Preparation method and application of alkylaluminoxane

Abstract

The preparation method and application of alkylaluminoxanes belong to the field of chemical products and chemical product reaction engineering. The present inventors accidentally discovered a method for preparing alkylaluminoxanes and found that adding an aluminum salt as a stabilizer during the preparation of alkylaluminoxanes can maintain the long-term stability of the alkylaluminoxane's properties. This method is suitable for the preparation of methylaluminoxane (MAO), ethylaluminoxane (EAO), butylaluminoxane (BAO), hexylaluminoxane (HAO), and the like. This preparation method is simple, safe, low-cost, easy to operate, requires minimal equipment, consumes little energy, and causes minimal environmental pollution.

Description

Technical Field

[0001] The present invention belongs to the field of chemical products and chemical product reaction engineering, and particularly relates to an alkylaluminoxane and a preparation method of the alkylaluminoxane, and the application of the alkylaluminoxane in ethylene polymerization, or copolymerization of ethylene and α-olefin, propylene polymerization, or copolymerization of propylene and α-olefin. Background Art

[0002] High-end polyolefin materials (including metallocene polyolefins, ultra-clean polyolefins, medical polyolefins, thermoplastic elastomers, and high-end pipes) are key pillars of the polyolefin industry and strategically important to the national economies of developed countries worldwide. Large international multinational corporations are rapidly developing new technologies and releasing a constant stream of new products and brands. They hold an absolute monopoly in high-tech, high-value-added polyolefin products, maintaining confidentiality and refusing to transfer their technology. This poses both a challenge and a driving force for the development of my country's polyolefin industry.

[0003] Polyolefins include polyethylene, polypropylene, polyvinyl chloride, and polystyrene. Polyethylene is the simplest general-purpose thermoplastic resin and elastomer, produced by the polymerization of ethylene monomers with the help of an initiator or catalyst. Polyethylene products are available in a wide variety of grades and varieties, meeting the needs of diverse industries. Polypropylene primarily comprises isotactic polypropylene (iPP) and its copolymers. Between 2020 and 2025, global demand is projected to grow at an average annual rate of nearly 4%, reaching 190 million tons / year in 2020 and 230 million tons / year in 2025. Demand for polyethylene is projected to grow at an average annual rate of 4.3%, exceeding 100 million tons / year in 2020. China is the primary driver of this growth, with a projected annual growth rate of 6.9%. ExxonMobil Chemical is the largest producer of PE, followed by Sinopec. Demand for polypropylene is expected to grow at an average annual rate of 4.7% over the next five years, with China's iPP production capacity expected to reach 30 million tons / year in 2020. Sinopec is the largest producer of iPP, followed by LyondellBasell. Catalysts for synthesizing polyolefins primarily utilize high-efficiency supported Ziegler–Natta catalysts via coordination polymerization. Other catalysts utilize metallocene catalysts, constrained geometry metallocene catalysts (CGC), and non-metallocene catalysts. In particular, metallocene catalysts, including CGC catalysts, are used to homopolymerize or copolymerize olefins such as ethylene, propylene, butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, or norbornene to produce polyolefins (mPE), polyolefins (POE), polypropylene (mPP), carbon monoxide (COC), propylene glycol (EPDM), polyethylene propylene (EPR), ultra-clean polypropylene (iPP), polypropylene oxide (POP), polypropylene glycol (PMP), and polyolefins (OBC). These catalysts have found widespread industrial application worldwide and are also experiencing rapid growth in my country's industrial sector.

[0004] However, a serious challenge currently facing the high-end polyolefin industry is the need for cocatalyst alkylaluminoxanes, including methylaluminoxane (MAO), ethylaluminoxane (EAO), butylaluminoxane (BAO), and hexylaluminoxane (HAO), when synthesizing polyolefins using metallocene catalysts, constrained geometry metallocene catalysts (CGC), non-metallocene catalysts, as well as high-efficiency ZN catalysts, supported metallocene catalysts, and supported non-metallocene catalysts. Although my country has introduced numerous industrial plants capable of producing metallocene polyolefins and high-end, ultra-clean iPP, including vinyl-based and propylene-based metallocene polyolefins, the main catalysts (metallocene and supported metallocene catalysts) must be purchased from large international petrochemical companies. Cocatalyst alkylaluminoxanes, such as methylaluminoxane (MAO), are completely imported. The technical challenges in synthesizing these cocatalyst alkylaluminoxanes lie in stabilizing their performance and synthesizing them.

[0005] The present inventors have accidentally discovered a method for preparing alkylaluminoxanes, and discovered that adding an aluminum salt as a stabilizer during the preparation of alkylaluminoxanes can maintain long-term stability in the properties of the alkylaluminoxanes. This method is suitable for the preparation of methylaluminoxane (MAO), ethylaluminoxane (EAO), butylaluminoxane (BAO), hexylaluminoxane (HAO), and the like. This preparation method is simple, safe, low-cost, easy to operate, requires minimal equipment, consumes little energy, and poses little environmental risk. Summary of the Invention

[0006] The present invention aims to provide an alkylaluminoxane solid or a method for preparing an alkylaluminoxane solid, wherein the alkylaluminoxane is methylaluminoxane (MAO), ethylaluminoxane (EAO), butylaluminoxane (BAO) or hexylaluminoxane (HAO), etc.; the prepared alkylaluminoxane solid has stable performance and can be stored for a long time; and the preparation method is simple, safe, low-cost, easy to operate, has low equipment requirements, low energy consumption, and low environmental pollution.

[0007] Another object of the present invention is to provide an alkyl aluminoxane solution or a method for preparing an alkyl aluminoxane solution, wherein the alkyl aluminoxane is a methyl aluminoxane solution, an ethyl aluminoxane solution, a butyl aluminoxane solution, or a hexyl aluminoxane solution; wherein the alkyl aluminoxane solution is a mixture of an alkyl aluminoxane dissolved in an inert organic solvent, wherein the inert organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane, or a C6-C20 cycloalkane; the prepared alkyl aluminoxane solution has stable performance and can be stored for a long time; and the preparation method is simple, safe, low-cost, easy to operate, has low equipment requirements, low energy consumption, and low environmental pollution.

[0008] Another object of the present invention is to provide a stabilizer for an alkylaluminoxane or an alkylaluminoxane solution, wherein the stabilizer for the alkylaluminoxane or the alkylaluminoxane solution is AlCl3, AlEt2Cl, AlEtCl2, aluminum sulfate, aluminum phosphate, aluminum nitrate, aluminum silicate, aluminum carbonate, ferric chloride, ferrous chloride, ferric sulfate, SiCl4, dimethylsilicon dichloride, methylsilicon trichloride, methylphenylsilicon dichloride, etc.

[0009] Alkyl aluminoxane, preparation method and application thereof, characterized in that: the preparation method of alkyl aluminoxane claimed in the present invention comprises adding a stabilizer during the preparation of the alkyl aluminoxane, wherein the stabilizer is AlCl3, AlEt2Cl, AlEtCl2, aluminum sulfate, aluminum phosphate, aluminum nitrate, aluminum silicate, aluminum carbonate, ferric chloride, ferrous chloride, ferric sulfate, SiCl4, dimethyl silicon dichloride, methyl silicon trichloride or methylphenyl silicon dichloride or a mixture thereof.

[0010] Alkyl aluminoxane, preparation method and application thereof, characterized in that: the preparation method of the alkyl aluminoxane claimed in the present invention comprises adding a stabilizer during the preparation of the alkyl aluminoxane, wherein the stabilizer is soluble in water or an inert organic solvent, and the molar ratio of the stabilizer to the alkyl aluminum is (0.2-60):100; the stabilizer is AlCl3, AlEt2Cl, AlEtCl2, aluminum sulfate, aluminum phosphate, aluminum nitrate, aluminum silicate, aluminum carbonate, ferric chloride, ferrous chloride, ferric sulfate, SiCl4, dimethyl silicon dichloride, methyl silicon trichloride or methylphenyl silicon dichloride or a mixture thereof; and the alkyl aluminum is trimethyl aluminum, triethyl aluminum, tributyl aluminum or trihexylaluminum.

[0011] Alkyl aluminoxane, preparation method and application thereof, characterized in that: the preparation method of the alkyl aluminoxane claimed in the present invention comprises dispersing an appropriate amount of water containing a stabilizer in an inert organic solvent to produce a mixture of the stabilizer, water and the inert organic solvent, wherein the molar ratio of water to alkyl aluminum is (10-100):100; wherein the inert organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane or a C6-C20 cycloalkane, etc.; wherein the stabilizer is AlCl3, AlEt2Cl, AlEtCl2, aluminum sulfate, aluminum phosphate, aluminum nitrate, aluminum silicate, aluminum carbonate, ferric chloride, ferrous chloride, ferric sulfate, SiCl4, dimethyl silicon dichloride, methyl silicon trichloride or methylphenyl silicon dichloride or a mixture thereof, etc.; wherein the mass ratio of the stabilizer to water is (0.5-60):100.

[0012] Alkyl aluminoxane, preparation method and application thereof are characterized in that: the preparation method of the alkyl aluminoxane claimed in the present invention is to dissolve alkyl aluminum in an inert organic solvent to produce an alkyl aluminum / inert organic solvent solution, wherein the mass ratio of alkyl aluminum to inert organic solvent is (0.1-100000):100; wherein the alkyl aluminum is trimethyl aluminum, triethyl aluminum, tributyl aluminum or trihexylaluminum, etc.; wherein the inert organic solvent is C6-C20 aromatic hydrocarbon, C6-C20 alkane or C6-C20 cycloalkane, etc.

[0013] Alkyl aluminoxane and its preparation method and application are characterized in that: the preparation method of the alkyl aluminoxane is as follows: alkyl aluminum and an organic solvent solution are contacted with a stabilizer and a mixture of water and an inert organic solvent in a reactor; wherein the alkyl aluminum and the inert organic solvent solution are added to the reactor multiple times or continuously; wherein the stabilizer and the mixture of water and an inert organic solvent are added to the reactor multiple times or continuously; wherein the stabilizer and the inert organic solvent solution are added to the reactor multiple times or continuously; wherein the stabilizer and the alkyl aluminum and the inert organic solvent solution are added to the reactor multiple times or continuously; wherein the inert organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane or a C6-C20 cycloalkane; wherein the alkyl aluminum and The mass ratio of alkyl aluminum to organic solvent in the organic solvent solution is (0.1-100000):100; wherein the mass ratio of water to organic solvent in the mixture of the stabilizer, water and inert organic solvent is (0.01-15):100; wherein the stabilizer is AlCl3, AlEt2Cl, AlEtCl2, aluminum sulfate, aluminum phosphate, aluminum nitrate, aluminum silicate, aluminum carbonate, ferric chloride, ferrous chloride, ferric sulfate, SiCl4, dimethyl silicon dichloride, methyl silicon trichloride or methylphenyl silicon dichloride or a mixture thereof; wherein the mass ratio of the stabilizer to water is (0.5-60):100; wherein the molar ratio of the stabilizer to alkyl aluminum is (0.2-60):100.

[0014] Alkyl aluminoxane, preparation method and application thereof are characterized in that: the preparation method of the alkyl aluminoxane claimed in the present invention is that before the alkyl aluminum and organic solvent solution are contacted with a stabilizer, water and an inert organic solvent mixture, an appropriate amount of organic solvent is added to the reaction kettle to improve the initial stirring effect; wherein the organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane or a C6-C20 cycloalkane.

[0015] Alkyl aluminoxane, preparation method and application thereof, characterized in that: the preparation method of the alkyl aluminoxane claimed in the present invention is to obtain the alkyl aluminoxane after a solution of alkyl aluminum and an inert organic solvent is contacted with a stabilizer, water and an inert organic solvent mixture in a reaction kettle for a sufficiently long time; wherein the alkyl aluminoxane product is an alkyl aluminoxane solution or an alkyl aluminoxane solid; wherein the alkyl aluminoxane solution is alkyl aluminoxane dissolved in an organic solvent; wherein the mass ratio of alkyl aluminoxane to organic solvent in the alkyl aluminoxane solution is (1-40):100; wherein the organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane or a C6-C20 cycloalkane; wherein the alkyl aluminoxane is methyl aluminoxane (MAO), ethyl aluminoxane, butyl aluminoxane or hexyl aluminoxane.

[0016] Alkyl aluminoxane, preparation method and application thereof are characterized in that: the preparation method of the alkyl aluminoxane claimed in the present invention comprises dissolving the alkyl aluminum in an organic solvent in a preparation tank to prepare an alkyl aluminum solution before the alkyl aluminum and inert organic solvent solution contacts a stabilizer, water and inert organic solvent mixture in a reaction kettle; wherein the organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane or a C6-C20 cycloalkane; wherein the mass ratio of the alkyl aluminum to the organic solvent in the alkyl aluminum solution is (0.1-100000):100; wherein the alkyl aluminum is trimethyl aluminum, triethyl aluminum, tributyl aluminum or trihexylaluminum.

[0017] Alkyl aluminoxane, preparation method and application thereof, characterized in that: the preparation method of the alkyl aluminoxane claimed in the present invention comprises dispersing water in an organic solvent in a preparation tank to produce a mixture of the stabilizer, water and inert organic solvent before a solution of alkyl aluminum and an inert organic solvent contacts a mixture of a stabilizer, water and an inert organic solvent in a reaction kettle, wherein the mass ratio of water to organic solvent is (0.01-15):100; wherein the organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane or a C6-C20 cycloalkane.

[0018] The preparation method of alkylaluminoxane is characterized in that: the alkylaluminoxane solid or alkylaluminoxane solution is used as a cocatalyst for olefin coordination polymerization, and forms a catalyst system with the catalyst for olefin coordination polymerization; wherein the catalyst for olefin coordination polymerization is a metallocene catalyst, a constrained geometry metallocene catalyst, a late transition metal catalyst, a high-efficiency ZN catalyst, a supported metallocene catalyst, a supported constrained geometry metallocene catalyst or a supported late transition metal catalyst; wherein the molar ratio of the cocatalyst to the catalyst is (5-500):1; wherein the olefin is ethylene or C3-C 100 Olefins, wherein the C3-C 100 It is C3~C 30 Olefins, C6~C30 Diolefins, C3~C 100 Oxygen-containing olefins, C3~C 100 Nitrogen-containing olefins or C3~C 100 Halogen-containing olefins or C3~C 100 Alkenes containing functional units; among which C3~C 30 The olefin is propylene butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene or norbornene or a mixture thereof; wherein the olefin coordination polymerization is ethylene polymerization, or copolymerization of ethylene and α-olefin, or copolymerization of propylene and α-olefin, the polymerization temperature is 0-200°C, the reaction time is 5-300min, and the gas pressure is 0.05-40MPa; wherein the process used for the olefin coordination polymerization is a solution polymerization process, a gas phase polymerization process, a liquid phase bulk polymerization process, a slurry polymerization process, a loop polymerization process or a combined polymerization process.

[0019] The preparation method of the alkylaluminoxane comprises the following steps:

[0020] (1) adding an alkyl aluminum and an inert organic solvent into an alkyl aluminum solution preparation tank, stirring at -10-60° C. for 0.1-5 hours to produce an alkyl aluminum solution; wherein the organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane, or a C6-C20 cycloalkane; wherein the mass ratio of the alkyl aluminum to the organic solvent in the alkyl aluminum solution is (0.1-100000):100; wherein the alkyl aluminum is trimethyl aluminum, triethyl aluminum, tributyl aluminum, or trihexylaluminum.

[0021] (2) adding a stabilizer and water into a preparation tank at 10-60° C. and stirring for 0.1-3 hours to produce a stabilizer aqueous solution; wherein the stabilizer is AlCl3, AlEt2Cl, AlEtCl2, aluminum sulfate, aluminum phosphate, aluminum nitrate, aluminum silicate, aluminum carbonate, ferric chloride, ferrous chloride, ferric sulfate, SiCl4, dimethylsilicon dichloride, methylsilicon trichloride or methylphenylsilicon dichloride or a mixture thereof; wherein the mass ratio of the stabilizer to water is (0.5-60):100.

[0022] (3) dispersing the stabilizer aqueous solution in an inert organic solvent in another preparation tank at -5-60°C and stirring for 1-10 hours to produce a mixture of stabilizer, water and inert organic solvent; wherein the mass ratio of water to organic solvent is (0.01-15):100; wherein the organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane or a C6-C20 cycloalkane, etc.; wherein the stabilizer is AlCl3, AlEt2Cl, AlEtCl2, aluminum sulfate, aluminum phosphate, aluminum nitrate, aluminum silicate, aluminum carbonate, ferric chloride, ferrous chloride, ferric sulfate, SiCl4, dimethylsilicon dichloride, methylsilicon trichloride or methylphenylsilicon dichloride or a mixture thereof; wherein the mass ratio of stabilizer to water is (0.5-60):100.

[0023] (4) Adding an organic solvent, not more than one-third of the volume of the reactor, to the reactor at -5-60°C is beneficial to improving the initial stirring effect; wherein the organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane, or a C6-C20 cycloalkane.

[0024] (5) The alkyl aluminum solution prepared in (1) and the stabilizer, water, and inert organic solvent mixture prepared in (3) are added to the reaction kettle (4) multiple times or continuously at -5-30°C. The alkyl aluminum and inert organic solvent solution in the reaction kettle (4) is contacted with the stabilizer, water, and inert organic solvent mixture and stirred for 0.1-3 hours.

[0025] (6) The mixed solution of (5) is transferred into the second reactor once, multiple times or continuously, and stirred at 20-100° C. for 0.5-12 hours.

[0026] (7) removing part of the organic solvent from the alkylaluminoxane solution obtained in (6) at 10-60° C. to obtain an alkylaluminoxane solution having a mass ratio of alkylaluminoxane to inert organic solvent of (1-40):100; or removing all of the inert organic solvent to obtain an alkylaluminoxane solid; wherein the inert organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane, or a C6-C20 cycloalkane; and wherein the alkylaluminoxane is methylaluminoxane (MAO), ethylaluminoxane, butylaluminoxane, or hexylaluminoxane.

[0027] Alkyl aluminoxane, its preparation method and application are characterized in that: the alkyl aluminoxane, its preparation method and application produce good results; the alkyl aluminoxane solid or alkyl aluminoxane solution has good stability and excellent performance as a co-catalyst; the co-catalyst has strong applicability, high catalytic activity and low fly ash content of the polymerization product; the reaction is smooth and safe, and intermittent or continuous production is possible; the alkyl aluminoxane solid or alkyl aluminoxane solution is used as a co-catalyst for olefin coordination polymerization, and forms a catalyst system with the catalyst for olefin coordination polymerization, wherein the catalyst for olefin coordination polymerization is a metallocene catalyst, a constrained geometry metallocene catalyst, a late transition metal catalyst, a non-metallocene catalyst, a high-efficiency ZN catalyst, a supported metallocene catalyst, a supported constrained geometry metallocene catalyst or a supported non-metallocene catalyst; the alkyl aluminoxane solid or alkyl aluminoxane solution is also used as a co-catalyst for olefin coordination polymerization.

[0028] The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the following embodiments. DETAILED DESCRIPTION

[0029] Example 1

[0030] (1) At 25°C, take 5 mL of trimethylaluminum and 50 mL of toluene in a 150 mL preparation tank and stir for 0.5 hours. (2) At 30°C, weigh 0.1 g of aluminum trichloride and 0.95 mL of water in a 150 mL preparation tank, stir for 2 hours, add 50 mL of toluene, and stir for 3 hours. (3) At 0°C, take 25 mL of toluene in a 500 mL reactor and stir. Then, add (1) and (2) to the reactor (3) continuously and stir for 1.5 hours; then transfer the mixture to a second 1000 mL reactor, heat to 35°C, and stir for 3 hours. (4) At 40°C, remove part of the solvent from the solution obtained in (3) using a vacuum pump to obtain 30 mL of methylaluminoxane toluene solution.

[0031] Example 2

[0032] (1) At 30°C, take 10 mL of trimethylaluminum and 80 mL of toluene in a 300 mL preparation tank and stir for 1 hour. (2) At 20°C, weigh 0.15 g of aluminum trichloride and 2 mL of water in a 250 mL preparation tank, stir for 2.5 hours, add 90 mL of toluene, and stir for 2 hours. (3) At 10°C, take 80 mL of toluene in a 1000 mL reactor and stir. Then, add (1) and (2) to the reactor continuously and stir for 2 hours; transfer the mixture into a second 1000 mL reactor in equal amounts three times, heat to 40°C, and stir for 3.5 hours. (4) At 45°C, remove all solvents from the solution obtained in (3) using a vacuum pump to obtain 6.3 g of methylaluminoxane as a white solid powder.

[0033] Example 3

[0034] (1) At 35°C, take 10 mL of triethylaluminum and 85 mL of toluene in a 300 mL preparation tank and stir for 1 hour. (2) At 35°C, weigh 0.15 g of aluminum sulfate and 1.5 mL of water in a 250 mL preparation tank, stir for 2.5 hours, add 90 mL of toluene, and stir for 3 hours. (3) At 25°C, take 70 mL of toluene in a 1000 mL reactor and stir. Then, add (1) and (2) to the reactor continuously and stir for 1 hour; transfer all of the mixture to a second 1000 mL reactor at once, heat to 40°C, and stir for 3.5 hours. (4) At 45°C, remove part of the solvent from the solution obtained in (3) using a vacuum pump to obtain 55 mL of ethylaluminoxane toluene solution.

[0035] Example 4

[0036] (1) At 30°C, take 20 mL of triisobutylaluminum and 110 mL of toluene in a 300 mL preparation tank and stir for 1 hour. (2) At 30°C, weigh 0.25 g of aluminum phosphate and 2.5 mL of water in a 300 mL preparation tank, stir for 2.5 hours, add 100 mL of toluene, and stir for 3.5 hours. (3) At 5°C, take 90 mL of toluene in a 1000 mL reactor and stir. Add (1) and (2) to the reactor in equal amounts in 5 times and stir for 0.5 hours; continuously transfer the mixture to a second 2000 mL reactor, heat to 60°C, and stir for 6 hours. (4) At 45°C, remove part of the solvent from the solution obtained in (3) using a vacuum pump to obtain 100 mL of butylaluminoxane toluene solution.

[0037] Example 5

[0038] (1) At 30°C, weigh 20 mL of trihexylaluminum and 110 mL of cyclohexane in a 300 mL preparation tank and stir for 1 hour. (2) At 30°C, weigh 0.5 mL of ethylaluminum dichloride and 2.5 mL of water in a 300 mL preparation tank and stir for 2.5 hours. Add 100 mL of hexane and stir for 3.5 hours. (3) At 5°C, weigh 90 mL of toluene in a 1000 mL reactor and stir. Add (1) and (2) to the reactor continuously and stir for 2.5 hours. Continuously transfer the mixture to a second 1000 mL reactor, heat to 40°C and stir for 8 hours. (4) At 45°C, remove part of the solvent from the solution obtained in (3) using a vacuum pump to obtain 80 mL of hexylaluminoxane solution.

[0039] Example 6

[0040] (1) At 30°C, weigh 20 mL of trimethylaluminum and 110 mL of toluene in a 300 mL preparation tank and stir for 1 hour. (2) At 30°C, weigh 0.5 g of dimethylsilane dichloride and 2.5 mL of water in a 300 mL preparation tank and stir for 2.5 hours. Add 100 mL of hexane and stir for 3.5 hours. (3) At 5°C, weigh 90 mL of toluene in a 1000 mL reactor and stir. (1) and (2) are added to the reactor continuously and stirred for 1.5 hours. The mixture is then transferred to a second 1000 mL reactor, heated to 80°C and stirred for 2 hours. (4) At 45°C, remove part of the solvent from the solution obtained in (3) using a vacuum pump to obtain 120 mL of methylaluminoxane toluene solution.

[0041] Example 7

[0042] (1) At 30°C, weigh 15 mL of trimethylaluminum and 100 mL of toluene in a 300 mL preparation tank and stir for 1 hour. (2) At 30°C, weigh 0.5 g of ferric chloride and 2.5 mL of water in a 300 mL preparation tank and stir for 2.5 hours. Add 100 mL of toluene and stir for 3.5 hours. (3) At 5°C, weigh 90 mL of toluene in a 1000 mL reactor and stir. Add (1) and (2) to the reactor continuously and stir for 1.5 hours. Continuously transfer the mixture to a second 1500 mL reactor, heat to 40°C, and stir for 10 hours. (4) At 45°C, remove part of the solvent from the solution obtained in (3) using a vacuum pump to obtain 90 mL of methylaluminoxane toluene solution.

[0043] Example 8

[0044] (1) At 30°C, weigh 15 mL of trimethylaluminum and 100 mL of toluene in a 300 mL preparation tank and stir for 1 hour. (2) At 30°C, weigh 0.5 g of phenylsilicon trichloride and 2.5 mL of water in a 300 mL preparation tank and stir for 2.5 hours. Add 100 mL of toluene and stir for 3.5 hours. (3) At 5°C, weigh 90 mL of toluene in a 1000 mL reactor and stir. (1) and (2) are continuously added to the reactor and stirred for 2.5 hours. The mixture is continuously transferred to a second 1000 mL reactor, heated to 40°C, and stirred for 4 hours. (4) At 45°C, remove part of the solvent from the solution obtained in (3) using a vacuum pump to obtain 90 mL of methylaluminoxane toluene solution.

[0045] Example 9

[0046] (1) At 30°C, add 15 mL of trimethylaluminum and 100 mL of toluene to a 300 mL preparation tank and stir for 1 hour. (2) At 30°C, add 2.5 mL of water to a 300 mL preparation tank and stir for 2.5 hours. Then, add 100 mL of toluene and stir for 3.5 hours. (3) At 30°C, add 1.5 mL of ethylaluminum dichloride to a 150 mL preparation tank and add 30 mL of toluene and stir for 0.8 hours. (4) At 5°C, add 90 mL of toluene to a 1000 mL reactor and stir. Then, add (1), (2) and (3) to the reactor continuously and stir for 2.5 hours. Then, transfer the mixture to a second 1000 mL reactor, heat it to 40°C and stir for 4 hours. (5) At 45°C, remove part of the solvent from the solution obtained in (4) using a vacuum pump to obtain 90 mL of methylaluminoxane toluene solution.

[0047] Example 10

[0048] (1) At 30°C, weigh 150 kg of trimethylaluminum, 2.5 kg of ethylaluminum dichloride, and 800 L of toluene in a 3000 L preparation tank and stir for 1 hour. (2) At 30°C, weigh 0.5 kg of aluminum trichloride and 3.75 L of water in a 1000 L preparation tank and stir for 2.5 hours. Add 500 L of toluene and stir for 3.5 hours. (3) At 5°C, weigh 200 L of toluene in a 3 cubic meter reactor and stir. (1) and (2) are continuously added to the reactor and stirred for 3 hours. The mixture is continuously transferred to a second 250 L reactor, heated to 40°C, and stirred for 8 hours. (4) At 45°C, remove part of the solvent from the solution obtained in (3) using a vacuum pump to obtain 1200 L of methylaluminoxane toluene solution.

[0049] Application Example 1

[0050] The alkylaluminoxane prepared in Examples 1 to 9 was used as a cocatalyst in a catalyst system with the metallocene catalyst dimethylsilylbisindenyl zirconium dichloride. 10 mg of dimethylsilylbisindenyl zirconium dichloride and 1.5 mL (or 1.5 mg) of the cocatalyst methylaluminoxane (MAO) were weighed into a 10-liter stainless steel polymerization kettle. 1.5 kg of liquid propylene and 0.1 MPa of hydrogen were added. The temperature was raised to 60°C and the reaction was allowed to proceed for 45 minutes. The resulting iPP (1000 g) had a melting point of 158.6°C and an isotacticity of 97%.

[0051] Application Example 2

[0052] The alkylaluminoxanes prepared in Examples 1 to 9 were used as co-catalysts in a catalyst system with a high-efficiency ZN catalyst. 9 mg of the high-efficiency ZN catalyst (for catalyst preparation methods, see CN202111027715.2) and 1.5 mL (or 1.5 mg) of methylaluminoxane (MAO) as the co-catalyst were weighed into a 10-liter stainless steel polymerization kettle. 1.5 kg of liquid propylene and 0.1 MPa of hydrogen were added. The temperature was raised to 75°C and the reaction was allowed to proceed for 60 minutes. The resulting iPP (iPP) was 960 g with a melting point of 165.2°C, an isotacticity of 98.1%, and a fly ash content of 16 ppm.

[0053] Application Example 3

[0054] The alkylaluminoxanes prepared in Examples 1 to 9 were used as cocatalysts in a catalyst system with the metallocene catalyst dimethylsilylcyclopentadienylanilinotitanium dichloride. 5 mg of dimethylsilylcyclopentadienylanilinotitanium dichloride (catalyst preparation method, see ZL201810589447.5) and 2 mL of methylaluminoxane (MAO) as the cocatalyst were weighed into a 10 L stainless steel polymerizer. Hydrogen was introduced to 0.1 MPa, and ethylene was added to 0.8 MPa. The temperature was raised to 65°C and the reaction was allowed to proceed for 20 minutes. This yielded 300 g of polyethylene.

[0055] Application Example 4

[0056] The alkylaluminoxane prepared in Examples 1 to 9 was used as a co-catalyst, and the metallocene catalyst dimethylsilylcyclopentadienylanilinotitanium dichloride was used to form a catalyst system. 5 mg of dimethylsilylcyclopentadienylanilinotitanium dichloride (catalyst preparation method, see ZL201810589447.5) and 1.5 mL of methylaluminoxane (MAO) as a co-catalyst were weighed into a 10 L stainless steel polymerizer. 3 L of cyclohexane and 50 mL of 1-octene were added, and hydrogen was introduced to 0.1 MPa and ethylene to 0.75 MPa. The mixture was heated to 65°C and reacted for 20 minutes. This yielded 310 g of copolymerized ethylene.

[0057] Application Example 5

[0058] The alkylaluminoxanes prepared in Examples 1 to 9 were used as cocatalysts in a catalyst system with the metallocene catalyst dimethylsilylbisindenyl zirconium dichloride. 8 mg of dimethylsilylbisindenyl zirconium dichloride and 3 mL of the cocatalyst ethylaluminoxane (EAO) were weighed into a 10-L stainless steel polymerizer. 35 mL of 1-hexene, 1.5 kg of liquid propylene, and 0.1 MPa of hydrogen were added. The temperature was raised to 60°C and the reaction was allowed to proceed for 40 minutes. This yielded 950 g of copolymerized polypropylene.

[0059] Application Example 6

[0060] The alkylaluminoxanes prepared in Examples 1 to 9 were used as co-catalysts in a catalyst system with a high-efficiency ZN catalyst. 9 mg of the high-efficiency ZN catalyst (for catalyst preparation methods, see CN202111027715.2) and 1.5 mL (or 1.5 mg) of the co-catalyst hexylaluminoxane (HAO) were weighed into a 10-liter stainless steel polymerization reactor. 2.5 kg of liquid 1-butene and 0.05 MPa of hydrogen were added. The temperature was raised to 35°C and the reaction was allowed to proceed for 50 minutes. This yielded 980 g of polybutene (PB) with a melting point of 123.2°C.

Claims

1. A method for preparing an alkylaluminoxane, characterized in that: Alkyl aluminum, water, and a stabilizer are contacted in an inert organic solvent to produce an alkyl aluminoxane; wherein the molar ratio of the alkyl aluminum to the stabilizer and water is 100:(0.2-60):(10-100); wherein the alkyl aluminum is trimethyl aluminum, triethyl aluminum, tributyl aluminum, or trihexyl aluminum, or a mixture thereof; wherein the stabilizer is AlCl3, Et2AlCl, EtAlCl2, aluminum sulfate, aluminum phosphate, aluminum nitrate, aluminum silicate, aluminum carbonate, ferric chloride, ferrous chloride, ferric sulfate, SiCl4, dimethyl silicon dichloride, methyl silicon trichloride, or methylphenyl silicon dichloride, or a mixture thereof; wherein the water is deionized water or purified water; wherein the inert organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane, or a C6-C20 cycloalkane; wherein the alkyl aluminoxane is methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane, or hexyl aluminoxane; It is characterized in that it includes the following steps: (1) adding alkyl aluminum and an inert organic solvent into an alkyl aluminum solution preparation tank, stirring at -10-60°C for 0.1-5 hours to produce an alkyl aluminum solution; wherein the mass ratio of the alkyl aluminum to the organic solvent in the alkyl aluminum solution is (0.1-1000):100; (2) Add stabilizer and water to a preparation tank at 10-60°C and stir for 0.1-3 hours to produce a stabilizer aqueous solution; wherein the mass ratio of stabilizer to water is (0.5-60):100; (3) dispersing the stabilizer aqueous solution in an inert organic solvent in a preparation tank at -5 to 60°C and stirring for 1 to 10 hours to produce a mixture of the stabilizer, water, and the organic solvent; wherein the mass ratio of water to the inert organic solvent is (0.01-15):100; wherein the inert organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane, or a C6-C20 cycloalkane; and wherein the mass ratio of the stabilizer to water is (0.5-60):100; (4) adding an inert organic solvent, not more than one-third of the volume of the reactor, to a reaction kettle at -5 to 60°C; wherein the inert organic solvent is a C6-C20 aromatic hydrocarbon, a C6-C20 alkane, or a C6-C20 cycloalkane; (5) adding the alkyl aluminum solution prepared in step (1) and the stabilizer, water, and inert organic solvent mixture prepared in step (3) to the reaction kettle in step (4) at -5 to 30°C, contacting the alkyl aluminum and inert organic solvent solution with the stabilizer, water, and inert organic solvent mixture in the reaction kettle in step (4) and stirring for 0.1 to 3 hours; (6) Transfer the product of step (5) into a second reactor and stir at 20-100°C for 0.5-12 hours; (7) At 10-60° C., removing a portion of the organic solvent from the alkyl aluminoxane solution obtained in step (6) to obtain an alkyl aluminoxane solution having a mass ratio of alkyl aluminoxane to inert organic solvent of (1-40):100; or removing all of the organic solvent to obtain an alkyl aluminoxane solid.

2. The use of the alkylaluminoxane prepared by the preparation method according to claim 1, characterized in that: Alkyl aluminoxane is used as a co-catalyst for olefin coordination polymerization, and forms a catalyst system with an olefin coordination polymerization catalyst; wherein the olefin coordination polymerization catalyst is a metallocene catalyst, a late transition metal catalyst, a ZN catalyst, a supported metallocene catalyst or a supported late transition metal catalyst; Wherein, the molar ratio of the cocatalyst to the catalyst is (5-500):1; wherein the olefin is ethylene or C3-C 100 olefins; wherein the olefin coordination polymerization is ethylene polymerization, or copolymerization of ethylene and α-olefin, propylene polymerization, or copolymerization of propylene and α-olefin, the polymerization temperature is 0-200°C, the reaction time is 5-300min, and the gas pressure is 0.05-40MPa; wherein the process adopted by the olefin coordination polymerization is a solution polymerization process, a gas phase polymerization process, a liquid phase bulk polymerization process, a slurry polymerization process, a loop polymerization process or a combined polymerization process.