A catalyst component for ethylene polymerization, a method for preparing the same, a catalyst and use thereof

Abstract

The application belongs to the technical field of catalysts, and discloses a catalyst component for ethylene polymerization, a preparation method, a catalyst and application, the catalyst component comprises the reaction products of the following components: 1) a spherical or spherical-like solid catalyst component B; 2) an alcohol compound; 3) a second organic epoxy compound; 4) a second titanium compound; 5) an electron donor selected from an electron donor a and / or an electron donor b; the spherical or spherical-like solid catalyst component B comprises the reaction products of a magnesium complex, an organic acid anhydride compound, an acetate compound and a first titanium compound. The catalyst has high polymerization activity for ethylene polymerization, and the prepared polyethylene powder has high molecular weight and low ash content.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalyst technology, in particular, relates to a catalyst component for ethylene polymerization, a preparation method of the catalyst component, and a catalyst comprising the catalyst component, and application of the catalyst component and the catalyst. BACKGROUND

[0002] Ultra high molecular weight polyethylene (UHMWPE) is a special polyethylene variety with a molecular weight greater than 1.5 million. Most of the commercial UHMWPE is currently prepared by Ziegler-Natta catalyst (Z-N catalyst), which has unparalleled wear resistance, impact resistance, self-lubrication, corrosion resistance, low temperature resistance, hygiene, non-toxicity, non-stickiness, non-water absorption, small density and other comprehensive properties compared with ordinary polyethylene and other engineering plastics.

[0003] According to the feedback results of UHMWPE market applications, spherical / ellipsoidal UHMWPE powder with narrow particle size distribution and high bulk density has good application value, and this requires the development of high-performance Ziegler-Natta type polyethylene catalyst.

[0004] Ziegler-Natta type olefin polymerization catalyst particles have a special ability to replicate the morphology to the polyolefin powder particles prepared therefrom. For example, spherical / ellipsoidal catalyst particles usually generate spherical / ellipsoidal powder particles, and high porosity catalyst particles usually generate high porosity powder particles. Spherical / ellipsoidal polyolefin powder particles have good flowability, and if a simple method for preparing the above-mentioned powder particles can be found, it has good industrial prospects. The dissolution and precipitation type catalyst preparation process is short and controllable, and is a good choice. The N series polyolefin catalyst of Beijing Research Institute of Chemical Industry is a typical representative of the dissolution and precipitation type catalyst. The catalyst particles of this type are non-spherical, and the particle size is usually less than 50 μm. The powder particles obtained by ethylene polymerization are also non-spherical. If we want to prepare narrow distribution, spherical / ellipsoidal N type polyolefin catalyst particles, we need to achieve accurate control of the precipitation and shaping of the catalyst particles.

[0005] As disclosed in patent document CN201410531766.2, when an organic acid anhydride / acetic ester / cyclic ketone compound is introduced into the system as a complex electron donor, spherical / ellipsoidal N-type-like polyethylene catalyst particles are first prepared. As disclosed in patent document CN202011158568.8, when an organic acid anhydride / acetic ester / diether compound / cyclotrioxime and / or cyclotetraoxime is introduced into the system as a complex electron donor, spherical / ellipsoidal UHMWPE powder particles with a viscosity average molecular weight greater than 7 million, a narrow particle size distribution, and a high bulk density can be prepared. However, the above-mentioned spherical / ellipsoidal polyethylene catalysts have relatively low polymerization activity, which cannot meet the requirements of some slurry polyethylene industrial production devices for high-activity catalysts and the requirements of downstream enterprises for UHMWPE powder particles with low ash content.

[0006] Therefore, there is an urgent need to develop a high-activity spherical / ellipsoidal polyethylene catalyst capable of producing spherical / ellipsoidal UHMWPE powder particles with high molecular weight and low ash content. SUMMARY

[0007] In view of the above, the inventors of the present application have found that treating the spherical / spherical-like solid catalyst component B with an alcohol compound, an organic epoxy compound, a titanium-containing compound, an electron donor (electron donor a and / or electron donor b) can not only significantly improve the polymerization activity of the catalyst, but also polymerize spherical / ellipsoidal UHMWPE powder particles with high molecular weight and low ash content. Based on this, the purpose of the present application is to provide a catalyst component for ethylene polymerization, a preparation method thereof, a catalyst, and an application.

[0008] The first aspect of the present application provides a catalyst component for ethylene polymerization, which comprises the reaction product of the following components:

[0009] 1) a spherical or spherical-like solid catalyst component B;

[0010] 2) an alcohol compound;

[0011] 3) a second organic epoxy compound;

[0012] 4) a second titanium compound;

[0013] 5) an electron donor selected from electron donor a and / or electron donor b;

[0014] The spherical or spherical-like solid catalyst component B comprises the reaction product of a magnesium complex, an organic acid anhydride compound, an acetic ester compound, and a first titanium compound.

[0015] The second aspect of the present application provides a method for preparing the above-mentioned catalyst component for ethylene polymerization, which is selected from the following method I or method II, wherein,

[0016] Method I comprises the following steps:

[0017] (1) dispersing the spherical or spheroid solid catalyst component B in an inert solvent and forming a suspension;

[0018] (2) contacting the suspension obtained in step (1) with an alcohol compound and a second organic epoxide compound;

[0019] (3) removing unreacted substances and solvent from the mixture obtained in step (2), washing, and preparing a suspension containing a solid intermediate;

[0020] (4) contacting the suspension obtained in step (3) with an alcohol compound, a second titanium compound, an electron donor a and / or an electron donor b and reacting;

[0021] (5) removing unreacted substances and solvent from the mixture obtained in step (4), washing, and obtaining the catalyst component;

[0022] Method II comprises the following steps:

[0023] 1) dispersing the spherical or spheroid solid catalyst component B in an inert solvent and forming a suspension;

[0024] 2) contacting the suspension obtained in step 1) with an alcohol compound and a second organic epoxide compound;

[0025] 3) contacting the suspension obtained in step 2) with a second titanium compound, an electron donor a and / or an electron donor b and reacting;

[0026] 4) removing unreacted substances and solvent from the mixture obtained in step 3), washing, and obtaining the catalyst component.

[0027] The third aspect of the present application provides a catalyst for ethylene polymerization, which comprises the following components:

[0028] M) the above-mentioned catalyst component or the catalyst component prepared by the above-mentioned preparation method;

[0029] N) an organic aluminum compound with the general formula of AlR' d X' 3-d , wherein R' is hydrogen or C1-C 20 hydrocarbon group, X' is a halogen atom, preferably fluorine, chlorine or bromine, and 0

[0030] The fourth aspect of the present application 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 the preparation of ultra-high molecular weight polyethylene.

[0031] The catalyst of the present application has higher polymerization activity for ethylene polymerization, and the prepared polyethylene powder has a viscosity average molecular weight greater than 7.5 million, an ash content less than 40 ppm and a bulk density greater than 0.41 g / mL.

[0032] Other features and advantages of the present application will be described in detail in the following specific embodiments. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 Electron micrograph of the spherical or spherical-like solid catalyst component B1.

[0034] Figure 2 Electron micrograph of the spherical or spherical-like solid catalyst component B1.

[0035] Figure 3 Electron micrograph of the catalyst component 1.

[0036] Figure 4 Electron micrograph of the polymer prepared in Example 1.

[0037] Figure 5 Electron micrograph of the polymer prepared in Example 1.

[0038] Figure 6 Electron micrograph of the polymer prepared in Comparative Example 1. DETAILED DESCRIPTION

[0039] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are merely intended to illustrate and explain the present application, and are not intended to limit the present application.

[0040] According to the first aspect of the present application, the present application provides a catalyst component for ethylene polymerization, which comprises the reaction product of the following components:

[0041] 1) a spherical or spherical-like solid catalyst component B;

[0042] 2) an alcohol compound;

[0043] 3) a second organic epoxy compound;

[0044] 4) a second titanium compound;

[0045] 5) an electron donor selected from electron donor a and / or electron donor b;

[0046] The spherical or spherical-like solid catalyst component B comprises a reaction product of a magnesium complex, an organic acid anhydride compound, an acetic acid ester compound and a first titanium compound.

[0047] In the present application, the magnesium complex is a complex formed by dissolving a magnesium halide in a solvent system containing a first organic epoxide compound and an organic phosphorus compound.

[0048] According to the present application, the magnesium halide can be magnesium dichloride, magnesium dibromide, magnesium difluoride or magnesium diiodide, preferably magnesium dichloride.

[0049] In the present application, the first organic epoxide compound can be selected from at least one of oxides of aliphatic olefins, aliphatic diolefins, halogenated aliphatic olefins or halogenated aliphatic diolefins, glycidyl ethers and internal ethers having 2 to 10 carbon atoms. Specifically, the first organic epoxide compound can be at least one of oxirane, oxetane, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether and butyl glycidyl ether. 18

[0050] In the present application, the organic phosphorus compound can be a hydrocarbyl ester or a halogenated hydrocarbyl 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.

[0051] According to the present application, the organic acid anhydride compound has a structure represented by formula (I):

[0052]

[0053] In formula (I), R5and R6are the same or different, each 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 R5and R6may be optionally annelated.

[0054] Preferably, the organic acid anhydride compound is at least one selected from acetic anhydride, propionic anhydride, butyric anhydride, acrylic anhydride, phthalic anhydride, butenyl anhydride and maleic anhydride.

[0055] In the present application, the acetic acid ester compound has a general formula CH3COOR7, wherein R7is C1-C 10 alkyl, C2-C 10 alkenyl, C3-C 10 cycloalkyl, C2-C 10 alkynyl or C6-C​10 The aromatic hydrocarbon group, preferably, R7 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl or n-hexyl.

[0056] Specifically, the acetate compound may be selected from at least one of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, and n-octyl acetate.

[0057] According to the present invention, the general formula of the first titanium compound is Ti(OR8). a X b R8 is C1-C 10 The first titanium compound can be an aliphatic or aromatic hydrocarbon group, where 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 can be at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraethoxy, titanium monochlorotriethoxy, titanium trichloride, titanium dichlorodiethoxy, and titanium trichloromonoethoxy.

[0058] In this invention, the preparation method of the spherical or near-spherical solid catalyst component B includes the following steps:

[0059] S1, dissolve magnesium halide in a solvent system containing an organic epoxy compound and an organophosphorus compound to form a homogeneous solution;

[0060] S2, react the solution obtained in step S1 with organic acid anhydride compounds and acetate compounds, then contact it with the first titanium compound, and then heat it to precipitate magnesium / titanium-containing solid particles;

[0061] S3, remove unreacted substances and solvent from the mixture obtained in step S2, wash, and obtain solid catalyst component B.

[0062] 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 acid 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.

[0063] Preferably, in step S1, the dissolution temperature is 50-70℃ and the time is 1-3 hours.

[0064] Preferably, in step S2, the reaction temperature of the solution with the organic acid anhydride compound and the acetic ester 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℃ to -20℃, and then the first titanium compound is contacted therewith; the temperature is gradually increased, the rate of the temperature increase can be 0.2-2℃ / min, and the temperature is increased to 75℃-100℃.

[0065] According to the present application, the alcohol compound is selected from at least one of C1-C 18 aliphatic or aromatic alcohols, preferably at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isooctanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and isohexylene glycol.

[0066] In the present application, the second organic epoxy compound can be selected from at least one of C2-C 18 aliphatic olefins, aliphatic diolefins, halogenated aliphatic olefins or halogenated aliphatic diolefins, oxides, glycidyl ethers and internal ethers. The second organic epoxy compound is preferably at least one of oxirane, oxetane, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether and butyl glycidyl ether. The second organic epoxy compound in the present application can be the same as or different from the first organic epoxy compound.

[0067] According to the present application, the general formula of the second titanium compound is Ti(OR8) a X b wherein R8 is a C1-C 10 aliphatic or aromatic hydrocarbon group, X is halogen, preferably fluorine, chlorine or bromine, a is 0, 1 or 2, b is an integer of 1-4, and a+b=3 or 4. The second titanium compound is preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraethoxide, chlorotriethoxy titanium, titanium trichloride, dichlorodiethoxy titanium and chlorotriethoxy titanium. The second titanium compound in the present application can be the same as or different from the first titanium compound.

[0068] In the present application, the structure of the electron donor a is shown in general formula (II), and the structure of the electron donor b is shown in formula (III):

[0069]

[0070] In formula (II), R1 and R2 are independently methyl or ethyl, and R3 and R4 are independently hydrogen or methyl;

[0071] In formula (III), R9 and R 10 are independently methyl or ethyl, R 11 , R 12 , R13 and R 14 are the same or different, independently hydrogen, halogen, C1-C6linear alkyl, C1-C6branched alkyl or C1-C6alkoxy; preferably, R 10 is C1-C6linear alkyl, C1-C6branched alkyl or C1-C6alkoxy; preferably, R 10 is C1-C6linear alkyl, C1-C6branched alkyl or C1-C6alkoxy; preferably, R 10 is C1-C6linear alkyl, C1-C6branched alkyl or C1-C6alkoxy; preferably, R 11 , R 12 , R 13 and R 14 are the same or different, independently hydrogen, fluorine, chlorine, bromine, iodine, C1-C6linear alkyl, C1-C6branched alkyl or C1-C6alkoxy.

[0072] Preferably, the electron donor a is selected from at least one of 2,2-dimethyl-1,3-diethoxy-propane, 2,2-dimethyl-1,3-dimethoxy-propane, 2,2-dimethyl-1-ethoxy-3-methoxy-propane and 1-ethoxy-3-methoxy-propane.

[0073] Preferably, the electron donor b is selected from at least one of o-dimethyl ether, o-diethyl ether and 1-ethoxy-2-methoxybenzene.

[0074] Preferably, the amount of the alcohol compound is 0.05-2.0 moles, the amount of the second organic epoxide compound is 0.01-0.5 moles, the amount of the second titanium compound is 0.5-15 moles, the amount of the electron donor a is 0-1.0 moles, the amount of the electron donor b is 0-1.0 moles, and the amounts of the electron donor a and the electron donor b are not both 0 moles, per mole of magnesium in the spherical or spheroidal solid catalyst component B.

[0075] According to a second aspect of the present application, the present application provides a method for preparing the above-mentioned catalyst component for ethylene polymerization, which is selected from the following Method I or Method II, wherein,

[0076] Method I comprises the following steps:

[0077] (1) dispersing the spherical or spheroidal solid catalyst component B in an inert solvent, and forming a suspension;

[0078] (2) contacting the suspension obtained in step (1) with an alcohol compound and a second organic epoxide compound;

[0079] (3) removing unreacted substances and solvent from the mixture obtained in step (2), washing, and preparing a suspension containing a solid intermediate;

[0080] (4) contacting the suspension obtained in step (3) with an alcohol compound, a second titanium compound, an electron donor a and / or an electron donor b, and reacting;

[0081] (5) removing unreacted substances and solvent from the mixture obtained in step (4), washing, to obtain the catalyst component.

[0082] In step (2) of the present application, the system temperature is first lowered to -60 to 20°C, then the alcohol compound and the second organic epoxide compound are added for reaction, and the reaction time is 0.5 to 2 hours.

[0083] According to the present application, in step (4), the system temperature is first lowered to -30 to 0°C, then the alcohol compound and the second titanium compound are added, the temperature is raised to 50 to 90°C, and after constant temperature for 0.5 to 2 hours, the electron donor a and / or the electron donor b are added, and constant temperature is continued for 0.5 to 2 hours.

[0084] Method two comprises the following steps:

[0085] 1) dispersing the spherical or spherical-like solid catalyst component B in an inert solvent, and forming a suspension;

[0086] 2) contacting the suspension obtained in step 1) with the alcohol compound and the second organic epoxide compound for reaction;

[0087] 3) contacting the suspension obtained in step 2) with the second titanium compound, the electron donor a and / or the electron donor b for reaction;

[0088] 4) removing unreacted substances and solvent from the mixture obtained in step 3), washing, to obtain the catalyst component.

[0089] In step 2) of the present application, the system temperature is first lowered to -60 to 20°C, then the alcohol compound and the second organic epoxide compound are added for reaction, and the reaction time is 0.5 to 2 hours.

[0090] According to the present application, in step 3), the system temperature is first lowered to -30 to 0°C, then the second titanium compound is added, the temperature is raised to 50 to 90°C, and after constant temperature for 0.5 to 2 hours, the electron donor a and / or the electron donor b are added, and constant temperature is continued for 0.5 to 2 hours.

[0091] In the present application, the inert solvent can be isobutane, hexane, heptane, cyclohexane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, xylene, and the like saturated aliphatic hydrocarbons or aromatic hydrocarbons.

[0092] According to the present application, "aliphatic hydrocarbon group" refers to straight or branched chain hydrocarbon group, consisting of only carbon and hydrogen atoms, and specific examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, ethenyl, 1-propenyl, allyl, ethynyl, 1-propynyl, 2-propynyl, butynyl, etc. "Aromatic hydrocarbon group" refers to hydrocarbon group having benzene ring, including aryl group, aryl-substituted hydrocarbon group or hydrocarbon-substituted aryl group, such as phenyl, benzyl, anthryl and naphthyl, etc.

[0093] According to a third aspect of the present application, the present application provides a catalyst for ethylene polymerization, which comprises the following components:

[0094] M) the catalyst component as described above or the catalyst component prepared by the preparation method as described above;

[0095] N) an organic aluminum compound of the general formula AlR' d X' 3-d wherein R' is hydrogen or C1-C 20 hydrocarbon group, and X' is halogen atom, preferably fluorine, chlorine or bromine, and 0 < d < 3.

[0096] In the present application, 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., and preferably Al(CH2CH3)3, Al(i-Bu)3.

[0097] According to the present application, the molar ratio of aluminum in component N) to titanium in component M) can be 5:1-500:1, preferably 20:1-200:1, and more preferably 50:1-100:1.

[0098] According to a fourth aspect of the present application, the present application provides the use of the catalyst component as described above, the catalyst component prepared by the preparation method as described above or the catalyst as described above in the preparation of ultra-high molecular weight polyethylene.

[0099] The substances and parameters not defined in the present application can be selected according to the prior art, which are conventional technical means in the art.

[0100] The present application will be further described in conjunction with the following examples, but is not limited by these examples.

[0101] In the following preparation examples, examples and comparative examples, the relevant data are obtained according to the following test methods:

[0102] 1. Morphology of the spherical or spheroidal solid catalyst component B / catalyst component / polymer: FEI XL-30 / Hitachi S-4800 type scanning electron microscope was used.

[0103] 2. Bulk density of the polymer: it was determined using the Test Method for Apparent Density, Volume Factor, and Pourability of Plastics (ASTM D1895).

[0104] 3. Viscosity average molecular weight of the polymer: it was determined according to ASTM D4020-18.

[0105] 4. Ash value of the polymer: the polymer powder particles were first burned with a muffle at 500 degrees to completely remove the organic components, and then the ash after burning was analyzed using ICP MAS to determine the ash content.

[0106] Preparation Example 1

[0107] 4.8 grams of magnesium chloride, 90 mL of toluene, 5.0 mL of epichlorohydrin, 15.0 mL of tri-n-butyl phosphate were added to the reaction kettle, and the reaction was carried out at a stirring speed of 450 rpm and a temperature of 60°C for 2 hours. 1.1 g of phthalic anhydride and 0.7 mL of ethyl acetate were added, and the temperature was kept constant for 1 hour. The temperature was lowered to -40°C, 70 mL of titanium tetrachloride was added dropwise, and the temperature was gradually raised to 90°C. The temperature was kept constant for 1 hour. The mother liquor was filtered off, washed with inert diluent toluene and organic solvent hexane several times, and dried to obtain spherical or spheroidal solid catalyst component B1. The electron micrograph is shown in Figure 1 、 Figure 2 .

[0108] Preparation Example 2

[0109] 4.8 grams of magnesium chloride, 90 mL of toluene, 5.0 mL of epichlorohydrin, 15.0 mL of tri-n-butyl phosphate were added to the reaction kettle, and the reaction was carried out at a stirring speed of 450 rpm and a temperature of 60°C for 2 hours. 1.1 g of phthalic anhydride and 0.7 mL of ethyl acetate were added, and the temperature was kept constant for 1 hour. The temperature was lowered to -40°C, 70 mL of titanium tetrachloride was added dropwise, and the temperature was gradually raised to 90°C. The temperature was kept constant for 1 hour. The mother liquor was filtered off, washed with inert diluent toluene and organic solvent hexane several times, and dried to obtain spherical or spheroidal solid catalyst component B1. The electron micrograph is shown in

[0110] Example 1

[0111] (1) Preparation of catalyst component 1

[0112] A 6.5 g spherical or spheroidal solid catalyst component B1 (containing 0.051 mol of magnesium) and 85 mL of toluene were introduced into a reactor, the system was cooled to -10 °C, and 2.0 mL of butanol and 1.0 mL of epichlorohydrin were slowly added dropwise, and the reaction was carried out at constant temperature for 30 min. 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 -10 °C. 1.0 mL of butanol and 15 mL of titanium tetrachloride were slowly added dropwise, and the temperature was raised to 60 °C over 1 h and then maintained at constant temperature for 1 h. 0.3 mL of 2,2-dimethyl-1,3-diethoxy-propane was added, and the constant temperature was maintained for another 1 h. The mother liquor was filtered off, washed several times with an inert diluent and dried. Catalyst component 1 with good flowability was obtained, and its electron micrograph is shown in Figure 3 .

[0113] (2) Polymerization reaction

[0114] A 2 L stainless steel reactor was sufficiently replaced with high-purity nitrogen, 1 L of hexane and 1.0 mL of 1 M triethylaluminum were added, and then the catalyst component 1 prepared above (containing 0.6 mg of titanium) was added, and the temperature was raised to 60 °C. Ethylene was introduced to make the total pressure in the reactor 1.0 MPa (gauge pressure), and the polymerization was carried out at 70 °C for 2 h. The polymerization results are shown in Table 1, and the electron micrograph of the polymer is shown in Figure 4 , 5 .

[0115] Example 2

[0116] (1) Preparation of catalyst component 2

[0117] A 6.5 g spherical or spheroidal solid catalyst component B1 and 85 mL of toluene were introduced into a reactor, the system was cooled to 0 °C, and 3.0 mL of butanol and 1.0 mL of epichlorohydrin were slowly added dropwise, and the reaction was carried out at constant temperature for 1 h. 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. 3.0 mL of butanol and 30 mL of titanium tetrachloride were slowly added dropwise, and the temperature was raised to 60 °C over 1 h and then maintained at constant temperature for 1 h. 0.4 mL of 1-ethoxy-3-methoxy-propane was added, and the constant temperature was maintained for another 1 h. The mother liquor was filtered off, washed several times with an inert diluent and dried. Catalyst component 2 with good flowability was obtained.

[0118] (2) Polymerization reaction: same as Example 1, catalyst component 2 was used, and the polymerization results are shown in Table 1.

[0119] Example 3

[0120] (1) Preparation of catalyst component 3

[0121] Into a reaction vessel was placed 6.5 g of spherical or spheroidal solid catalyst component B2 (containing 0.051 mol of magnesium) and 85 mL of toluene, the system was cooled to 0°C and 3.0 mL of isooctanol and 1.5 mL of epichlorohydrin were added dropwise. The reaction was carried out at constant temperature for 1 h. The mother liquors were filtered off and washed once with an inert diluent. 80 mL of hexane were added and the system was cooled to 0°C. 1.0 mL of butanol and 20 mL of titanium tetrachloride were added dropwise. The temperature was raised to 60°C over 1 h and then maintained at constant temperature for 1 h. 0.5 mL of o-dithyl ether was added and the temperature was maintained for a further hour. The mother liquors were filtered off and the product was washed several times with an inert diluent and dried. Catalyst component 3 was obtained, which had good flow properties.

[0122] (2) Polymerization: as in Example 1, using catalyst component 3. The polymerization results are reported in Table 1.

[0123] Example 4

[0124] (1) Preparation of catalyst component 4

[0125] Into a reaction vessel was placed 6.5 g of spherical or spheroidal solid catalyst component B2 and 85 mL of toluene, the system was cooled to 0°C and 2.0 mL of butanol, 0.5 mL of ethanol and 1.5 mL of epichlorohydrin were added dropwise. The reaction was carried out at constant temperature for 1 h. The mother liquors were filtered off and washed once with an inert diluent. 80 mL of hexane were added and the system was cooled to 0°C. 2.0 mL of butanol and 40 mL of titanium tetrachloride were added dropwise. The temperature was raised to 60°C over 1 h and then maintained at constant temperature for 1 h. 0.5 mL of o-dithyl ether was added and the temperature was maintained for a further hour. The mother liquors were filtered off and the product was washed several times with an inert diluent and dried. Catalyst component 4 was obtained, which had good flow properties.

[0126] (2) Polymerization: as in Example 1, using catalyst component 4. The polymerization results are reported in Table 1.

[0127] Example 5

[0128] (1) Preparation of catalyst component 5

[0129] Into a reaction vessel was placed 6.5 g of spherical or spheroidal solid catalyst component B2 and 85 mL of toluene, the system was cooled to 0°C and 2.0 mL of butanol and 1.5 mL of epichlorohydrin were added dropwise. The temperature was raised to 60°C over 1 h and then maintained at constant temperature for 1 h. 40 mL of titanium tetrachloride were added dropwise. The temperature was raised to 60°C over 1 h and then maintained at constant temperature for 1 h. 0.5 mL of o-dithyl ether was added and the temperature was maintained for a further hour. The mother liquors were filtered off and the product was washed several times with an inert diluent and dried. Catalyst component 5 was obtained, which had good flow properties.

[0130] (2) Polymerization: as in Example 1, using catalyst component 5. The polymerization results are reported in Table 1.

[0131] Comparative Example 1

[0132] (1) The spherical or spheroidal solid catalyst component Bl prepared in Preparation Example 1 was used as the catalyst component Dl.

[0133] (2) Polymerization: Same as Example 1, using the catalyst component Dl, the polymerization results are shown in Table 1, and the electron micrograph of the polymer is shown in Figure 6

[0134] Comparative Example 2

[0135] (1) Preparation of the catalyst component D2

[0136] Into a reactor, 6.5 g of the spherical or spheroidal solid catalyst component Bl and 85 mL of toluene were charged, and the system was cooled to -10°C. 2.0 mL of butanol was slowly added dropwise, and the reaction was carried out at a constant temperature for 30 min. 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 -10°C. 1.0 mL of butanol and 15 mL of titanium tetrachloride were slowly added dropwise, and the temperature was raised to 60°C over 1 h, and then maintained at a constant temperature for 1 h. 0.3 mL of 2,2-dimethyl-l,3-diethoxy-propane was added, and the temperature was maintained at a constant temperature for 1 h. The mother liquor was filtered off, and washed with an inert diluent several times, and then dried. The catalyst component D2 was obtained.

[0137] (2) Polymerization: Same as Example 1, using the catalyst component D2, the polymerization results are shown in Table 1.

[0138] Comparative Example 3

[0139] (1) Preparation of the catalyst component D3

[0140] Into a reactor, 6.5 g of the spherical or spheroidal solid catalyst component Bl and 85 mL of toluene were charged, and the system was cooled to -10°C. 1.0 mL of epichlorohydrin was slowly added dropwise, and the reaction was carried out at a constant temperature for 30 min. 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 -10°C. 1.0 mL of butanol and 15 mL of titanium tetrachloride were slowly added dropwise, and the temperature was raised to 60°C over 1 h, and then maintained at a constant temperature for 1 h. 0.3 mL of 2,2-dimethyl-l,3-diethoxy-propane was added, and the temperature was maintained at a constant temperature for 1 h. The mother liquor was filtered off, and washed with an inert diluent several times, and then dried. The catalyst component D3 was obtained.

[0141] (2) Polymerization: Same as Example 1, using the catalyst component D3, the polymerization results are shown in Table 1.

[0142] Comparative Example 4

[0143] (1) Preparation of the catalyst component D4

[0144] ​Into a reaction vessel was added 6.5 g of spherical or spheroidal solid catalyst component B1 and 85 mL of toluene, the system was cooled to -10°C, 2.0 mL of butanol and 1.0 mL of epichlorohydrin were slowly added dropwise, and the system was kept at constant temperature for 30 min. The mother liquor was filtered off and washed once with inert diluent. 80 mL of hexane was added, the system was cooled to -10°C. 1.0 mL of butanol and 15 mL of titanium tetrachloride were slowly added dropwise, the temperature was raised to 60°C in 1 h, and then kept at constant temperature for 1 h. The mother liquor was filtered off and washed several times with inert diluent and dried. Catalyst component D4 was obtained.

[0145] (2) Polymerization: same as Example 1, using catalyst component D4, the polymerization results are shown in Table 1.

[0146] Table 1

[0147]

[0148] From Table 1, it can be seen that, compared with the comparative examples, the catalyst component obtained by reacting the spherical or spheroidal solid catalyst component B with the alcohol compound, the second organic epoxide compound, the electron donor, the second titanium compound according to the present application has higher polymerization activity for ethylene, the viscosity average molecular weight of the obtained powder is significantly increased, which can be more than 7.5 million, and the ash content of the powder is significantly reduced. If there is no electron donor, second organic epoxide compound, etc. in the reactants, the above effects cannot be achieved.

[0149] The above has described various embodiments of the present application, the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes are obvious 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 contains the reaction products of the following components: 1) Spherical or near-spherical solid catalyst component B; 2) Alcohols; 3) Second organic epoxy compounds; 4) Second titanium compounds; 5) An electron donor, wherein the electron donor is selected from electron donor a and / or electron donor b; The structure of electron donor a is shown in general formula (II), and the structure of electron donor b is shown in formula (III): （Ⅱ） （Ⅲ） In formula (II), R1 and R2 are independently methyl or ethyl, and R3 and R4 are independently hydrogen or methyl; In equation (Ⅲ), R9 and R 10 Independently methyl or ethyl, R 11 R 12 R 13 and R 14 Whether the same or different, independently of hydrogen, halogen, C1-C 10 Straight-chain alkyl, C1-C 10 Branched alkyl or C1-C 10 alkoxy groups; The spherical or near-spherical solid catalyst component B comprises the reaction product of a magnesium complex, an organic acid anhydride compound, an acetate compound, and a first titanium compound.

2. The catalyst component for ethylene polymerization according to claim 1, wherein, The magnesium complex is a complex formed by dissolving magnesium halide in a solvent system containing a first organic epoxy compound and an organophosphorus compound. The first organic epoxy compound and the second organic epoxy compound are respectively selected from C2-C 18 At least one of the following: aliphatic olefins, aliphatic dienes, haloaliphatic olefins or oxides of haloaliphatic dienes, glycidyl ethers and internal ethers. The organophosphorus compound is a hydrocarbon ester or haloalkyl ester of phosphoric 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 selected from ethylene oxide, propylene oxide, butane 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 selected from at least one of triethyl phosphate, tri-n-butyl phosphate, triisooctyl 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): （Ⅰ） In formula (Ⅰ), R5 and R6 may be the same or different, and each is independently hydrogen or C1-C. 10 Alkyl, C2-C 10 alkenyl, C2-C 10 alkynyl group, C3-C 10 cycloalkyl or C6-C 10 Aromatic hydrocarbon groups, and R5 and R6 can form rings in any way; The general formula of the acetate compounds is CH3COOR7, where 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 selected from at least one of acetic anhydride, propionic anhydride, butyric anhydride, acrylic anhydride, phthalic anhydride, butenoic 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 for both the first and second titanium compounds is Ti(OR8). a X b R8 is C1-C 10 The aliphatic or aromatic hydrocarbon group, where X is a halogen, a is 0, 1 or 2, b is an integer from 1 to 4, and a+b=3 or 4.

9. The catalyst component for ethylene polymerization according to claim 8, wherein, X represents 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 selected from titanium tetrachloride, titanium tetrabromide, titanium monochlorotriethoxy, titanium trichloride, titanium dichlorodiethoxy, and titanium trichloromonoethoxy.

11. The catalyst component for ethylene polymerization according to claim 2, wherein, The preparation method of the spherical or near-spherical solid catalyst component B includes the following steps: S1, dissolve magnesium halide in a solvent system containing an organic epoxy compound and an organophosphorus compound to form a homogeneous solution; S2, react the solution obtained in step S1 with organic acid anhydride compounds and acetate compounds, then contact it with the first titanium compound, and then heat it to precipitate magnesium / titanium-containing solid particles; S3, remove unreacted substances and solvent from the mixture obtained in step S2, wash, and obtain solid catalyst component B.

12. The catalyst component for ethylene polymerization according to claim 11, wherein, Based on one 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 acid 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℃ and the 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 organic acid anhydride compounds and acetate compounds is 0.5-2 hours. The temperature of the system after the reaction is lowered to -60℃ to -20℃, and then it is contacted with the first titanium compound; the temperature is then raised to 75℃-100℃.

15. The catalyst component for ethylene polymerization according to claim 1, wherein, The alcohols are selected from C1-C1. 18 Fatty alcohols or aromatic alcohols.

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

17. The catalyst component for ethylene polymerization according to claim 15, wherein, For each mole of magnesium in spherical or near-spherical solid catalyst component B, the amount of alcohol compound is 0.05-2.0 moles; the amount of second organic epoxy compound is 0.01-0.5 moles; the amount of second titanium compound is 0.5-15 moles; the amount of electron donor a is 0-1.0 moles; the amount of electron donor b is 0-1.0 moles; and the amounts of electron donor a and electron donor b are not both 0 moles.

18. The catalyst component for ethylene polymerization according to claim 1, wherein, R 11 R 12 R 13 and R 14 Whether the same or different, it is independently hydrogen, fluorine, chlorine, bromine, iodine, C1-C6 straight-chain alkyl, C1-C6 branched alkyl or C1-C6 alkoxy.

19. The catalyst component for ethylene polymerization according to claim 1, wherein, The electron donor a is selected from at least one of 2,2-dimethyl-1,3-diethoxy-propane, 2,2-dimethyl-1,3-dimethoxy-propane, 2,2-dimethyl-1-ethoxy-3-methoxy-propane, and 1-ethoxy-3-methoxy-propane.

20. The catalyst component for ethylene polymerization according to claim 1, wherein, The electron donor b is selected from at least one of o-phenylene dimethyl ether, o-phenylene diethyl ether, and 1-ethoxy-2-methoxybenzene.

21. A method for preparing the catalyst component for ethylene polymerization according to any one of claims 1-20, characterized in that, The preparation method is selected from either method one or method two below, wherein, Method 1 includes the following steps: (1) Disperse spherical or near-spherical solid catalyst component B in an inert solvent to form a suspension; (2) The suspension obtained in step (1) is reacted with an alcohol compound and a second organic epoxy compound; (3) Remove unreacted substances and solvent from the mixture obtained in step (2), wash it, and prepare a suspension containing solid intermediates; (4) The suspension obtained in step (3) is reacted with an alcohol compound, a second titanium compound, an electron donor a and / or an electron donor b; (5) Remove unreacted substances and solvent from the mixture obtained in step (4), wash it, and obtain the catalyst component; Method 2 includes the following steps: 1) Disperse spherical or near-spherical solid catalyst component B in an inert solvent to form a suspension; 2) The suspension obtained in step 1) is reacted with an alcohol compound and a second organic epoxy compound; 3) The suspension obtained in step 2) is brought into contact with the second titanium compound, electron donor a and / or electron donor b to react; 4) Remove unreacted substances and solvent from the mixture obtained in step 3), wash, and obtain the catalyst component; In step (2), the system temperature is first lowered to -60℃ to 20℃, and then alcohol compounds and second organic epoxy compounds are added to react for 0.5-2 hours.

22. The method for preparing the catalyst component for ethylene polymerization according to claim 21, wherein, In step (4), the system temperature is first lowered to -30°C to 0°C, then alcohol compounds and second titanium compounds are added, the temperature is raised to 50-90°C, and the temperature is kept constant for 0.5-2 hours. Then electron donor a and / or electron donor b are added, and the temperature is kept constant for another 0.5-2 hours.

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

24. The method for preparing the catalyst component for ethylene polymerization according to claim 21, wherein, In step 3), the system temperature is first lowered to -30°C to 0°C, then the second titanium compound is added, the temperature is raised to 50-90°C, and the temperature is held for 0.5-2 hours. Then, electron donor a and / or electron donor b are added, and the temperature is held for another 0.5-2 hours.

25. A catalyst for ethylene polymerization, characterized in that, The catalyst comprises the following components: M) The catalyst component according to any one of claims 1-20 or the catalyst component prepared by any one of claims 21-24; N) The general formula is AlR' d X' 3-d Organoaluminum compounds, wherein R' is hydrogen or C l -C 20 Hydrocarbon group, X' is a halogen atom, 0 <d≤3。 26. The catalyst for ethylene polymerization according to claim 25, wherein, X' is fluorine, chlorine, or bromine.

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

1.

28. The catalyst for ethylene polymerization according to claim 27, wherein, The molar ratio of aluminum in component N to titanium in component M is 50:1-100:

1.

29. The use of the catalyst component according to any one of claims 1-20, the catalyst component prepared by the preparation method according to any one of claims 21-24, or the catalyst according to any one of claims 25-28 in the preparation of ultra-high molecular weight polyethylene.

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