Olefin polymerization catalyst precursor and olefin polymerization catalyst carrier and preparation method and application thereof

Abstract

The present invention discloses an olefin polymerization catalyst precursor and an olefin polymerization catalyst carrier, and a preparation method and application thereof. The olefin polymerization catalyst precursor comprises a solid component and a liquid component, wherein the solid component comprises a complex of a magnesium halide and an alkoxy titanium, a complex of an alkoxy magnesium and a tetravalent titanium halide, and a magnesium halide alcoholate; the liquid component comprises a mixture of a dispersant and a first alcohol compound; the chemical formula of the complex of a magnesium halide and an alkoxy titanium and the complex of an alkoxy magnesium and a tetravalent titanium halide is Mg m ·Ti n (R1O) m ·(R2O) m ·X 4n , wherein X is a halogen, m is a positive integer, and 1≤2n / m≤1.6. The olefin polymerization catalyst precursor of the present invention can use alkoxymagnesium that is not limited by particle morphology as an initial raw material, and adopt a non-toxic material system to complete the conversion of alkoxymagnesium into olefin polymerization catalyst precursor. The catalyst carrier particle of the present invention has good morphology.

Description

Technical Field

[0001] The invention relates to an olefin polymerization catalyst precursor, a preparation method and application thereof, and an olefin polymerization catalyst carrier using the precursor, a preparation method and application thereof. Background Art

[0002] At present, polymers and copolymers of low-order alpha-olefins, especially ethylene, propylene and butene, have been widely used. The manufacturing cost of these polymer products is low, and they also have many properties suitable for industrial applications. The most commonly used form of these polymers is a highly crystalline solid. In the polymerization process, whether it is polymerized by liquid phase, gas phase, slurry polymerization or any other common method, the morphology of the catalyst particles and the polymer particles is required to be in the required shape and size to varying degrees, wherein the morphology of the catalyst particles plays a decisive role, and the morphological structural characteristics of the main catalyst carrier determine the morphological characteristics of the main catalyst. Therefore, the formation, preparation and morphological characteristics of the catalyst carrier are crucial for producing polymer particles of qualified shape and size.

[0003] As is well known, there are mainly two ways to prepare Ziegler-Natta catalysts using alkoxymagnesium as initial material. The way to prepare Ziegler-Natta catalysts using alkoxymagnesium as initial material disclosed in Chinese patents CN101906017A and CN102399326 A is to first use metal magnesium, alcohols and halogenating agents to react under specific conditions to prepare alkoxymagnesium particles, then use alkoxymagnesium particles to control a certain temperature to contact with titanium halide, then react with as an internal electron donor compound, then process with titanium halide to obtain a solid catalyst component. The catalyst prepared by the method has a higher bulk density and good particle morphology, and has high activity during polymerization, and the obtained polymer has the characteristics of good stereoregularity, good particle morphology, and less fine powder content. However, when preparing alkoxymagnesium particle carriers, a part of carrier particles will be treated as hazardous waste because of form or size that are not suitable for subsequent catalyst preparation, increase processing costs, and cause waste of resources.

[0004] U.S. Patents US5082907A, US5151399A, US5229342A, US5106806A, US5146028A, US5066737A, US5124298A and US5077357A disclose various catalyst precursors containing magnesium and titanium, some of which are prepared using the above-mentioned alkoxymagnesium as a starting material. These precursors have no polymerization catalyst activity and do not contain any effective electron donors, but these precursors are used as starting materials in the subsequent conversion into active procatalysts. The magnesium and titanium-containing procatalyst is either formed by direct chlorination of the magnesium and titanium-containing precursor, or by reacting the magnesium and titanium-containing precursor with a tetravalent titanium halide, an optional hydrocarbon and an optional electron donor. The prepared procatalyst solid is then separated from the reaction slurry (by filtering, precipitation, crystallization, etc.), and then these main catalysts are reacted with cocatalysts and selectivity control agents to be converted into polymerization catalysts. US Pat. No. 5,034,361A discloses dissolving alkoxymagnesium in an alkanol solvent by allowing the alkoxymagnesium compound to interact with certain acidic substances. Then, the magnesium-containing catalyst precursor is reacted with various titanium compounds to prepare a catalyst precursor containing magnesium and titanium.

[0005] When alkoxymagnesium such as ethoxymagnesium is used as a starting material to form a procatalyst precursor, a cleaving agent is often required to break the aggregated ethoxymagnesium and react it with other components. As disclosed in U.S. Pat. Nos. 5,124,298A and 5,077,357A, the precursor is made with chlorobenzene as a solvent and o-cresol as a cleaving agent that chemically breaks the aggregated ethoxymagnesium. A small amount of o-cresol (1-3%) remains in the precursor product. In addition to being physiologically irritating, it will still become a polymerization catalyst poison if it is not effectively filtered out in the catalyst preparation step. In addition to the cleaving agents including physiologically irritating phenolic compounds such as p-cresol, 3-methoxyphenol, 4-dimethylaminophenol introduced in the above patents, there are many methods that use boric acid-containing solubilizing agents to complete the dissolution of alkoxymagnesium so that the reaction of the magnesium compound can be carried out in the liquid phase. This method is relatively complicated because a precipitant is required to precipitate the solid product, and because some raw materials are lost during the dissolution process, the cost is high and the efficiency is low.

[0006] Therefore, it is of great significance to find a substance or substance system that will neither irritate the personnel preparing the catalyst nor be toxic to the polymerization catalyst to promote the dissolution of alkoxymagnesium.

[0007] In addition, the existing solution for dissolving alkoxymagnesium needs to be precipitated in a specific manner to precipitate a catalyst carrier that meets the requirements of the catalyst particle morphology. The precipitation preparation process of the catalyst carrier requires the addition of a specific precipitation aid to improve the particle morphology of the precipitated solid component. To this end, the inventors have disclosed a series of precipitation aid systems containing 1,3-diol esters, and prepared olefin polymerization catalysts (CN102276765B, CN101993506B, CN101864009B, CN101643519B, CN103012627A, CN103012625A, CN103012626). The olefin polymerization catalyst prepared by the precipitation aid system containing 1,3-diol esters contains a small amount of 1,3-diol ester compounds, and the presence of these diol ester compounds greatly improves the particle morphology of the catalyst. However, the above particles have the problem that a toxic substance system is required to prepare the catalyst precursor, the catalyst particles contain catalyst toxic substances such as o-cresol, and the resulting catalyst carrier particles have poor morphology. Summary of the invention

[0008] In view of the above problems existing in the prior art, the present invention provides a new olefin polymerization catalyst precursor and olefin polymerization catalyst carrier. The olefin polymerization catalyst precursor can use alkoxymagnesium that is not restricted by particle morphology as the initial raw material, adopt a non-toxic material system to complete the conversion of alkoxymagnesium into olefin polymerization catalyst precursor, and complete the preparation of olefin polymerization catalyst precursor (dissolved solution). It can get rid of the limitation of alkoxymagnesium carrier particle morphology on catalyst preparation. Catalyst toxic substances such as o-cresol are not contained in the catalyst particles, and the obtained catalyst carrier particles have good morphology.

[0009] The first aspect of the present invention provides an olefin polymerization catalyst precursor, comprising a solid component and a liquid component, wherein the solid component comprises a complex of a magnesium halide and an alkoxy titanium, a complex of an alkoxy magnesium and a tetravalent titanium halide, and a magnesium halide alcoholate; the liquid component comprises a mixture of a dispersant and a first alcohol compound; the complex of a magnesium halide and an alkoxy titanium and the complex of an alkoxy magnesium and a tetravalent titanium halide have a general chemical formula of Mg m ·Ti n (R1O) m (R2O) m ·X 4n , wherein X is a halogen, m is a positive integer, 1≤2n / m≤1.6, preferably, 1≤2n / m≤1.2; R1 and R2 are the same or different, and each independently represents a C1-C2 with or without a substituent 10 A hydrocarbon group, a C6-C 20 of phenyl.

[0010] In the present invention, n / m is the molar ratio of the tetravalent titanium halide to the alkoxy magnesium added in step 1 during the preparation process.

[0011] In the present invention, the olefin polymerization catalyst precursor can utilize magnesium alkoxide as a starting material without being restricted in particle form.

[0012] In the present invention, the magnesium halide may be at least one of magnesium chloride, magnesium bromide and magnesium iodide.

[0013] In the present invention, the halogen element may be at least one of chlorine, bromine and iodine.

[0014] According to some embodiments of the present invention, R1 and R2 are C2-C4 hydrocarbon groups with or without substituents, C6-C 10 of phenyl.

[0015] According to some embodiments of the present invention, the substituent is selected from H, hydroxyl, halogen, and ether.

[0016] According to some embodiments of the present invention, OR1 and OR2 are the same or different, and are independently selected from one or more of ethoxy, propoxy, butoxy and phenoxy.

[0017] According to some embodiments of the present invention, the content of the complex of magnesium halide and alkoxytitanium is 10-99.8 wt % based on the total weight of the solid component.

[0018] According to some embodiments of the present invention, the content of the complex of alkoxymagnesium and tetravalent titanium halide is 0.01-90 wt % based on the total weight of the solid component.

[0019] According to some embodiments of the present invention, the content of the magnesium halide alcoholate is 0.01-10 wt % based on the total weight of the solid component.

[0020] According to some embodiments of the present invention, the content of the solid component is 10-90 wt % based on the total weight of the olefin polymerization catalyst precursor.

[0021] According to some embodiments of the present invention, the content of the liquid component is 10-90 wt % based on the total weight of the olefin polymerization catalyst precursor.

[0022] The second aspect of the present invention provides a method for preparing an olefin polymerization catalyst precursor, comprising: in the presence of a first dispersant, subjecting an alkoxy magnesium, a first alcohol compound and a tetravalent titanium halide to a first contact reaction.

[0023] According to some embodiments of the present invention, the structural formula of the magnesium alkoxide is Mg(R1O)(R2O), wherein R1 and R2 are the same or different and are independently C1-C2 with or without a substituent. 10 A hydrocarbon group, a C6-C 20 of phenyl.

[0024] According to some embodiments of the present invention, R1 and R2 are C2-C4 hydrocarbon groups with or without substituents, C6-C 10 of phenyl.

[0025] According to some embodiments of the present invention, the substituent is selected from H, hydroxyl, halogen, and ether.

[0026] According to some embodiments of the present invention, OR1 and OR2 are the same or different, and are independently selected from one or more of ethoxy, propoxy, butoxy and phenoxy.

[0027] According to some embodiments of the present invention, the alkoxy magnesium is selected from one or more of diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium and diphenoxy magnesium.

[0028] According to some embodiments of the present invention, the first alcohol compound is C1-C 10 At least one of the linear and branched alcohols, preferably C2-C 10 Preferably, the alcohol compound is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, amyl alcohol, isopentanol, hexanol, heptanol, octanol, isooctyl alcohol, nonanol and decanol.

[0029] According to some embodiments of the present invention, the molar ratio of the first alcohol compound to the alkoxymagnesium is 0.01-2:1, more preferably 0.02-0.4:1.

[0030] According to some embodiments of the present invention, the general formula of the tetravalent titanium halide is Ti(OR 10 ) m X 4－m The titanium compound shown in the general formula, R 10 is an alkyl group, preferably C1-C 10 X is a halogen, preferably Cl, Br or I; 0≤m≤3, m is an integer.

[0031] According to some embodiments of the present invention, the tetravalent titanium halide is selected from at least one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, alkoxy titanium trihalide, dialkoxy titanium dihalide and trialkoxy titanium halide.

[0032] According to some embodiments of the present invention, the molar ratio of tetravalent titanium halide to magnesium alkoxide is 0.25-1:1, preferably 0.5-0.8:1.

[0033] According to some embodiments of the present invention, the first dispersant can be various alkane compounds, aromatic hydrocarbon compounds or mineral oils commonly used in the art that do not chemically interact with alkoxy magnesium and alcohol compounds. Specific examples can be one or more of alkanes, cycloalkanes, aromatic hydrocarbons, kerosene, vaseline oil, and white oil, preferably one or more of decane, benzene, toluene, and xylene, and more preferably toluene.

[0034] According to some embodiments of the present invention, the molar ratio of the first dispersant to the magnesium alkoxide is 5-50:1, preferably 5-20:1.

[0035] According to the present invention, the order of adding the alkoxy magnesium, the first alcohol compound, the tetravalent titanium halide and the first dispersant is not specifically limited. Preferably, the order of adding can be first adding the alkoxy magnesium, then adding the dispersant and stirring to achieve dispersion, and then adding the tetravalent titanium halide and the first alcohol compound to carry out contact reaction.

[0036] According to some embodiments of the present invention, the purpose of the first contact reaction is to react the alkoxy magnesium, the first alcohol compound and the tetravalent titanium halide in the presence of a dispersant to form a slurry. The present invention does not specifically limit the conditions for the first contact reaction to form a slurry, which can be determined according to the specific alkoxy magnesium used. Preferably, the conditions of the first contact reaction include: a temperature of 10-150°C, preferably 60-120°C; a time of 1-10 hours, preferably 2-6 hours.

[0037] The third aspect of the present invention provides an olefin polymerization catalyst precursor obtained according to the above-mentioned preparation method. The olefin polymerization catalyst precursor comprises a solid component and a liquid component, wherein the solid component comprises a complex of a magnesium halide and an alkoxy titanium, a complex of an alkoxy magnesium and a tetravalent titanium halide, and a magnesium halide alcoholate; the liquid component comprises a mixture of a dispersant and a first alcohol compound; the chemical formula of the complex of a magnesium halide and an alkoxy titanium and the complex of an alkoxy magnesium and a tetravalent titanium halide is Mg m ·Ti n (R1O) m (R2O) m ·X 4n , wherein X is a halogen, m is a positive integer, 1≤2n / m≤1.6, preferably, 1≤2n / m≤1.2; R1 and R2 are the same or different, and each independently represents a C1-C2 with or without a substituent 10 A hydrocarbon group, a C6-C 20 of phenyl.

[0038] In the present invention, n / m is the molar ratio of the tetravalent titanium halide to the alkoxy magnesium added in step 1 during the preparation process.

[0039] In the present invention, the olefin polymerization catalyst precursor can utilize magnesium alkoxide as a starting material without being restricted in particle form.

[0040] In the present invention, the magnesium halide may be at least one of magnesium chloride, magnesium bromide and magnesium iodide.

[0041] In the present invention, the halogen element may be at least one of chlorine, bromine and iodine.

[0042] According to some embodiments of the present invention, R1 and R2 are C2-C4 hydrocarbon groups with or without substituents, C6-C 10 of phenyl.

[0043] According to some embodiments of the present invention, the substituent is selected from H, hydroxyl, halogen, and ether.

[0044] According to some embodiments of the present invention, OR1 and OR2 are the same or different, and are independently selected from one or more of ethoxy, propoxy, butoxy and phenoxy.

[0045] According to some embodiments of the present invention, the content of the complex of magnesium halide and alkoxytitanium is 10-99.8 wt % based on the total weight of the solid component.

[0046] According to some embodiments of the present invention, the content of the complex of alkoxymagnesium and tetravalent titanium halide is 0.01-90 wt % based on the total weight of the solid component.

[0047] According to some embodiments of the present invention, the content of the magnesium halide alcoholate is 0.01-10 wt % based on the total weight of the solid component.

[0048] According to some embodiments of the present invention, the content of the solid component is 10-90 wt % based on the total weight of the olefin polymerization catalyst precursor.

[0049] According to some embodiments of the present invention, the content of the liquid component is 10-90 wt % based on the total weight of the olefin polymerization catalyst precursor.

[0050] A fourth aspect of the present invention provides a method for preparing an olefin polymerization catalyst carrier, comprising:

[0051] (1) subjecting the above-mentioned olefin polymerization catalyst precursor or the olefin polymerization catalyst precursor obtained according to the above-mentioned preparation method to a second contact reaction with a second alcohol compound to obtain a solution;

[0052] (2) In the presence of a precipitation aid and a second dispersant, the solution obtained in step (1) is subjected to a third contact reaction with a titanium compound, the temperature is increased to precipitate a solid precipitate, a mixture containing a solid precipitate is obtained, and the mixture is separated.

[0053] According to some embodiments of the present invention, the second alcohol compound is one or more of aliphatic alcohol, alicyclic alcohol and aromatic alcohol; preferably C1-C 10 Straight chain fatty alcohols, C3-C 10 Branched chain fatty alcohols, C3-C 12 Alicyclic alcohols, C6-C 20 Aromatic alcohols and C7-C 20 One or more of the alkyl aromatic alcohols; more preferably, the second alcohol compound is selected from one or more of ethanol, propanol, butanol, 2-ethylhexanol, benzyl alcohol and phenylethyl alcohol.

[0054] According to some embodiments of the present invention, the molar ratio of the second alcohol compound to the alkoxymagnesium is 0.2-10:1, more preferably 2-5:1.

[0055] According to some embodiments of the present invention, the conditions of the second contact reaction include: temperature of 10-150° C., preferably 60-140° C.; time of 0.1-10 hours, preferably 0.5-6 hours.

[0056] According to some embodiments of the present invention, the precipitation aid includes precipitation aid a, precipitation aid b and precipitation aid c, wherein the precipitation aid a is a glycol ester compound, the precipitation aid b is an alkyl ester of an aliphatic or aromatic carboxylic acid, and the precipitation aid c is a titanate compound.

[0057] According to some embodiments of the present invention, relative to 1 mol of alkoxy magnesium calculated as magnesium element, the amount of the precipitation aid a is 0.005-0.1 mol, preferably 0.01-0.05 mol; the amount of the precipitation aid b is 0.01-0.5 mol, preferably 0.02-0.2 mol; the amount of the precipitation aid c is 0.01-0.3 mol, preferably 0.02-0.08 mol.

[0058] According to some embodiments of the present invention, the precipitation aid a is a diol ester compound represented by formula (I),

[0059]

[0060] In formula (I), R1-R2 are the same or different and are independently substituted or unsubstituted C1-C 20 Straight chain alkyl, substituted or unsubstituted C3-C 20branched alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C7-C 20 Alkaryl, substituted or unsubstituted C7-C 20 Aralkyl, substituted or unsubstituted C2-C 10 an olefin group or a substituted or unsubstituted C 10 -C 20 R3-R8 are the same or different and are independently hydrogen, halogen, substituted or unsubstituted C1-C 20 Straight chain alkyl, substituted or unsubstituted C3-C 20 branched alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C7-C 20 Alkaryl, substituted or unsubstituted C7-C 20 Aralkyl, substituted or unsubstituted C2-C 10 an olefin group or a substituted or unsubstituted C 10 -C 20 or at least one of R3-R6 forms a ring with at least one of R7-R8; preferably, the precipitation aid a is selected from 2-ethyl-1,3-propylene glycol dibenzoate, 2-propyl-1,3-propylene glycol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propylene glycol dibenzoate, 1,3-butylene glycol dimethyl benzoate, 2-methyl-1,3-butylene glycol dichlorobenzoate, 2,3-dimethyl- One or more of 1,3-butanediol dibenzoate, 1,3-pentanediol dipivalate, 2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol benzoic acid cinnamate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,4-heptanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate and 2-methyl-3,5-heptanediol dibenzoate.

[0061] According to some embodiments of the present invention, the amount of the precipitation aid a is 0.005-0.1 mol, preferably 0.01-0.05 mol, relative to 1 mol of alkoxy magnesium calculated as magnesium element.

[0062] According to some embodiments of the present invention, the precipitation aid b is a C1-C8 aliphatic carboxylic acid or a C7-C 10 The C1-C 10Preferably, the precipitation aid b is selected from one or more of ethyl benzoate, diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-isooctyl phthalate, di-n-octyl phthalate, diethyl adipate and dibutyl adipate.

[0063] According to some embodiments of the present invention, the amount of the precipitation aid b is 0.01-0.5 mol, preferably 0.02-0.2 mol, relative to 1 mol of alkoxy magnesium calculated as magnesium element.

[0064] According to some embodiments of the present invention, the precipitation aid c is a general formula of Ti(OR9) n X 4-n Titanate compounds, wherein R9 is C1-C 10 Alkyl or C3-C 10 cycloalkyl, X is halogen; 1≤n≤4, n is an integer; preferably, the precipitation aid c is selected from one or more of tetrabutyl titanate, tetraethyl titanate and isopropyl titanate.

[0065] According to some embodiments of the present invention, the amount of the precipitation aid c is 0.01-0.3 mol, preferably 0.02-0.08 mol, relative to 1 mol of alkoxy magnesium calculated as magnesium element.

[0066] According to some embodiments of the present invention, the second dispersant can be various alkane compounds, aromatic hydrocarbon compounds or mineral oils commonly used in the art that do not chemically interact with alkoxy magnesium and alcohol compounds. Specific examples can be one or more of alkanes, cycloalkanes, aromatic hydrocarbons, kerosene, vaseline oil, and white oil, preferably one or more of decane, benzene, toluene, and xylene, and more preferably toluene.

[0067] According to some embodiments of the present invention, the amount of the second dispersant is 0.01-50 moles, preferably 5-20 moles, relative to 1 mole of alkoxy magnesium calculated as magnesium element.

[0068] According to some embodiments of the present invention, the general formula of the titanium compound may be Ti(OR 10 ) m X 4－m The titanium compound shown in the general formula, R 10 is an alkyl group, preferably C1-C 10 X is a halogen, preferably Cl, Br or I; 0≤m≤3, m is an integer.

[0069] According to some embodiments of the present invention, the titanium compound is selected from at least one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, alkoxy titanium trihalide, dialkoxy titanium dihalide and trialkoxy titanium halide.

[0070] According to some embodiments of the present invention, in the presence of a precipitation aid, the catalyst precursor and the titanium compound are subjected to a third contact reaction to precipitate a solid precipitate, and the mixture containing the solid precipitate is not particularly limited. For example, the titanium compound can react with the catalyst precursor alone in the presence of a precipitation aid, or the titanium compound can be mixed with a dispersant and reacted with the catalyst precursor in the presence of a precipitation aid. Preferably, the titanium compound is mixed with a dispersant and reacted with the catalyst precursor in the presence of a precipitation aid. Generally, according to the preparation method of the catalyst component for olefin polymerization of the present invention, the dispersant mixed with the titanium compound can be at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.

[0071] According to some embodiments of the present invention, the third contact reaction is carried out in the presence of a precipitation aid, contacting the catalyst precursor with the titanium compound at a temperature of -40°C to 0°C for 3-5 hours, and then heating the temperature to 50-150°C; preferably, in the presence of a precipitation aid, contacting the catalyst precursor with the titanium compound at a temperature of -30°C to -20°C for 3.5-4.5 hours, and then heating the temperature to 90-130°C. In step 2, the titanium compound and the catalyst precursor can be first mixed at a temperature of -40°C to 0°C, and then the precipitation aid solution is added to contact for 3-5 hours, and then the temperature is raised to 50-150°C to obtain a mixture containing solid precipitates; or the precipitation aid solution is first added to the catalyst precursor, and then the temperature is raised to 50-150°C after contacting with the titanium compound at a temperature of -40°C to 0°C for 3-5 hours to obtain a mixture containing solid precipitates; preferably, the precipitation aid solution is first added to the catalyst precursor, and then the temperature is raised to 50-150°C after contacting with the titanium compound at a temperature of -40°C to 0°C for 3-5 hours to obtain a mixture containing solid precipitates; more preferably, the precipitation aid solution is first added to the catalyst precursor obtained in step 1, and then the temperature is raised to 90-130°C after contacting with the titanium compound at a temperature of -30°C to -20°C for 3.5-4.5 hours to obtain a mixture containing solid precipitates.

[0072] According to some specific embodiments of the present invention, preferably, the method for preparing an olefin polymerization catalyst precursor and a carrier includes but is not limited to the following steps:

[0073] (1) subjecting an alkoxy magnesium, a first alcohol compound and a tetravalent titanium halide to a first contact reaction in the presence of a first dispersant to form a dispersed slurry;

[0074] (2) adding a second alcohol compound to the slurry obtained in step (1) to carry out a second contact reaction to form a solution;

[0075] (3) in the presence of a precipitation aid, subjecting the solution obtained in step (2) to a third contact reaction with a titanium compound in the presence of a second dispersant to precipitate a solid precipitate, thereby obtaining a mixture containing a solid precipitate;

[0076] (4) The mixture obtained in step (3) is separated into solid components by precipitation, filtration, etc. to obtain an olefin polymerization catalyst carrier.

[0077] The fifth aspect of the present invention provides an olefin polymerization catalyst carrier obtained according to the above preparation method.

[0078] According to some embodiments of the present invention, based on the total weight of the olefin polymerization catalyst carrier, it contains 0.01-1 wt % of titanium, 0.1-3.5 wt % of precipitation aid a, and 0.1-4.5 wt % of precipitation aid b.

[0079] The sixth aspect of the present invention provides the above-mentioned olefin polymerization catalyst precursor, the above-mentioned method for preparing the olefin polymerization catalyst precursor, the above-mentioned method for preparing the olefin polymerization catalyst carrier, or the use of the above-mentioned olefin polymerization catalyst carrier in olefin polymerization.

[0080] According to some embodiments of the present invention, the olefin is an olefin represented by the general formula CH2=CHR, wherein R is selected from hydrogen or a C1-C6 alkyl group.

[0081] Beneficial effects of the present invention:

[0082] (1) The present invention uses alkoxymagnesium that is not restricted by particle shape as the initial raw material, and can use a non-toxic substance system to complete the conversion of alkoxymagnesium into an olefin polymerization catalyst precursor and complete the preparation of the olefin polymerization catalyst precursor.

[0083] (2) After the alkoxy magnesium solution is dissolved, a specific precipitation aid system is added to precipitate the solid component, thereby completing the preparation of the olefin polymerization catalyst support.

[0084] (3) The method for preparing an olefin polymerization catalyst carrier of the present invention can obtain a carrier with high yield and good particle morphology. DETAILED DESCRIPTION

[0085] In order to make the present invention easier to understand, the present invention will be described in detail below with reference to embodiments. These embodiments are only for illustration and are not intended to limit the application scope of the present invention.

[0086] The test method of the present invention and the equipment used in the test are as follows:

[0087] (1) Catalyst carrier yield: Catalyst carrier yield (%) = mass of catalyst carrier obtained / mass of magnesium chloride corresponding to the number of moles of alkoxymagnesium used × 100%.

[0088] 2. Titanium content in catalyst carrier: tested by 721 spectrophotometer

[0089] 3. Catalyst carrier particle size distribution: measured by Malvern 2000 n-hexane dispersant laser diffraction method.

[0090] 4. The content of the precipitation aid in the olefin polymerization catalyst support component is determined using a Waters 600E liquid chromatograph or an Agilent 7890 gas chromatograph.

[0091] 5. span=(D(90)-D(10)) / D(50).

[0092] [Example 1]

[0093] Preparation of catalyst support component A1:

[0094] (1) Preparation of olefin polymerization catalyst precursor:

[0095] In a reaction kettle that has been repeatedly replaced with high-purity nitrogen, 5.7 g (0.05 mol) of diethoxymagnesium, 40 mL (0.375 mol) of toluene, 1 mL (0.034 mol) of ethanol, and 2.75 mL (0.025 mol) of titanium tetrachloride were added in sequence, and the mixture was reacted for 4.0 hours at a stirring speed of 200 rpm and a temperature of 80°C to obtain a catalyst precursor product.

[0096] The olefin polymerization catalyst precursor comprises a solid component and a liquid component, wherein the solid component comprises a complex of magnesium chloride and alkoxytitanium, a complex of alkoxymagnesium and titanium tetrachloride, and a magnesium chloride alcoholate. The liquid component is a mixture of toluene and ethanol; the chemical formula of the complex of magnesium halide and alkoxytitanium and the complex of alkoxymagnesium and tetravalent titanium halide is Mg m ·Ti n (R1O) m (R2O) m ·Cl 4n , wherein X is chlorine, m is 2, n is 1, and 2n / m=1. n / m is the molar ratio of the tetravalent titanium halide added in step 1 to the alkoxymagnesium. R1O and R1O are both ethoxy groups. Based on the total weight of the solid component, the content of the complex of magnesium chloride and alkoxytitanium is 83% by weight, the content of the complex of alkoxymagnesium and titanium tetrachloride is 16% by weight, and the content of the magnesium chloride alcoholate is 1% by weight. Based on the total weight of the olefin polymerization catalyst precursor, the content of the solid component is 23% by weight, and the content of the liquid component is 77% by weight.

[0097] (2) Preparation of olefin polymerization catalyst carrier:

[0098] 27 mL (0.47 mol) of 2-ethylhexanol was added to the catalyst precursor product obtained in step (1), the temperature was raised to 110° C., and the reaction was carried out for 1 hour to obtain a magnesium compound alcohol solution. 1.0 mL (3.73 mmol) of diisobutyl phthalate, 1.0 mL (2.93 mmol) of tetrabutyl titanate, and 0.5 mL (1.8 mmol) of 3,5-heptanediol dibenzoate were added, the mixture was stirred for 60 minutes, and the mixture was cooled to room temperature to obtain a solution.

[0099] The prepared solution was added into a reactor fully replaced with nitrogen and filled with 60 mL (0.55 mol) of titanium tetrachloride and 40 mL (0.375 mol) of toluene at -20°C. They were stirred to make them fully contact at low temperature. After 5 hours, the temperature was raised to 110°C. Solid precipitates were precipitated during the heating process. After separation by filtration, they were washed 5 times with 120 mL (0.92 mol) of hexane and dried to obtain olefin polymerization catalyst carrier A1.

[0100] The analysis results of the titanium content of the catalyst carrier A1, the content of the precipitation aid a, the content of the precipitation aid b and the particle size distribution of the catalyst carrier components are shown in Table 1.

[0101] [Example 2]

[0102] Preparation of catalyst support A2:

[0103] The preparation method of catalyst carrier A2 is the same as the preparation method of A1 in Example 1, except that the amount of 3,5-heptanediol dibenzoate is replaced from 0.5 mL to 0.4 mL.

[0104] The results of the titanium content of the catalyst carrier A2, the content of the precipitation aid a, the content of the precipitation aid b and the particle size distribution of the catalyst carrier components are shown in Table 1.

[0105] [Example 3]

[0106] Preparation of catalyst carrier A3:

[0107] The preparation method of catalyst carrier A3 is the same as the preparation method of A1 in Example 1, except that the amount of 3,5-heptanediol dibenzoate is replaced from 0.5 mL to 0.6 mL.

[0108] The results of the titanium content of the catalyst carrier A3, the content of the precipitation aid a, the content of the precipitation aid b and the particle size distribution of the catalyst carrier components are shown in Table 1.

[0109] [Example 4]

[0110] Preparation of catalyst carrier A4:

[0111] The preparation method of catalyst carrier A4 is the same as the preparation method of A1 in Example 1, except that the amount of the second alcohol compound is replaced from 27 mL to 20 mL.

[0112] The results of the titanium content of the catalyst carrier A4, the content of the precipitation aid a, the content of the precipitation aid b and the particle size distribution of the catalyst carrier components are shown in Table 1.

[0113] [Example 5]

[0114] Preparation of catalyst carrier A5:

[0115] The preparation method of catalyst carrier A5 is the same as that of A1 in Example 1, except that the amount of tetravalent titanium halide in step (1) is replaced by 3 mL from 2.75 mL. The liquid component is a mixture of toluene and ethanol; the chemical formula of the complex of magnesium halide and alkoxy titanium and the complex of alkoxy magnesium and tetravalent titanium halide is Mg m ·Ti n (R1O) m (R2O) m ·Cl 4n , wherein X is chlorine, 2n / m=1.1. n / m is the molar ratio of the tetravalent titanium halide added in step 1 to the alkoxymagnesium. R1O and R1O are both ethoxy groups. Based on the total weight of the solid component, the content of the complex of magnesium chloride and alkoxytitanium is 86% by weight, the content of the complex of alkoxymagnesium and titanium tetrachloride is 13% by weight, and the content of the magnesium chloride alcoholate is 1% by weight. Based on the total weight of the olefin polymerization catalyst precursor, the content of the solid component is 24% by weight, and the content of the liquid component is 76% by weight.

[0116] The results of the titanium content of the catalyst carrier A5, the content of the precipitation aid a, the content of the precipitation aid b and the particle size distribution of the catalyst carrier components are shown in Table 1.

[0117] [Example 6]

[0118] Preparation of catalyst carrier A6:

[0119] The preparation method of catalyst carrier A6 is the same as the preparation method of A1 in Example 1, except that the amount of ethanol in step (1) is replaced from 1 mL to 0.3 mL.

[0120] The results of the titanium content of catalyst carrier A6, the content of precipitation aid a, the content of precipitation aid b and the particle size distribution of the catalyst carrier components are shown in Table 1.

[0121] [Example 7]

[0122] Preparation of catalyst carrier A7:

[0123] The preparation method of catalyst carrier A7 is the same as the preparation method of A1 in Example 1, except that tetrabutyl titanate is replaced by tetraethyl titanate.

[0124] The results of the titanium content of the catalyst carrier A7, the content of the precipitation aid a, the content of the precipitation aid b and the particle size distribution of the catalyst carrier components are shown in Table 1.

[0125] [Example 8]

[0126] Catalyst carrier A8 preparation:

[0127] The preparation method of catalyst carrier A8 is the same as the preparation method of A1 in Example 1, except that the reaction time in step (1) is replaced from 4 hours to 2 hours.

[0128] The olefin polymerization catalyst precursor has a solid component and a liquid component, wherein the solid component contains a complex of magnesium chloride and alkoxy titanium, a complex of alkoxy magnesium and titanium tetrachloride, and a magnesium chloride alcoholate. The liquid component is a mixture of toluene and ethanol; based on the total weight of the solid component, the content of the complex of magnesium chloride and alkoxy titanium is 61 weight percent, the content of the complex of alkoxy magnesium and titanium tetrachloride is 38 weight percent, and the content of the magnesium chloride alcoholate is 1 weight percent. Based on the total weight of the olefin polymerization catalyst precursor, the content of the solid component is 23 weight percent, and the content of the liquid component is 77 weight percent.

[0129] The results of the titanium content of the catalyst carrier A8, the content of the precipitation aid a, the content of the precipitation aid b and the particle size distribution of the catalyst carrier components are shown in Table 1.

[0130] [Example 9]

[0131] Catalyst carrier A9 preparation:

[0132] The preparation method of catalyst carrier A9 is the same as the preparation method of A1 in Example 1, except that the reaction time in step (1) is replaced from 4 hours to 6 hours.

[0133] The results of the titanium content of the catalyst carrier A9, the content of the precipitation aid a, the content of the precipitation aid b and the particle size distribution of the catalyst carrier components are shown in Table 1.

[0134] [Example 10]

[0135] Catalyst carrier A10 preparation:

[0136] The preparation method of catalyst carrier A10 is the same as the preparation method of A1 in Example 1, except that the reaction time in step (1) is replaced from 4 hours to 0.5 hours.

[0137] The results of the titanium content of the catalyst carrier A10, the content of the precipitation aid a, the content of the precipitation aid b and the particle size distribution of the catalyst carrier components are shown in Table 1.

[0138] [Comparative Example 1]

[0139] Preparation of catalyst support D1:

[0140] The preparation method of catalyst carrier D1 is the same as the preparation method of A1 in Example 1, except that the ethanol in step (1) is not added.

[0141] The results of the titanium content of the catalyst carrier D1, the content of the precipitation aid a, the content of the precipitation aid b and the particle size distribution of the catalyst carrier components are shown in Table 1.

[0142] [Comparative Example 2]

[0143] Preparation of catalyst carrier D2:

[0144] The preparation method of catalyst carrier D2 is the same as the preparation method of A1 in Example 1, except that the amount of tetravalent titanium halide in step (1) is replaced from 2.75 mL to 0.5 mL.

[0145] The olefin polymerization catalyst precursor has a solid component and a liquid component, wherein the solid component contains a complex of magnesium chloride and alkoxytitanium, a complex of alkoxymagnesium and titanium tetrachloride, and a magnesium chloride alcoholate. The liquid component is a mixture of toluene and ethanol. The chemical formula of the complex of magnesium halide and alkoxytitanium and the complex of alkoxymagnesium and tetravalent titanium halide is Mg m ·Ti n (R1O) m (R2O) m ·Cl 4n , wherein X is chlorine, 2n / m=0.18.

[0146] The results of the titanium content of the catalyst carrier D2, the content of the precipitation aid a, the content of the precipitation aid b and the particle size distribution of the catalyst carrier components are shown in Table 1.

[0147] Table 1. Catalyst support results

[0148]

[0149]

[0150] It can be seen from the data in Table 1 that the polyolefin catalyst carrier prepared by dissolving out irregular alkoxy magnesium in the present invention has good performance in terms of composition, yield, particle morphology, etc.

[0151] It can be seen from the three groups of data in Examples 1, 2 and 3 that the size of the precipitated particles can be adjusted by adjusting the dosage of the precipitation aid a. The larger the dosage, the larger the precipitated particle size. Examples 4 and 5 show that the amount of the second alcohol compound used and the amount of the tetravalent titanium halide used in step (1) will affect the size of the precipitated particles.

[0152] The solid catalyst component prepared in the embodiment has the characteristics of high yield, high activity, and suitable particle size. Compared with Comparative Example 1 (no ethanol is added in step 1) and Comparative Example 2 (insufficient amount of titanium tetrachloride in step 1), in the comparative example, no addition of ethanol and insufficient titanium tetrachloride will lead to insufficient dissolution process in step (2), thereby greatly reducing the yield of the precipitated solid component and affecting the overall performance of the catalyst carrier.

[0153] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this field, under the technical enlightenment provided by the present invention, as common knowledge in the field, other equivalent variations and improvements can also be made, which should also be regarded as the protection scope of the present invention.

Claims

1. An olefin polymerization catalyst precursor, comprising a solid component and a liquid component, wherein: The solid component comprises a complex of a magnesium halide and an alkoxytitanium, a complex of an alkoxymagnesium and a tetravalent titanium halide, and a magnesium halide alcoholate; The liquid component comprises a mixture of a dispersant and a first alcohol compound; The chemical formula of the complex of magnesium halide and alkoxy titanium and the complex of alkoxy magnesium and tetravalent titanium halide is Mg m ·Ti n (R1O) m (R2O) m ·X 4n , wherein X is a halogen, m is a positive integer, 1≤2n / m≤1.6; R1 and R2 are the same or different, and each independently represents a C1-C2 with or without a substituent 10 A hydrocarbon group, a C6-C 20 Phenyl; The method for preparing the olefin polymerization catalyst precursor comprises: in the presence of a dispersant, subjecting an alkoxy magnesium, a first alcohol compound and a tetravalent titanium halide to a first contact reaction.

2. The olefin polymerization catalyst precursor according to claim 1, characterized in that 1≤2n / m≤1.

2.

3. The olefin polymerization catalyst precursor according to claim 1, characterized in that The R1 and R2 are C2-C4 hydrocarbon groups which may have a substituent or not, C6-C 10 Phenyl; Wherein, the substituent is selected from H, hydroxyl, halogen, and ether.

4. The olefin polymerization catalyst precursor according to claim 1, characterized in that OR1 and OR2 are the same or different and are independently selected from one or more of ethoxy, propoxy, butoxy and phenoxy.

5. The olefin polymerization catalyst precursor according to any one of claims 1 to 4, characterized in that Based on the total weight of the solid components, the content of the complex of magnesium halide and alkoxy titanium is 10-99.8% by weight, the content of the complex of alkoxy magnesium and tetravalent titanium halide is 0.01-90% by weight, and the content of magnesium halide alcoholate is 0.01-10% by weight; and / or, Based on the total weight of the olefin polymerization catalyst precursor, the content of the solid component is 10-90% by weight, and the content of the liquid component is 10-90% by weight.

6. The method for preparing the olefin polymerization catalyst precursor according to claim 1, comprising: In the presence of a first dispersant, a first contact reaction is carried out between an alkoxymagnesium compound, a first alcohol compound and a tetravalent titanium halide.

7. The preparation method according to claim 6, characterized in that: The structural formula of the magnesium alkoxide is Mg(R1O)(R2O), wherein R1 and R2 are the same or different and are independently C1-C2 with or without a substituent. 10 A hydrocarbon group, a C6-C 20 of phenyl.

8. The preparation method according to claim 7, characterized in that: OR1 and OR2 are the same or different and are independently selected from one or more of ethoxy, propoxy, butoxy and phenoxy.

9. The preparation method according to claim 7, characterized in that: The alkoxy magnesium is selected from one or more of diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium and diphenoxy magnesium.

10. The preparation method according to any one of claims 6 to 9, characterized in that: The first alcohol compound is C1-C 10 At least one of a linear and branched alcohol; The molar ratio of the first alcohol compound to the alkoxy magnesium is 0.01-2:

1.

11. The preparation method according to claim 10, characterized in that: The alcohol compound is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, hexanol, heptanol, octanol, isooctyl alcohol, nonanol and decanol; The molar ratio of the first alcohol compound to the alkoxy magnesium is 0.02-0.4:

1.

12. The preparation method according to any one of claims 6 to 9, characterized in that: The general formula of the tetravalent titanium halide is Ti(OR 10 ) m X 4－m The titanium compound shown in the general formula, R 10 is an alkyl group; X is a halogen; 0≤m≤3, m is an integer; The molar ratio of tetravalent titanium halide to magnesium alkoxide is 0.25-1:1; The conditions of the first contact reaction include: temperature of 10-150° C.; time of 1-10 hours.

13. The preparation method according to claim 12, characterized in that: R 10 C1-C 10 An alkyl group; X is Cl, Br or I; The molar ratio of tetravalent titanium halide to magnesium alkoxide is 0.5-0.8:1; The conditions of the first contact reaction include: temperature of 60-120° C.; time of 2-6 hours.

14. The preparation method according to claim 12, characterized in that: The tetravalent titanium halide is selected from at least one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, alkoxy titanium trihalide, dialkoxy titanium dihalide and trialkoxy titanium halide.

15. A method for preparing an olefin polymerization catalyst carrier, comprising: (1) subjecting the olefin polymerization catalyst precursor according to any one of claims 1 to 5 or the olefin polymerization catalyst precursor obtained by the preparation method according to any one of claims 6 to 14 to a second contact reaction with a second alcohol compound to obtain a solution; (2) In the presence of a precipitation aid and a second dispersant, the solution obtained in step (1) is subjected to a third contact reaction with a titanium compound, the temperature is increased to precipitate a solid precipitate, a mixture containing a solid precipitate is obtained, and the mixture is separated.

16. The preparation method according to claim 15, characterized in that: The second alcohol compound is one or more of aliphatic alcohol, alicyclic alcohol and aromatic alcohol; The molar ratio of the second alcohol compound to the olefin polymerization catalyst precursor calculated as alkoxymagnesium is 0.2-10:1; The conditions of the second contact reaction include: temperature of 10-150° C.; time of 0.1-10 hours; The conditions of the third contact reaction include: temperature of -40°C to 0°C; time of 3-5 hours; and / or, The temperature is raised to 50-150°C.

17. The preparation method according to claim 16, characterized in that: The second alcohol compound is one or more of a C1-C10 straight-chain fatty alcohol, a C3-C10 branched-chain fatty alcohol, a C3-C12 alicyclic alcohol, a C6-C20 aromatic alcohol, and a C7-C20 alkyl aromatic alcohol; The molar ratio of the second alcohol compound to the olefin polymerization catalyst precursor calculated as alkoxymagnesium is 2-5:1; The conditions of the second contact reaction include: a temperature of 60-140°C; The time is 0.5-6 hours.

18. The preparation method according to claim 17, characterized in that: The second alcohol compound is selected from one or more of ethanol, propanol, butanol, 2-ethylhexanol, benzyl alcohol and phenylethyl alcohol.

19. The preparation method according to any one of claims 15 to 18, characterized in that: The precipitation aid comprises precipitation aid a, precipitation aid b and precipitation aid c, wherein the precipitation aid a is a glycol ester compound, the precipitation aid b is an alkyl ester of an aliphatic or aromatic carboxylic acid, and the precipitation aid c is a titanate compound.

20. The preparation method according to claim 19, characterized in that: The precipitation aid a is a diol ester compound represented by formula (I), In formula (I), R1-R2 are the same or different and are independently substituted or unsubstituted C1-C 20 Straight chain alkyl, substituted or unsubstituted C3-C 20 branched alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 20 Aryl, substituted or unsubstituted C7-C 20 Alkaryl, substituted or unsubstituted C7-C 20 Aralkyl, substituted or unsubstituted C2-C 10 an olefin group or a substituted or unsubstituted C 10 -C 20 R3-R8 are the same or different and are independently hydrogen, halogen, substituted or unsubstituted C1-C 20 Straight chain alkyl, substituted or unsubstituted C3-C 20 branched alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C7-C 20 Alkaryl, substituted or unsubstituted C7-C 20 Aralkyl, substituted or unsubstituted C2-C 10 an olefin group or a substituted or unsubstituted C 10 -C 20 or at least one of R3-R6 forms a ring with at least one of R7-R8; The precipitation aid b is a C1-C8 aliphatic carboxylic acid or a C7-C 10 The C1-C 10 Alkyl esters of The precipitation aid c is a general formula of Ti(OR9) n X 4-n Titanate compounds, wherein R9 is C1-C 10 Alkyl or C3-C 10 cycloalkyl, X is halogen; 1≤n≤4, n is an integer; Relative to 1 mol of alkoxymagnesium calculated as magnesium element, the amount of the precipitation aid a is 0.005-0.1 mol; the amount of the precipitation aid b is 0.01-0.5 mol; the amount of the precipitation aid c is 0.01-0.3 mol; The amount of the second dispersant used is 0.01-50 moles relative to 1 mole of the magnesium alkoxide calculated as the magnesium element.

21. The preparation method according to claim 20, characterized in that: In formula (I), the precipitation aid a is selected from one or more of 2-ethyl-1,3-propylene glycol dibenzoate, 2-propyl-1,3-propylene glycol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propylene glycol dibenzoate, 1,3-butylene glycol dimethyl benzoate, 2-methyl-1,3-butylene glycol di-m-chlorobenzoate, 2,3-dimethyl-1,3-butylene glycol dibenzoate, 1,3-pentanediol dipivalate, 2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol benzoic acid cinnamate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,4-heptanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate and 2-methyl-3,5-heptanediol dibenzoate; The precipitation aid b is selected from one or more of ethyl benzoate, diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl adipate and dibutyl adipate; The precipitation aid c is selected from one or more of tetrabutyl titanate, tetraethyl titanate and isopropyl titanate; Relative to 1 mol of alkoxymagnesium calculated as magnesium element, the amount of the precipitation aid a is 0.01-0.05 mol; the amount of the precipitation aid b is 0.02-0.2 mol; the amount of the precipitation aid c is 0.02-0.08 mol; The amount of the second dispersant used is 5-20 moles relative to 1 mole of the magnesium alkoxide calculated as the magnesium element.

22. An olefin polymerization catalyst carrier obtained according to the preparation method according to any one of claims 15 to 21; containing 0.01 to 1 wt% of titanium, 0.1 to 3.5 wt% of precipitation aid a, and 0.1 to 4.5 wt% of precipitation aid b, based on the total weight of the olefin polymerization catalyst carrier.

23. Use of the olefin polymerization catalyst precursor according to any one of claims 1 to 5, the method for preparing the olefin polymerization catalyst precursor according to any one of claims 6 to 14, the method for preparing the olefin polymerization catalyst carrier according to any one of claims 15 to 21 or the olefin polymerization catalyst carrier according to claim 22 in olefin polymerization.

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