阅读说明：本技术 固体催化剂组分及制备方法与烯烃聚合催化剂和应用 (Solid catalyst component, preparation method thereof, olefin polymerization catalyst and application ) 是由 郭正阳 周俊领 刘萃莲 王迎 唐璐 雷世龙 于 2019-10-28 设计创作，主要内容包括：本发明属于催化剂领域,涉及一种固体催化剂组分及制备方法与烯烃聚合催化剂和应用。该固体催化剂组分含有钛元素、镁元素、烷氧基化合物、磷元素和卤素,其中,以固体催化剂组分的总重量计,所述钛元素的含量为1～15wt％,所述镁元素的含量为10～30wt％,所述磷元素的含量为0.01～1wt％,所述烷氧基化合物的含量为1～10wt％,所述卤素的含量为40～70wt％；所述固体催化剂组分的休止角为20～40°。本发明的固体催化剂组分和催化剂的粒形较好,流动性好,堆积密度较高,催化剂活性高,制备的聚合物粒度分布集中,堆积密度高,而且生产工艺简单,生产成本相对较低。(The invention belongs to the field of catalysts, and relates to a solid catalyst component, a preparation method thereof, an olefin polymerization catalyst and application thereof. The solid catalyst component contains titanium element, magnesium element, alkoxy compound, phosphorus element and halogen, wherein the content of the titanium element is 1-15 wt%, the content of the magnesium element is 10-30 wt%, the content of the phosphorus element is 0.01-1 wt%, the content of the alkoxy compound is 1-10 wt%, and the content of the halogen element is 40-70 wt% based on the total weight of the solid catalyst component; the angle of repose of the solid catalyst component is 20-40 degrees. The solid catalyst component and the catalyst have the advantages of good particle shape, good fluidity, higher bulk density, high catalyst activity, centralized particle size distribution of the prepared polymer, high bulk density, simple production process and relatively low production cost.)

1. The solid catalyst component is characterized by comprising 1-15 wt% of titanium element, 10-30 wt% of magnesium element, 0.01-1 wt% of phosphorus element, 1-10 wt% of alkoxy compound and 40-70 wt% of halogen, based on the total weight of the solid catalyst component; the angle of repose of the solid catalyst component is 20-40 degrees.

2. The solid catalyst component according to claim 1, wherein the content of the titanium element is 2 to 10 wt%, the content of the magnesium element is 15 to 25 wt%, the content of the phosphorus element is 0.1 to 0.8 wt%, the content of the alkoxy compound is 2 to 8 wt%, and the content of the halogen element is 50 to 65 wt% based on the total weight of the solid catalyst component; the angle of repose of the solid catalyst component is 25-35 °.

3. The solid catalyst component according to claim 1 or 2 in which the solid catalyst component has an average particle size of 2 to 10 microns, preferably 3 to 8 microns; the bulk density is 0.30 to 0.50 g/ml, preferably 0.35 to 0.45 g/ml.

4. A method for preparing a solid catalyst component comprising the steps of: dissolving a magnesium compound in a solvent system containing at least one organic epoxy compound, at least one organic phosphorus compound, at least one organic alcohol compound and at least one inert diluent to form a uniform solution, adding a precipitation aid into the solution, then reducing the temperature of the system and adding a titanium compound to obtain a suspension system containing a solid component, then raising the temperature of the system, and filtering, washing and drying the suspension system to obtain the solid catalyst component; wherein the titanium compound is added into the system for multiple times.

5. The preparation method according to claim 4, wherein the amount of the first added titanium compound is 5 to 30%, preferably 8 to 20%, and more preferably 9 to 15% of the total amount of the total titanium compounds; the time interval between the first addition of the titanium compound and the next addition of the titanium compound is 20-80%, preferably 40-70% of the total time required for adding all the titanium compounds into the system.

6. The method according to claim 5, wherein a part of the titanium compound is added during the cooling of the system, and the rest of the titanium compound is added after the cooling of the system.

7. The preparation method according to claim 6, wherein the titanium compound is added to the system in two times, a first part of the titanium compound is added during the cooling process of the system, and the rest is added after the cooling process of the system; preferably, when the system is cooled to the first target temperature, a first part of the titanium compound is added, then the system is continuously cooled to the final target temperature, and the rest part of the titanium compound is added.

8. The production method according to claim 4, wherein the system temperature is reduced to-30 ℃ to 30 ℃, preferably to-30 ℃ to 10 ℃.

9. The preparation method of claim 4, wherein the temperature of the suspension system is raised to 60-110 ℃, and the method further comprises stirring the suspension system at the temperature for 0.5-8 h, and then filtering, washing and drying the suspension system.

10. The process according to any one of claims 4 to 9, wherein the titanium compound has the formula ti (or)_aX_bWherein R is C₁～C₁₄X is a halogen atom, a is an integer of 0 to 2, b is an integer of 0 to 4, a + b is 3 or 4; preferably selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium chlorotriethoxyxide, titanium dichlorodiethoxide, titanium trichloromonoethoxyxide and titanium trichloride in at least one, further preferably selected from titanium tetrachloride, titanium trichloromonoethoxyxide and titanium trichloride in at least oneOne kind of the material is selected;

the titanium compound is added in the form of a titanium halide, or a mixture of a titanium halide and an inert diluent.

11. The production method according to any one of claims 4 to 9,

the magnesium compound is at least one of magnesium halide, magnesium alcoholate and magnesium haloalcoholate;

the organic epoxy compound is selected from C₂～C₈At least one of an oxide, glycidyl ether and internal ether of an aliphatic olefin, diolefin or halogenated aliphatic olefin or diolefin of (a);

the organophosphorus compound is selected from hydrocarbyl and/or halohydrocarbyl esters of orthophosphoric acid and/or phosphorous acid;

the organic alcohol compound is selected from C₂～C₁₀The fatty alcohol of (a);

the precipitation aid is selected from at least one of organic acid, organic acid anhydride, organic ether and organic ketone;

the inert diluent is selected from C₆～C₁₀And/or C₆～C₈The aromatic hydrocarbon of (1).

12. The production method according to any one of claims 4 to 9, wherein the organic epoxy compound is used in an amount of 0.2 to 10 moles, preferably 0.5 to 4 moles, per mole of the magnesium halide; the dosage of the organic phosphorus compound is 0.1-3 mol, preferably 0.3-1 mol; the amount of the organic alcohol compound is 0.1 to 10 moles, preferably 0.5 to 5 moles; the dosage of the inert diluent is 0.5-5L; the amount of the titanium compound is 1 to 15 mol, preferably 2 to 10 mol.

13. A solid catalyst component obtained by the production method according to any one of claims 4 to 12.

14. An olefin polymerization catalyst comprising the following components:

A. the solid catalyst component of any one of claims 1 to 3, 13;

B. an organoaluminum compound.

15. Use of the solid catalyst component according to any of claims 1-3, 13 and/or the olefin polymerization catalyst according to claim 14 in ethylene polymerization, preferably in ethylene slurry polymerization.

Technical Field

The invention belongs to the field of catalysts, and particularly relates to a solid catalyst component, a preparation method of the solid catalyst component, the solid catalyst component prepared by the preparation method, an olefin polymerization catalyst containing the solid catalyst component, and applications of the solid catalyst component and the olefin polymerization catalyst.

Background

In the polymerization of olefins, particularly in the homopolymerization of ethylene or the copolymerization of ethylene and α -olefins, catalyst components containing magnesium, titanium, halogen and an electron donor as essential components are mostly used.

In fact, the above catalyst components are mainly composed of magnesium chloride, titanium chloride and electron donors. The early catalyst component is prepared by mixing and grinding magnesium chloride, titanium tetrachloride and electron donor, and the catalyst has low activity, the prepared polymer has wide particle size distribution, and more coarse powder and fine powder, and is basically eliminated at present. In the polymerization of olefins, the morphology of the catalyst components has a decisive influence on the morphology of the polymers prepared, and therefore attempts have been made for many years to improve the morphology of the catalyst particles in order to obtain polymers with better particle morphology.

There are two main ways to improve the particle morphology of the catalyst components.

One is to load the catalyst component on the porous spherical silica gel with fixed shape, for example, Chinese patent application CN1158136A discloses a main catalyst for producing ethylene high polymer, which comprises an inorganic carrier (preferably active silica carrier), a chlorine compound loaded on the carrier, a magnesium compound loaded on the carrier, a titanium compound loaded on the carrier. The catalyst is characterized in that: the catalyst has spherical particle shape, good fluidity and good hydrogen regulation sensitivity, the polymerization activity is reduced less along with the increase of the addition amount of the chain transfer agent (hydrogen), and the catalyst is more suitable for producing the polyethylene resin with wide molecular weight distribution. However, the catalyst has most silica gel and low content of active catalyst components, so the catalyst has low activity, is suitable for a gas phase process and a slurry polyethylene process device, and has complex production process and high production cost.

The other method is to dissolve a magnesium compound into a uniform solution, and then react the magnesium compound with a titanium compound to separate out magnesium chloride particles and simultaneously load titanium chloride and an electron donor, as disclosed in chinese patent ZL85100997.2(N), chinese patent application CN1112373A (RZ), CN1229092A (CT), CN1958620A (BCE), and the like. The method generally dissolves a magnesium compound in a polar solvent, and the magnesium compound and titanium tetrachloride contact and react through a dissolving solution to separate out catalyst component particles containing titanium magnesium and electron donors.

For example, chinese patent ZL85100997.2 discloses a magnesium halide prepared by dissolving a magnesium halide in an organic epoxy compound and an organic phosphorus compound to form a homogeneous solution, and reacting the homogeneous solution with at least one precipitation aid and a halide of titanium transition metal and its derivatives. Because the organic epoxy compound and the organic phosphorus compound which do not contain active hydrogen are used as solvents, the magnesium chloride is slowly dissolved, and the reaction with titanium tetrachloride is convenient to control, the particle shape of the precipitated particles is better and is similar to a sphere, and the prepared polymer has better particle shape and higher bulk density. However, the catalyst has very low activity and insensitive hydrogen regulation when used for slurry polymerization of ethylene.

For example, in chinese patent application CN1112373A, magnesium chloride is dissolved in isooctanol using decane as a dispersant, and silane is added as a precipitating agent to precipitate catalyst component particles by reaction with titanium tetrachloride. The solvent used in the system is isooctanol, the raw materials are simple, the activity of the catalyst component is higher during the ethylene polymerization, the hydrogen regulation performance is better, but the catalyst needs high temperature for dissolution, the viscosity of the prepared solution is very high, the using amount of titanium tetrachloride is more, and the post-treatment process of the solvent is complex.

For example, chinese patent application CN1229092A discloses a catalyst for ethylene polymerization or copolymerization, which is prepared by dissolving magnesium halide in organic epoxy compound, organic phosphorus compound, and adding a low carbon alcohol as electron donor activator to form a homogeneous solution, and reacting with at least one acid anhydride type precipitant aid, halide of transition metal titanium and its derivatives.

For example, in chinese patent application CN1958620A, the catalyst is prepared by dissolving magnesium halide in an organic epoxy compound, an organic phosphorus compound and a lower alcohol to form a homogeneous solution, and reacting with at least one silane compound and halides of transition metal titanium and its derivatives, the catalyst has high activity when used in slurry polymerization of ethylene, the particle shape of the catalyst is improved, but the problems of less regular catalyst particle shape, poor flowability, relatively dispersed particle size distribution of the prepared polymer, low bulk density, etc. still exist.

Disclosure of Invention

The object of the present invention is to overcome the above mentioned drawbacks of the prior art and to provide a solid catalyst component and a process for its preparation and an olefin polymerization catalyst.

The first aspect of the invention provides a solid catalyst component, which contains titanium element, magnesium element, alkoxy compound, phosphorus element and halogen, wherein the content of the titanium element is 1-15 wt%, the content of the magnesium element is 10-30 wt%, the content of the phosphorus element is 0.01-1 wt%, the content of the alkoxy compound is 1-10 wt%, and the content of the halogen element is 40-70 wt% based on the total weight of the solid catalyst component; the angle of repose of the solid catalyst component is 20-40 degrees.

A second aspect of the present invention provides a method for preparing a solid catalyst component, comprising the steps of: dissolving a magnesium compound in a solvent system containing at least one organic epoxy compound, at least one organic phosphorus compound, at least one organic alcohol compound and at least one inert diluent to form a uniform solution, adding a precipitation aid into the solution, then reducing the temperature of the system and adding a titanium compound to obtain a suspension system containing a solid component, then raising the temperature of the system, and filtering, washing and drying the suspension system to obtain the solid catalyst component; wherein the titanium compound is added into the system for multiple times.

The third aspect of the present invention provides a solid catalyst component obtained by the above production method.

A fourth aspect of the present invention provides an olefin polymerization catalyst comprising the following components:

A. the above solid catalyst component;

B. an organoaluminum compound.

A fifth aspect of the present invention provides the use of the above solid catalyst component and/or olefin polymerization catalyst in ethylene polymerization.

The solid catalyst component and the catalyst have the advantages of good particle shape, good fluidity, higher bulk density, high catalyst activity, centralized particle size distribution of the prepared polymer, high bulk density, simple production process and relatively low production cost. The solid catalyst component and the catalyst are particularly suitable for slurry polymerization of ethylene.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The first aspect of the invention provides a solid catalyst component, which contains titanium element, magnesium element, alkoxy compound, phosphorus element and halogen, wherein the content of the titanium element is 1-15 wt%, the content of the magnesium element is 10-30 wt%, the content of the phosphorus element is 0.01-1 wt%, the content of the alkoxy compound is 1-10 wt%, and the content of the halogen element is 40-70 wt% based on the total weight of the solid catalyst component; the angle of repose of the solid catalyst component is 20-40 degrees.

According to the present invention, preferably, the content of the titanium element is 2 to 10 wt%, the content of the magnesium element is 15 to 25 wt%, the content of the phosphorus element is 0.1 to 0.8 wt%, the content of the alkoxy compound is 2 to 8 wt%, and the content of the halogen element is 50 to 65 wt%, based on the total weight of the solid catalyst component.

According to the present invention, it is preferable that the angle of repose of the solid catalyst component is 25 to 35 °.

According to the present invention, preferably, the average particle size of the solid catalyst component is 2 to 10 micrometers, preferably 3 to 8 micrometers; the bulk density is 0.30 to 0.50 g/ml, preferably 0.35 to 0.45 g/ml.

In the present invention, the catalyst particle size distribution is determined by means of a Mastersizer 2000 instrument (Malvern, UK). The bulk density of the solid catalyst component is determined by reference to ASTM D1895-96; the angle of repose of the solid component of the catalyst is determined with reference to GB-T11986-98.

A second aspect of the present invention provides a method for preparing a solid catalyst component, comprising the steps of: dissolving a magnesium compound in a solvent system containing at least one organic epoxy compound, at least one organic phosphorus compound, at least one organic alcohol compound and at least one inert diluent to form a uniform solution, adding a precipitation aid into the solution, then reducing the temperature of the system and adding a titanium compound to obtain a suspension system containing a solid component, then raising the temperature of the system, and filtering, washing and drying the suspension system to obtain the solid catalyst component; wherein the titanium compound is added into the system for multiple times.

Compared with the prior art, the method optimizes the adding mode of the titanium compound, and in the prior art, the titanium compound is added into the system at one time. The inventors of the present invention have found in their studies that the addition of a titanium compound in portions improves the morphology and performance parameters of the resulting solid catalyst component.

In the present invention, the number of times of adding the titanium compound is not particularly limited, and may be two, three, or more.

According to the method of the present invention, preferably, the amount of the first added titanium compound is 5 to 20%, more preferably 8 to 20%, and still more preferably 9 to 15% of the total amount of all titanium compounds; the time interval between the first addition of the titanium compound and the next addition of the titanium compound is 20-80%, preferably 40-70% of the total time required for adding all the titanium compounds into the system. The morphology and performance parameters of the obtained solid catalyst component can be further improved by further finely controlling the addition mode of the titanium compound.

In the method of the invention, the titanium compound can be added at the initial stage of cooling the system, at the middle stage of cooling or after the cooling is finished. Preferably, part of the titanium compound is added during the cooling process of the system, and the rest of the titanium compound is added after the cooling process of the system.

From the viewpoint of considering both the performance of the obtained solid catalyst component and the convenience of operation, the titanium compound is added into the system twice, the first part of the titanium compound is added in the process of cooling the system, and the rest is added after the process of cooling the system. More specifically, when the system is cooled to a first target temperature, a first portion of the titanium compound is added, then the system is continuously cooled to a final target temperature, and the remaining portion of the titanium compound is added.

Generally, in the preparation of the solid catalyst component, the temperature of the system (i.e., the final target temperature) is lowered to-30 ℃ to 30 ℃, preferably to-30 ℃ to 10 ℃.

According to a specific embodiment of the invention, when the temperature of the system is reduced to-15 ℃ to 0 ℃, a first part of titanium compound is added, then the temperature of the system is continuously reduced to-30 ℃ to-20 ℃, and the rest part of titanium compound is added.

In a manner similar to the manner in which the titanium compound is added in the prior art, the titanium compound is added slowly dropwise each time.

According to a specific embodiment of the invention, the temperature of the system is raised to 60-110 ℃, the method further comprises stirring the suspension system for 0.5-8 hours at the temperature, and then filtering, washing and drying the suspension system.

According to the present invention, the formation of a homogeneous solution may be achieved using conditions conventional in the art, such as by heating to facilitate dissolution of the components, for example at a temperature of 50-60 ℃.

In the present invention, the titanium compound may be various titanium compounds commonly used in the preparation of solid components of olefin polymerization catalysts, for example, the titanium compound has the general formula Ti (OR)_aX_bWherein R is C₁～C₁₄X is a halogen atom, a is an integer of 0 to 2, b is an integer of 0 to 4, a + b is 3 or 4; it is preferably at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium and titanium trichloride, and it is further preferably at least one selected from the group consisting of titanium tetrachloride, trichloromonoethoxytitanium and titanium trichloride. The titanium compound may be added in the form of a halide of titanium alone or in the form of a mixture of a halide of titanium with an inert diluent.

The particular types of components used in the present invention can be selected as is conventional in the art.

The magnesium compound may be at least one of a halide of magnesium, an alcoholate of magnesium, and a haloalcoholate of magnesium; specifically, the method includes but is not limited to: magnesium chloride.

The organic epoxy compound may be selected from C₂～C₈At least one of an oxide, glycidyl ether and internal ether of an aliphatic olefin, diolefin or halogenated aliphatic olefin or diolefin of (a); specifically, the method includes but is not limited to: ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, or mixtures thereof.

The organophosphorus compound is selected from hydrocarbyl and/or halohydrocarbyl esters of orthophosphoric acid and/or phosphorous acid; specifically, the method includes but is not limited to: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, benzyl phosphite, or mixtures thereof.

The organic alcohol compound is selected from C₂～C₁₀The fatty alcohol of (a); specifically, the method includes but is not limited to: methanol, ethanol, propanol, butanol, hexanol, diethylhexanol, or mixtures thereof.

The precipitation aid is selected from at least one of organic acid, organic acid anhydride, organic ether and organic ketone; specifically, the method includes but is not limited to: acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether, pentyl ether, or a mixture thereof.

The inert diluent is selected from C₆～C₁₀And/or C₆～C₈The aromatic hydrocarbon of (1). Specifically, the method includes but is not limited to: hexane, heptane, octane, decane, benzene, toluene, xylene, or a mixture thereof, or a derivative thereof.

The amounts of the above components may also be selected as is conventional in the art. Specifically, the amount of the organic epoxy compound is 0.2 to 10 mol, preferably 0.5 to 4 mol, per mol of the magnesium halide; the dosage of the organic phosphorus compound is 0.1-3 mol, preferably 0.3-1 mol; the amount of the organic alcohol compound is 0.1 to 10 moles, preferably 0.5 to 5 moles; the dosage of the inert diluent is 0.5-5L; the amount of the titanium compound is 1 to 15 mol, preferably 2 to 10 mol.

The third aspect of the present invention provides a solid catalyst component obtained by the above production method. The solid catalyst component of the present invention is in the form of particles.

A fourth aspect of the present invention provides an olefin polymerization catalyst comprising the following components:

A. the above solid catalyst component;

B. an organoaluminum compound.

The general formula of the organic aluminum compound is AlR'_nX’_3-nWherein R' may be hydrogen or C₁～C₂₀In particular alkyl, aralkyl, aryl; x' is halogen, in particular chlorine and bromine; 0<n is less than or equal to 3. Specific compounds are as follows: and alkylaluminum halides such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloroate, with triethylaluminum and triisobutylaluminum being more preferable.

In the catalyst of the present invention, the molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component is 5 to 5000: 1, preferably 20 to 500: 1.

a fifth aspect of the present invention provides the use of the above solid catalyst component and/or olefin polymerization catalyst in ethylene polymerization. The solid catalyst component and the olefin polymerization catalyst of the present invention are particularly suitable for slurry polymerization of ethylene.

The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples.

In the following examples:

the catalyst particle size distribution was determined using a Mastersizer 2000 instrument (Malvern, uk).

The apparent Bulk Density (BD) of the catalyst and polymer was determined in accordance with ASTM D1895-96.

The angle of repose is determined with reference to GB-T11986-98.

The contents of elements titanium, magnesium and chlorine in the catalyst are determined by a chemical analysis method, the content of alkoxy is determined by gas chromatography, and the content of phosphorus is determined by X-ray energy spectrum analysis.

Catalyst component ethylene polymerization evaluation method: a2-liter polymerization vessel was alternately charged with nitrogen and evacuated three times, and 1.0 liter of n-hexane, 2mmol of triethylaluminum and 10 mg of the above solid catalyst component were added. The temperature of the reaction kettle is raised to 60 ℃, then ethylene is introduced until the kettle pressure is 0.7MPa, and the reaction lasts for 2 hours. And after the reaction is finished, cooling, separating and collecting the polymer.

Example 1

Adding 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epoxy chloropropane, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol into a reaction kettle repeatedly replaced by high-purity nitrogen in sequence, reacting for 1 hour at the temperature of 55 ℃, then adding 1.6 g of phthalic anhydride, continuing to react for 1 hour, cooling to-10 ℃, slowly adding 30 ml of mixed solution consisting of 80 ml of titanium tetrachloride and 200 ml of toluene dropwise for 30 minutes, cooling to-30 ℃ after 90 minutes, and adding the rest of the mixed solution dropwise for 90 minutes. Heating to 90 ℃ within 4 hours, keeping the temperature for 1.5 hours, filtering out mother liquor, washing with toluene twice, then washing with hexane for 3 times, and drying the residual solid product to obtain the solid titanium catalyst component.

Example 2

Adding 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epoxy chloropropane, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol into a reaction kettle repeatedly replaced by high-purity nitrogen in sequence, reacting for 1 hour at the temperature of 55 ℃, then adding 1.6 g of phthalic anhydride, continuing to react for 1 hour, cooling to-10 ℃, slowly adding 50 ml of mixed solution consisting of 80 ml of titanium tetrachloride and 200 ml of toluene dropwise for 45 minutes, cooling to-30 ℃ after 120 minutes, and adding the rest of the mixed solution dropwise for 120 minutes. Heating to 90 ℃ within 4 hours, keeping the temperature for 1.5 hours, filtering out mother liquor, washing with toluene twice, then washing with hexane for 3 times, and drying the residual solid product to obtain the solid titanium catalyst component.

Example 3

Adding 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epoxy chloropropane, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol into a reaction kettle repeatedly replaced by high-purity nitrogen in sequence, reacting for 1 hour at the temperature of 55 ℃, then adding 1.6 g of phthalic anhydride, continuing to react for 1 hour, cooling to-20 ℃, slowly adding 55 ml of mixed solution consisting of 80 ml of titanium tetrachloride and 200 ml of toluene dropwise for 60 minutes, cooling to-30 ℃ after 120 minutes, and adding the rest of the mixed solution dropwise for 90 minutes. Heating to 90 ℃ within 4 hours, keeping the temperature for 1.5 hours, filtering out mother liquor, washing with toluene twice, then washing with hexane for 3 times, and drying the residual solid product to obtain the solid titanium catalyst component.

Example 4

Adding 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epoxy chloropropane, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol into a reaction kettle repeatedly replaced by high-purity nitrogen in sequence, reacting for 1 hour at the temperature of 55 ℃, then adding 1.6 g of phthalic anhydride, continuing to react for 1 hour, cooling to-10 ℃, slowly adding 30 ml of mixed solution consisting of 80 ml of titanium tetrachloride and 200 ml of toluene dropwise for 30 minutes, keeping for 90 minutes, and adding the rest of mixed solution dropwise for 90 minutes. Heating to 90 ℃ within 4 hours, keeping the temperature for 1.5 hours, filtering out mother liquor, washing with toluene twice, then washing with hexane for 3 times, and drying the residual solid product to obtain the solid titanium catalyst component.

Example 5

Adding 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epoxy chloropropane, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol into a reaction kettle repeatedly replaced by high-purity nitrogen in sequence, reacting for 1 hour at the temperature of 55 ℃, then adding 1.6 g of phthalic anhydride, continuing to react for 1 hour, cooling to-10 ℃, slowly adding 30 ml of mixed solution consisting of 80 ml of titanium tetrachloride and 200 ml of toluene dropwise for 30 minutes, cooling to-30 ℃ after 60 minutes, and adding the rest of the mixed solution dropwise for 120 minutes. Heating to 90 ℃ within 4 hours, keeping the temperature for 1.5 hours, filtering out mother liquor, washing with toluene twice, then washing with hexane for 3 times, and drying the residual solid product to obtain the solid titanium catalyst component.

Example 6

Adding 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epoxy chloropropane, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol into a reaction kettle repeatedly replaced by high-purity nitrogen in sequence, reacting for 1 hour at the temperature of 55 ℃, then adding 1.6 g of phthalic anhydride, continuing to react for 1 hour, cooling to-10 ℃, slowly adding 80 ml of mixed solution consisting of 80 ml of titanium tetrachloride and 200 ml of toluene dropwise for 60 minutes, cooling to-30 ℃ after 60 minutes, and adding the rest of the mixed solution dropwise for 90 minutes. Heating to 90 ℃ within 4 hours, keeping the temperature for 1.5 hours, filtering out mother liquor, washing with toluene twice, then washing with hexane for 3 times, and drying the residual solid product to obtain the solid titanium catalyst component.

Comparative example 1

In a reaction kettle repeatedly replaced by high-purity nitrogen, 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epichlorohydrin, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol are sequentially added, the mixture is reacted for 1 hour at the temperature of 55 ℃, then 1.6 g of phthalic anhydride is added, the reaction is continued for 1 hour, the temperature is reduced to-10 ℃, 80 ml of titanium tetrachloride is dropwise added at the temperature, the temperature is increased to 90 ℃ within 4 hours, the temperature is kept for 1.5 hours, then mother liquor is filtered, the mother liquor is washed twice by toluene, then the mother liquor is washed by hexane for 3 times, and the residual solid product is dried to obtain the solid titanium catalyst component.

Comparative example 2

In a reaction kettle repeatedly replaced by high-purity nitrogen, 9.6 g of anhydrous magnesium chloride, 110 ml of toluene, 6.0 ml of epichlorohydrin, 7.2 ml of tributyl phosphate and 15.2 ml of ethanol are sequentially added, the mixture is reacted for 1 hour at the temperature of 55 ℃, then 1.6 g of phthalic anhydride is added, the reaction is continued for 1 hour, the temperature is reduced to-30 ℃, 80 ml of titanium tetrachloride is dropwise added at the temperature, the temperature is increased to 90 ℃ within 4 hours, the temperature is kept for 1.5 hours, then mother liquor is filtered, the mother liquor is washed twice by toluene, then the mother liquor is washed by hexane for 3 times, and the residual solid product is dried to obtain the solid titanium catalyst component.

Comparative example 3

The catalyst component was prepared according to the method of example 4 in chinese patent application CN 1958620A.

Comparative example 4

The catalyst component was prepared according to the procedure of example 1 in chinese patent ZL 85100997.2.

Comparative example 5

The catalyst component was prepared according to the method of example 1 in chinese patent application CN 1091748A.

Test example

The catalyst components prepared in the above examples and comparative examples were tested as shown in the following Table 1, and the ethylene polymerization evaluation data are shown in the following Table 2.

Table 1 catalyst testing data

Table 2 ethylene polymerization evaluation data

As can be seen from the data in Table 1, the catalyst component particles of the present invention have a higher bulk density, a smaller angle of repose and a better flowability. The data in Table 2 show that the catalyst component of the present invention has high activity, and the prepared polymer has high bulk density, concentrated particle size distribution and less coarse powder and fine powder.

Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.