CN116041571B - Catalyst system for loading siloxane compounds and preparation method and application thereof - Google Patents

Catalyst system for loading siloxane compounds and preparation method and application thereof Download PDF

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CN116041571B
CN116041571B CN202111261916.9A CN202111261916A CN116041571B CN 116041571 B CN116041571 B CN 116041571B CN 202111261916 A CN202111261916 A CN 202111261916A CN 116041571 B CN116041571 B CN 116041571B
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titanium
compound
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CN116041571A (en
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寇鹏
李秉毅
马永华
梁迎迎
黄廷杰
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to the field of olefin polymerization catalysts, and provides a catalyst system for supporting siloxane compounds and an olefin polymerization catalyst containing the same. The supported siloxane compound catalyst system contains a product obtained by the reaction of a main catalytic metal component and multi-element siloxane, so that the activity of the obtained catalyst is higher, and in addition, the catalyst has higher dispersibility and excellent catalytic effect due to the superfine inorganic oxide carrier added into the catalyst component. The polymer prepared by the catalyst has higher melt index and low oligomer content.

Description

Catalyst system for loading siloxane compounds and preparation method and application thereof
Technical Field
The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a catalyst system for supporting siloxane compounds, and a preparation method and application thereof.
Background
The catalyst systems comprising the Ti/Mg complex are the catalyst systems commonly used in the polyolefin industry. The primary catalyst used earlier in the production of polyethylene by UNIPOL process unit from Univation is a silica gel supported M-1 type catalyst (UCAT-a). Because silica gel is used as a carrier, the catalyst has higher fluidity and mechanical strength, has better effect when being directly applied to a gas-phase fluidized bed, and can control the particle performance of the polymer to a certain extent. However, with continuous production practice, the M-1 type titanium catalyst has the problem that the stability of solid feeding is difficult to ensure, and the catalyst system is easy to generate the phenomena of pipe blockage, bridging and the like; meanwhile, the catalyst has higher electrostatic sensitivity to impurities in a reaction system, so that the reactor is flaked and caked; and the M-1 type catalyst has lower efficiency, and the ash content in the resin product is higher, so that the catalyst cost per unit product is higher, and the quality of the film product is influenced. Based on the deficiency of the M-1 type solid catalyst, a slurry catalyst-J type catalyst (UCAT-J) is developed in the year Univation to replace the original M-1 type polyethylene catalyst, and is popularized and applied in the sea and the outside, and the J type catalyst is used for replacing the M-1 type catalyst at present and becomes a new development direction of UNIPOL technology. The J-type catalyst is developed to overcome the defects of the M-1 type catalyst, and the main components of the J-type catalyst are basically the same as those of the M-1 type catalyst, but have obvious differences in preparation process. The J-type slurry polyethylene catalyst overcomes the defects of difficult control of the addition amount, difficult uniform feeding, static generation and the like in the solid feeding process due to slurry feeding. And the activity of the catalyst is improved by 3-4 times due to the adoption of silica gel which is thinner than that of the M-1 type catalyst and the higher tetrahydrofuran content.
In the homopolymerization of ethylene or the copolymerization of ethylene with alpha-olefins, the performance of the catalyst affects the performance of the polymer. The catalyst can produce some oligomers while catalyzing ethylene polymerization, the oligomers change stress conditions among polyethylene molecules, the usability and processability of the product are affected, and the yield strength, the elongation, the rigidity and the like of the product are affected. The amount of oligomer is generally measured by the amount of hexane extract, and therefore, the amount of hexane extract is also an important index for measuring the performance of the catalyst.
CN112812205A discloses a catalyst component for olefin polymerization, a catalyst, a preparation method and application thereof, and is particularly suitable for gas-phase fluidized bed process. The catalyst component comprises a catalyst component 1 and a catalyst component 2; wherein catalyst component 1 comprises: 1) A superfine inorganic oxide support, and 2) a reaction and coordination product of magnesium halide, titanium halide, an electron donor compound, and a nitrogen-oxygen-containing heterocyclic compound; the catalyst component 2 is a heterocyclic compound containing an S atom. The catalyst comprises the reaction product of: (A) the catalyst component of the present invention; and (B) an organoaluminum compound of the general formula AlRdX-d. The catalyst of the invention has high activity in the field of gas phase polymerization, and the obtained polymer has higher bulk density and more importantly, has good copolymerization performance, and provides a foundation for improving the production stability of a gas phase fluidized bed and developing new products.
CN101376680a discloses a catalyst component for ethylene polymerization or copolymerization, a preparation method thereof and application of the catalyst composed of the catalyst component in ethylene polymerization or copolymerization. It is characterized by that on a solid matter containing magnesium/titanium at least one inorganic titanium compound, at least one organic titanium compound, at least one electron donor and at least one activating agent are loaded. The invention provides a solid catalyst component which has high efficiency, high hydrogen sensitivity and can obtain a polymer with low fine powder content, has relatively narrow particle size distribution and smaller average particle diameter, has higher catalyst activity, is suitable for slurry polymerization or gas phase polymerization of ethylene, and is particularly suitable for a gas phase fluidized bed polymerization process of ethylene in which the catalyst is fed in a slurry form. However, industrial experiments show that the catalyst is not suitable for the high-load high-condensation-rate fluidized bed production process and is easy to generate powder stickiness.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a catalyst system for supporting siloxane compounds, wherein the catalyst system for supporting siloxane compounds contains main catalytic metal components and multi-element siloxane, so that the activity of the obtained catalyst is higher.
It is an object of the present invention to provide a siloxane-based supported catalyst system comprising an inorganic oxide support, and a product obtained by reacting a magnesium halide, an alkyl disiloxane-based compound, a titanium halide and an electron donor compound.
Preferably, the method comprises the steps of,
The content of the inorganic oxide carrier in the catalyst system is 5-50%, preferably 10-30%, more preferably 15-25% by mass; and/or the number of the groups of groups,
The magnesium halide is used in an amount of 0.1 to 15mol, preferably 1 to 10mol, more preferably 2 to 7mol, per mol of titanium halide; the alkyl disiloxane compound is used in an amount of 0.01 to 10mol, preferably 0.05 to 5mol, more preferably 0.1 to 3mol; the electron donor compound is used in an amount of 1 to 600mol, preferably 20 to 300mol, more preferably 100 to 200mol; and/or the number of the groups of groups,
The titanium content of the catalyst system is 0.1 to 6% by mass, preferably 0.5 to 4% by mass, more preferably 1.5 to 2.5% by mass.
In the above-mentioned catalyst system, the catalyst,
The inorganic oxide support may be selected conventionally according to the prior art in the field, and may be selected from at least one of oxides of silicon, aluminum, preferably from at least one of alumina, silica, more preferably from silica;
The particle size of the inorganic oxide carrier is 0.01 to 10. Mu.m, preferably 0.01 to 5. Mu.m, more preferably 0.01 to 1. Mu.m;
The magnesium halide is at least one selected from magnesium chloride, magnesium bromide and magnesium iodide;
The titanium halide is at least one selected from titanium trichloride, titanium tetrachloride, titanium tribromide and titanium tetrabromide, preferably at least one selected from titanium trichloride and titanium tetrachloride;
the electron donor compound is at least one selected from esters, ethers and ketones, preferably at least one selected from alkyl esters of C1-C4 saturated aliphatic carboxylic acids, alkyl esters of C7-C8 aromatic carboxylic acids, C2-C6 aliphatic ethers, C3-C4 cyclic ethers and C3-C6 saturated aliphatic ketones, more preferably at least one selected from methyl formate, ethyl formate, isopropyl formate, n-propyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, diethyl ether, propyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone, most preferably at least one selected from methyl formate, ethyl acetate, butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone, and particularly preferably tetrahydrofuran;
The general formula of the alkyl disiloxane compound is R 1R2R3SiOSiR4R5R6, wherein R 1、R2、R3、R4、R5、R6 is the same or different and is independently selected from at least one of H, C-C5 saturated or unsaturated hydrocarbon groups, C3-C8 cycloalkyl groups and C6-C10 aryl groups, preferably from at least one of H, C-C5 saturated alkyl groups, C3-C8 cycloalkyl groups and C6-C10 aryl groups, and is not hydrogen at the same time, more preferably from H, C-C5 saturated alkyl groups and at least one of C6-C10 aryl groups; preferably, the alkyl disiloxane compound is at least one selected from hexamethyldisiloxane, tetramethyl disiloxane and hexaethyl disiloxane.
The second object of the present invention is to provide a method for preparing the catalyst system carrying siloxane compounds, which comprises the steps of reacting components including magnesium halide, alkyl disiloxane compounds, titanium halide and electron donor compounds to obtain a mother solution, adding the mother solution into the inorganic oxide carrier, mixing to obtain slurry, and spray drying to obtain the catalyst system.
Wherein the spray drying conditions include: the inlet temperature is 80-240 ℃, preferably 120-220 ℃; the outlet temperature is 60-130 ℃, preferably 90-110 ℃;
the reaction temperature of the mother solution obtained by the reaction is 50-80 ℃ and the reaction time is 2-5 h.
In the preparation method, the inorganic oxide carrier is dried by adopting a conventional drying process and then is mixed with a reaction product of magnesium halide, alkyl disiloxane compound, titanium halide and electron donor compound to form slurry suitable for spray drying, wherein the content of the inorganic oxide carrier in the slurry is 5-50wt%, preferably 10-30wt%.
It is a further object of the present invention to provide an olefin polymerization catalyst comprising:
component (A): the catalyst system for supporting the siloxane compound or the catalyst system for supporting the siloxane compound, which is obtained by the preparation method;
Component (B): an organoaluminum compound.
In the catalyst, the general formula of the organic aluminum compound is AlR nX3-n, wherein R is hydrogen or C 1-C20 alkyl, X is halogen, preferably chlorine, bromine and iodine, and n is more than 0 and less than or equal to 3; preferably, the organic aluminum compound may be at least one selected from triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride;
the molar ratio of aluminum in the component (B) to titanium in the component (A) is 2:1 to 400:1, preferably 10:1 to 200:1.
The fourth object of the present invention is to provide an application of the above-mentioned olefin polymerization catalyst in olefin polymerization, wherein the catalyst system comprising the organoaluminum compound and the supported siloxane compound is activated by adding the components into a hydrocarbon organic solvent, and then the olefin polymerization is initiated. Wherein the hydrocarbon solvent includes, but is not limited to: isopentane, hexane, heptane, toluene, xylene, naphtha, mineral oil.
In order to make the solid catalyst component obtained after spray-drying suitable for use in producing ethylene polymers, it is necessary to reduce the titanium atoms in the catalyst component to a state that allows ethylene to be efficiently polymerized using an activator component (e.g., an organoaluminum compound). Generally, the above catalyst component is reacted with an activator component in a hydrocarbon solvent to obtain a catalyst capable of catalyzing olefin polymerization; the catalyst component and the activator component can also be added into a reaction system in the polymerization process to react in a hydrocarbon organic solvent, thereby initiating the olefin polymerization reaction.
The catalyst of the invention is suitable for homo-polymerization of various kinds of ethylene or copolymerization of ethylene and alpha-olefin, wherein the alpha-olefin can be selected from one of propylene, butene, pentene, hexene, octene and 4-methylpentene-1. The polymerization process can adopt a gas phase method, a slurry method and a solution method, and is more suitable for gas phase fluidized bed polymerization. The conditions for the polymerization of the olefin may be conventionally selected according to the prior art and will not be described in detail herein.
According to the invention, an inorganic oxide carrier is used as a carrier, an electron donor compound is adopted to dissolve magnesium halide, an alkyl disiloxane compound and titanium halide are added to react to prepare a mother solution, finally a catalyst system for loading the siloxane compound is prepared in a spray forming mode, and then a high-activity catalyst is obtained through activation, so that a polymer prepared by the catalyst has a higher melt index, and a hexane extract is low and an oligomer content is low. The oxygen atoms in the alkyl disiloxane compound contain two pairs of lone pair electrons, have stronger electron donating effect, and can effectively improve the polymerization efficiency of the active center of the catalyst after being coordinated with the active center.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The test instruments and test conditions used in the examples are as follows:
1. Catalyst activity: expressed as weight of resin obtained per gram of catalyst;
2. Polymer Melt Index (MI): 6932 melt index meter, CEAST company, italy;
3. hexane extractables content in polymer powder (wt%): extracting dry polymer powder by using hexane, specifically leaching the polymer by using hexane for 4 hours, wherein the weight difference between the polymer powder before and after extraction accounts for the weight of the polymer powder before extraction, namely the hexane extractable content in the polymer powder;
4. determination of titanium content in the catalyst component: dissolving a catalyst sample with 1M sulfuric acid, measuring a dissolving solution by using a spectrophotometer, and calculating by using a working curve to obtain titanium content;
5. the superfine inorganic oxide content is obtained by calculating the mass ratio of the fed amount to the produced catalyst.
The raw materials used in the examples were all commercial products.
Example 1
(1) Preparation of the catalyst component
To a 250mL three-necked flask purged with nitrogen, 2.25gTiCl 4, 6.0g of anhydrous MgCl 2, 2.1mL of hexamethyldisiloxane and 150mL of tetrahydrofuran were successively added, and the mixture was stirred and heated to 65℃to perform a constant temperature reaction for 3 hours and then cooled to 35℃to obtain a mother liquor.
9 G of silica gel (Cabot Corporation TS-610 with the particle size of 0.02-0.1 μm) is added into a 250mL three-necked flask which is blown off by nitrogen, the cooled mother liquor is added, the temperature is kept at 35 ℃, after stirring for 1 hour, the mother liquor after mixing the silica gel is spray dried by a spray dryer, and the spray conditions are as follows: the catalyst component was obtained at an inlet temperature of 195℃and an outlet temperature of 110℃with a titanium content of 2.25% by weight and a silica content of 25% by weight.
(2) Slurry polymerization of ethylene
1L of hexane is added into a 2L polymerization kettle blown and discharged by nitrogen, 4mL of 1M triethylaluminum/hexane and 0.02g of catalyst are added, the temperature is raised to 75 ℃, 0.18Mpa of hydrogen is added, 0.75Mpa of ethylene is added after the hydrogenation is finished, the temperature is raised to 85 ℃, and the temperature is reduced and the material is discharged after the reaction is carried out for 2 hours. The polymerization results are shown in Table 1.
Example 2
(1) Preparation of the catalyst component
The difference from example 1 is that: the amount of hexamethyldisiloxane was 4.2mL, and the titanium content of the resulting catalyst component was 2.34wt% and the silica content was 23wt%.
(2) Slurry polymerization of ethylene
The polymerization results are shown in Table 1, as in example 1.
Example 3
(1) Preparation of the catalyst component
The same as in example 1 except that hexamethyldisiloxane was used in an amount of 1.0mL, the titanium content of the obtained catalyst component was 2.18% by weight, and the silica content was 26% by weight.
(2) Slurry polymerization of ethylene
The polymerization results are shown in Table 1, as in example 1.
Example 4
(1) Preparation of the catalyst component
The same as in example 1 except that hexamethyldisiloxane was changed to hexaethyldisiloxane in an amount of 1.5mL, the titanium content of the obtained catalyst component was 2.21% by weight, and the silica content was 23% by weight.
(2) Slurry polymerization of ethylene
The polymerization results are shown in Table 1, as in example 1.
Example 5
(1) Preparation of the catalyst component
The same as in example 1 except that hexamethyldisiloxane was changed to tetramethyldisiloxane in an amount of 0.9mL, the obtained catalyst component had a titanium content of 2.28% by weight and a silica content of 26% by weight.
(2) Slurry polymerization of ethylene
The polymerization results are shown in Table 1, as in example 1.
Comparative example 1
(1) Preparation of the catalyst component
To a 250mL three-necked flask purged with nitrogen, 2.25g TiC1 4, 6.0g anhydrous MgCl 2 and 150mL tetrahydrofuran were successively added, and the mixture was stirred and heated to 65℃to perform a constant temperature reaction for 3 hours and cooled to 35℃to obtain a mother liquor.
9G of silica gel (Cabot Corporation TS-610 with the particle size of 0.02-0.1 μm) is added into a 250mL three-necked flask which is blown off by nitrogen, the cooled mother solution is added, the temperature is kept at 35 ℃, the mixture is stirred for 1 hour, and the mother solution obtained after the silica gel is mixed is subjected to spray drying by a spray dryer under the spray conditions: the catalyst component was obtained at an inlet temperature of 195℃and an outlet temperature of 110℃with a titanium content of 2.2% by weight and a silica content of 25% by weight.
(2) Slurry polymerization of ethylene
1L of hexane is added into a 2L polymerization kettle blown off by nitrogen, 2mL of 1M triethylaluminum/hexane and 0.01g of catalyst are added, the temperature is raised to 75 ℃, 0.18Mpa of hydrogen is added, 0.75Mpa of ethylene is added after the hydrogenation is finished, the temperature is raised to 85 ℃, and the temperature is reduced and the material is discharged after the reaction is carried out for 2 hours. The polymerization results are shown in Table 1.
TABLE 1 catalyst Performance obtained in examples and comparative examples
As can be seen from the polymerization data in Table 1, the catalyst activity of the present invention was higher under the same polymerization conditions, and the resulting polymer had a higher melt index and a lower hexane extractables content.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or 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 various embodiments described.

Claims (16)

1. The catalyst system for supporting siloxane compounds comprises an inorganic oxide carrier and a product obtained by reacting magnesium halide, alkyl disiloxane compounds, titanium halide and electron donor compounds, wherein the inorganic oxide carrier is at least one of silicon oxide and aluminum oxide; the electron donor compound is at least one selected from methyl formate, ethyl formate, isopropyl formate, n-propyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, diethyl ether, propyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone; the alkyl disiloxane compound is at least one selected from hexamethyldisiloxane, tetramethyl disiloxane and hexaethyldisiloxane; in the catalyst system, the content of the inorganic oxide carrier is 5-50% by mass percent; the dosage of the magnesium halide is 0.1-15 mol, the dosage of the alkyl disiloxane compound is 0.01-10 mol, and the dosage of the electron donor compound is 1-600 mol; the titanium content in the catalyst system is 0.1-6% by mass.
2. The catalyst system of claim 1, wherein the catalyst system comprises,
In the catalyst system, the content of the inorganic oxide carrier is 10-30% by mass percent; and/or the number of the groups of groups,
The dosage of the magnesium halide is 1-10 mol, the dosage of the alkyl disiloxane compound is 0.05-5 mol, and the dosage of the electron donor compound is 20-300 mol; and/or the number of the groups of groups,
The titanium content in the catalyst system is 0.5-4% by mass.
3. The catalyst system of claim 2, wherein the catalyst system comprises,
In the catalyst system, the content of the inorganic oxide carrier is 15-25% by mass percent; and/or the number of the groups of groups,
The dosage of the magnesium halide is 2-7 mol based on each mol of titanium halide; the dosage of the alkyl disiloxane compound is 0.1-3 mol; the dosage of the electron donor compound is 100-200 mol; and/or the number of the groups of groups,
The titanium content in the catalyst system is 1.5-2.5% by mass.
4. The catalyst system of claim 1, wherein the catalyst system comprises,
The inorganic oxide carrier is at least one selected from alumina and silica; and/or the number of the groups of groups,
The particle size of the inorganic oxide carrier is 0.01-10 mu m; and/or the number of the groups of groups,
The magnesium halide is at least one selected from magnesium chloride, magnesium bromide and magnesium iodide; and/or the number of the groups of groups,
The titanium halide is at least one selected from titanium trichloride, titanium tetrachloride, titanium tribromide and titanium tetrabromide.
5. The catalyst system of claim 4, wherein the catalyst system comprises,
The inorganic oxide carrier is selected from silicon dioxide; and/or the number of the groups of groups,
The particle size of the inorganic oxide carrier is 0.01-5 mu m; and/or the number of the groups of groups,
The titanium halide is at least one selected from titanium trichloride and titanium tetrachloride.
6. The catalyst system of claim 5, wherein the catalyst system comprises,
The particle size of the inorganic oxide carrier is 0.01-1 mu m.
7. The catalyst system of claim 1, wherein the catalyst system comprises,
The electron donor compound is at least one selected from methyl formate, ethyl acetate, n-butyl acetate, isobutyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone.
8. A method for preparing the catalyst system according to any one of claims 1 to 7, comprising the steps of reacting components comprising the magnesium halide, the alkyl disiloxane compound, the titanium halide and the electron donor compound to obtain a mother solution, adding the mother solution into the inorganic oxide carrier, mixing to obtain a slurry, and spray-drying to obtain the catalyst system.
9. The method according to claim 8, wherein,
The spray drying conditions include: the inlet temperature is 80-240 ℃, and the outlet temperature is 60-130 ℃.
10. The method according to claim 9, wherein,
The spray drying conditions include: the inlet temperature is 120-220 ℃, and the outlet temperature is 90-110 ℃.
11. The method according to claim 8, wherein,
The reaction temperature of the mother solution obtained by the reaction is 50-80 ℃, and the reaction time is 2-5 h.
12. An olefin polymerization catalyst comprising:
Component (A): the catalyst system of any one of claims 1 to 7 or the catalyst system obtained by the production method of any one of claims 8 to 11;
Component (B): an organoaluminum compound.
13. The olefin polymerization catalyst according to claim 12, wherein,
The general formula of the organic aluminum compound is AlR nX3-n, wherein R is hydrogen or C1-C20 alkyl, X is halogen, and n is more than 0 and less than or equal to 3; and/or the number of the groups of groups,
The molar ratio of aluminum in the component (B) to titanium in the component (A) is 2: 1-400: 1.
14. The olefin polymerization catalyst according to claim 13, wherein,
The general formula of the organic aluminum compound is AlR nX3-n, wherein R is hydrogen or C1-C20 alkyl, X is chlorine, bromine and iodine, and n is more than 0 and less than or equal to 3.
15. The olefin polymerization catalyst according to claim 14, wherein,
The organic aluminum compound is at least one selected from triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and diethyl aluminum chloride; and/or the number of the groups of groups,
The molar ratio of aluminum in the component (B) to titanium in the component (A) is 10: 1-200: 1.
16. Use of the olefin polymerization catalyst according to any one of claims 12 to 15 in olefin polymerization reactions.
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CN110799550A (en) * 2017-06-27 2020-02-14 东邦钛株式会社 Process for producing solid catalyst component for olefin polymerization containing vanadium compound, catalyst for olefin polymerization, and process for producing olefin polymer

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