2

[0115] (1) Preparation of catalyst component 2

[0116] Add 6.5g of spherical or quasi-spherical solid catalyst component B1 and 85mL of toluene into the reactor, cool the system to 0℃, slowly add 3.0mL of butanol and 1.0mL of epichlorohydrin, and react at constant temperature for 1h. Filter out the mother liquor and wash once with an inert diluent. Add 80mL of hexane and cool the system to 0℃. Slowly add 3.0mL of butanol and 30mL of titanium tetrachloride, raise the temperature to 60℃ in 1h, and then keep the temperature constant for 1h. Filter out the mother liquor, wash several times with an inert diluent and then dry. A catalyst component 2 with good fluidity is obtained, and its performance parameters are shown in Table 1. The electron microscope photo is shown in Table 1. Figure 5 shown.

[0117] (2) Polymerization: The same as in Example 1, using catalyst component 2, the polymerization results are shown in Table 2, and the electron microscope photos of the polymer obtained by low hydrogen-to-ethanol polymerization are shown in Table 2. Figure 6 、 Figure 7 As shown, the electron microscope photo of the polymer obtained by high hydrogen-to-ethyl ratio polymerization is as follows Figure 8 、 Figure 9 .

[0118] Example 3

[0119] (1) Preparation of catalyst component 3

[0120] 6.5g of spherical or quasi-spherical solid catalyst component B2 (containing 0.051mol magnesium) and 85mL of toluene were added to the reactor, the system was cooled to 0°C, 3.0mL of isooctyl alcohol and 1.5mL of epichlorohydrin were slowly added dropwise, and the reaction was kept at a constant temperature for 1h. The mother liquor was filtered off and washed once with an inert diluent. 80mL of hexane was added and the system was cooled to 0°C. 1.0mL of butanol and 20mL of titanium tetrachloride were slowly added dropwise, the temperature was raised to 60°C with 1h, and then the temperature was kept constant for 1h. The mother liquor was filtered off, washed several times with an inert diluent, and then dried. Catalyst component 3 with good fluidity was obtained, and its performance parameters are shown in Table 1.

[0121] (2) Polymerization: The same as in Example 1, using catalyst component 3, the polymerization results are shown in Table 2.

[0122] Example 4

[0123] (1) Preparation of catalyst component 4

[0124] 6.5 g of spherical or quasi-spherical solid catalyst component B2 and 85 mL of toluene were added to the reactor, the system was cooled to 0 ° C, 2.0 mL of butanol, 0.5 mL of ethanol and 1.5 mL of epichlorohydrin were slowly added dropwise, and the reaction was kept at constant temperature for 1 hour. The mother liquor was filtered off and washed once with an inert diluent. 80 mL of hexane was added and the system was cooled to 0 ° C. 2.0 mL of butanol and 40 mL of titanium tetrachloride were slowly added dropwise, the temperature was raised to 60 ° C for 1 hour, and then the temperature was kept constant for 1 hour. The mother liquor was filtered off, washed several times with an inert diluent and then dried. Catalyst component 4 with good fluidity was obtained, and its performance parameters are shown in Table 1.

[0125] (2) Polymerization: The same as in Example 1, using catalyst component 4. The polymerization results are shown in Table 2.

[0126] Example 5

[0127] (1) Preparation of catalyst component 5

[0128] Add 6.5 g of spherical or quasi-spherical solid catalyst component B2 and 85 mL of toluene to a reactor. Cool the system to 0°C, slowly add 2.0 mL of butanol and 1.5 mL of epichlorohydrin dropwise, and maintain the reaction at this temperature for 1 hour. Slowly add 40 mL of titanium tetrachloride dropwise, raise the temperature to 60°C over 1 hour, and then maintain the temperature for 1 hour. Filter the mother liquor, wash the mixture several times with an inert diluent, and then dry it. This yields catalyst component 5 with good fluidity.

[0129] (2) Polymerization: The same as in Example 1, using catalyst component 5, the polymerization results are shown in Table 1.

[0130] Comparative Example 1

[0131] (1) The spherical or quasi-spherical solid catalyst component B1 obtained in Preparation Example 1 was used as catalyst component D1.

[0132] (2) Polymerization: The same as in Example 1, using catalyst component D1. The polymerization results are shown in Table 2.

[0133] Comparative Example 2

[0134] (1) Preparation of catalyst component D2

[0135] Add 6.5g of spherical or quasi-spherical solid catalyst component B1 and 85mL of toluene into the reactor, cool the system to 0℃, slowly add 3.0mL of butanol, and react at constant temperature for 1h. Filter out the mother liquor and wash once with an inert diluent. Add 80mL of hexane and cool the system to 0℃. Slowly add 3.0mL of butanol and 30mL of titanium tetrachloride, heat to 60℃ in 1h, and then keep constant temperature for 1h. Filter out the mother liquor, wash several times with an inert diluent and then dry. Catalyst component D2 is obtained, and its performance parameters are shown in Table 1. The electron microscope photo is shown in Figure 10 shown.

[0136] (2) Polymerization: The same as in Example 1, using catalyst component D2, the polymerization results are shown in Table 2, and the electron microscope photos of the polymer obtained by low hydrogen-to-ethylene ratio polymerization are shown in Table 2. Figure 11 、 Figure 12 shown.

[0137] Comparative Example 3

[0138] (1) Preparation of catalyst component D3

[0139] 6.5 g of spherical or quasi-spherical solid catalyst component B2 and 85 mL of toluene were added to a reactor. The system was cooled to 0°C, and 1.5 mL of epichlorohydrin was slowly added dropwise. The reaction was kept at this temperature for 1 hour. The mother liquor was filtered off and the mixture was washed once with an inert diluent. 80 mL of hexane was added, and the system was cooled to 0°C. 40 mL of titanium tetrachloride was slowly added dropwise, and the temperature was raised to 60°C over 1 hour, and then kept at this temperature for 1 hour. The mother liquor was filtered off, and the mixture was washed several times with an inert diluent, and then dried. Catalyst component D3 was obtained, and its performance parameters are shown in Table 1.

[0140] (2) Polymerization: The same as in Example 1, using catalyst component D3. The polymerization results are shown in Table 2.

[0141] Table 1

[0142] Solid catalyst component B Catalyst components Particle size (μm) Titanium content (wt%) Preparation Example 1 B1 - 5.5 2.5 Preparation Example 2 B2 - 6.2 2.2 Example 1 B1 1 5.4 4.8 Example 2 B1 2 5.5 5.0 Example 3 B2 3 6.1 4.5 Example 4 B2 4 6.3 4.7 Example 5 B2 5 6.5 3.5 Comparative Example 1 B1 D1 5.5 2.5 Comparative Example 2 B1 D2 5.6 3.0 Comparative Example 3 B2 D3 6.3 2.3

[0143] As shown in Table 1, the particle size of solid catalyst component B directly affects the particle size of the catalyst components. In addition, after the treatment of solid catalyst component B, the titanium content of catalyst components 1-5 increased significantly, while the titanium content of catalyst components D1-D3 changed little, indicating that the catalyst component preparation of the present invention can effectively increase the titanium content of the catalyst.

[0144] Table 2

[0145]

[0146] As can be seen from Table 2, compared with the comparative example, the catalyst component obtained by reacting an alcohol compound, a second organic epoxy compound, a second titanium compound and a spherical or quasi-spherical solid catalyst component B in the present invention has significantly increased polymerization activity and powder melt index at low / high hydrogen-to-ethanol ratios, which indicates that the catalyst component of the present invention can effectively improve the polymerization activity and hydrogen adjustment sensitivity of the catalyst.

[0147] While various embodiments of the present invention have been described above, the above description is intended to be illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A catalyst component for ethylene polymerization, characterized in that The catalyst component comprises the reaction product of: 1) Spherical or quasi-spherical solid catalyst component B; 2) alcohol compounds; 3) a second organic epoxy compound; 4) a second titanium compound; The spherical or quasi-spherical solid catalyst component B comprises a reaction product of a magnesium complex, an organic acid anhydride compound, an acetate compound and a first titanium compound; The magnesium complex is a complex formed by dissolving magnesium halide in a solvent system containing a first organic epoxy compound and an organic phosphorus compound.

2. The catalyst component for ethylene polymerization according to claim 1, wherein The first organic epoxy compound and the second organic epoxy compound are selected from C2-C 18 At least one of an oxide, a glycidyl ether, and an internal ether of an aliphatic olefin, an aliphatic diene, a halogenated aliphatic olefin, or a halogenated aliphatic diene; The organic phosphorus compound is a hydrocarbon ester or a halogenated hydrocarbon ester of orthophosphoric acid or phosphorous acid.

3. The catalyst component for ethylene polymerization according to claim 2, wherein The first organic epoxy compound and the second organic epoxy compound are independently at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether and butyl glycidyl ether.

4. The catalyst component for ethylene polymerization according to claim 2, wherein The organophosphorus compound is at least one selected from triethyl phosphate, tri-n-butyl phosphate, tri-isooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite and di-n-butyl phosphite.

5. The catalyst component for ethylene polymerization according to claim 1, wherein The structure of the organic acid anhydride compound is shown in formula (I): In formula (I), R5 and R6 are the same or different and are independently hydrogen, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C3-C 10 Cycloalkyl or C6-C 10 Aromatic hydrocarbon group, and R5 and R6 can form a ring; The general formula of the acetate compound is CH3COOR7, wherein R7 is C1-C 10 Alkyl, C2-C 10 Alkenyl, C3-C 10 Cycloalkyl, C2-C 10 Alkynyl or C6-C 10 Aromatic hydrocarbon groups.

6. The catalyst component for ethylene polymerization according to claim 5, wherein The organic acid anhydride compound is at least one selected from acetic anhydride, propionic anhydride, butyric anhydride, acrylic anhydride, phthalic anhydride, crotonic anhydride and maleic anhydride.

7. The catalyst component for ethylene polymerization according to claim 5, wherein R7 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl or n-hexyl.

8. The catalyst component for ethylene polymerization according to claim 1, wherein The general formula of the first titanium compound and the second titanium compound is Ti(OR8) a X b , where R8 is C1-C 10 an aliphatic or aromatic hydrocarbon group, X is a halogen, a is 0, 1 or 2, b is an integer of 1-4, and a+b=3 or 4.

9. The catalyst component for ethylene polymerization according to claim 8, wherein X is fluorine, chlorine or bromine.

10. The catalyst component for ethylene polymerization according to claim 8, wherein The first titanium compound and the second titanium compound are independently at least one of titanium tetrachloride, titanium tetrabromide, triethoxytitanium monochloride, titanium trichloride, diethoxytitanium dichloride and monoethoxytitanium trichloride.

11. The catalyst component for ethylene polymerization according to claim 1, wherein The preparation method of the spherical or quasi-spherical solid catalyst component B comprises the following steps: S1, dissolving magnesium halide in a solvent system containing a first organic epoxy compound and an organic phosphorus compound to form a uniform solution; S2, reacting the solution obtained in step S1 with an organic acid anhydride compound and an acetate compound, and then contacting the solution with a first titanium compound, and then heating the solution to precipitate magnesium / titanium-containing solid particles; S3, removing unreacted materials and solvent from the mixture obtained in step S2, washing the mixture, and obtaining a solid catalyst component B.

12. The catalyst component for ethylene polymerization according to claim 11, wherein Calculated per mole of magnesium halide, the amount of the first organic epoxy compound is 0.2-10 moles; the amount of the organic phosphorus compound is 0.1-10 moles; the amount of the organic anhydride compound is 0.03-1.0 moles; the amount of the acetate compound is 0.01-1 moles; and the amount of the first titanium compound is 0.5-120 moles.

13. The catalyst component for ethylene polymerization according to claim 11, wherein In step S1, the dissolution temperature is 50-70° C. and the dissolution time is 1-3 hours.

14. The catalyst component for ethylene polymerization according to claim 11, wherein In step S2, the reaction time of the solution with the organic anhydride compound and the acetate compound is 0.5-2 hours, the temperature of the system after the reaction is reduced to -60°C to -20°C, and then contacted with the first titanium compound; and the temperature is raised to 75°C-100°C.

15. The catalyst component for ethylene polymerization according to claim 1, wherein The alcohol compound is selected from C1-C 18 fatty alcohol or aromatic alcohol.

16. The catalyst component for ethylene polymerization according to claim 15, wherein The alcohol compound is at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isooctyl alcohol, benzyl alcohol, phenylethyl alcohol, ethylene glycol, propylene glycol, butanediol, hexanediol and isohexanediol.

17. The catalyst component for ethylene polymerization according to claim 1, wherein Based on each mole of magnesium in the spherical or quasi-spherical solid catalyst component B, the amount of the alcohol compound used is 0.05-2.0 moles; the amount of the second organic epoxy compound used is 0.01-0.5 moles; and the amount of the second titanium compound used is 0.5-15 moles.

18. The method for preparing a catalyst component for ethylene polymerization according to any one of claims 1 to 17, characterized in that: The preparation method is selected from the following method 1 or method 2, wherein: Method 1 includes the following steps: (1) dispersing a spherical or quasi-spherical solid catalyst component B in an inert solvent to form a suspension; (2) contacting the suspension obtained in step (1) with an alcohol compound and a second organic epoxy compound; (3) removing unreacted materials and solvent from the mixture obtained in step (2), washing the mixture, and preparing a suspension containing a solid intermediate; (4) contacting the suspension obtained in step (3) with an alcohol compound and a second titanium compound to react; (5) removing unreacted substances and solvent from the mixture obtained in step (4), washing the mixture, and obtaining the catalyst component; Method 2 includes the following steps: 1) dispersing a spherical or quasi-spherical solid catalyst component B in an inert solvent to form a suspension; 2) contacting the suspension obtained in step 1) with an alcohol compound and a second organic epoxy compound for reaction; 3) contacting the suspension obtained in step 2) with a second titanium compound to react; 4) removing unreacted substances and solvent from the mixture obtained in step 3), and washing the mixture to obtain the catalyst component.

19. The method for preparing a catalyst component for ethylene polymerization according to claim 18, wherein: In step (2), the system temperature is first lowered to -60°C to 20°C, and then the alcohol compound and the second organic epoxy compound are added to react for 0.5-2 hours.

20. The method for preparing a catalyst component for ethylene polymerization according to claim 18, wherein: In step (4), the system temperature is first lowered to -30°C to 0°C, and then the alcohol compound and the second titanium compound are added, and the temperature is raised to 50-90°C and kept constant for 0.5-2 hours.

21. The method for preparing a catalyst component for ethylene polymerization according to claim 18, wherein: In step 2), the system temperature is first lowered to -60°C to 20°C, and then the alcohol compound and the second organic epoxy compound are added to react for 0.5-2 hours.

22. The method for preparing a catalyst component for ethylene polymerization according to claim 18, wherein: In step 3), the system temperature is first lowered to -30°C to 0°C, and then the second titanium compound is added, and the temperature is raised to 50-90°C and kept constant for 0.5-2 hours.

23. A catalyst for ethylene polymerization, characterized in that The catalyst comprises the following components: M) the catalyst component according to any one of claims 1 to 17 or the catalyst component prepared by the preparation method according to any one of claims 18 to 22; N) general formula is AlR' d X' 3-d An organoaluminum compound, wherein R' is hydrogen or C l -C 20 Hydrocarbon group, X' is a halogen atom, 0 <d≤3。 24. The catalyst for ethylene polymerization according to claim 23, wherein X' is fluorine, chlorine or bromine.

25. The catalyst for ethylene polymerization according to claim 23, wherein The molar ratio of the aluminum in component N) to the titanium in component M) is 20:1 to 200:

1.

26. The catalyst for ethylene polymerization according to claim 25, wherein The molar ratio of aluminum in component N) to titanium in component M) is 50:1 to 100:

1.

27. Use of the catalyst component according to any one of claims 1 to 17, the catalyst component prepared by the preparation method according to any one of claims 18 to 22, or the catalyst according to any one of claims 23 to 26 in ethylene polymerization.

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