A process and apparatus for the preparation of alkylaluminoxanes using packed column water phase transfer

Abstract

The present application relates to a method and device for preparing alkylaluminoxane by using a packed column water-carrying method. The method comprises: using a packed column to meter water, and injecting the water into a solution of alkylaluminum and a first inert organic solvent under the driving of a mobile phase to react, thereby obtaining a mixed solution containing alkylaluminoxane. The method uses the technology of a packed column which can carry out trace metering of water, so that the amount of water relative to the amount of alkylaluminum in the inert organic solvent solution can maximize the generation of alkylaluminoxane rather than aluminum hydroxide compounds or aluminum trioxide. In the experimental operation, relevant configurations and operation technologies are combined, so that the reaction is smoothly and controllably carried out, and alkylaluminoxane is prepared at a high yield.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of preparation of alkylaluminoxane, and particularly relates to a method and device for preparing alkylaluminoxane by using a packed column water loading method. BACKGROUND

[0002] Alkylaluminoxane is an important cocatalyst or catalyst for olefin oligomerization and polymerization, among which the effect of methylaluminoxane is the most significant. The main effects of alkylaluminoxane are embodied as follows: 1) group exchange reaction with transition metals in the main catalyst; 2) capturing groups of transition metal centers to form cationic single-activity catalytic centers; 3) removing impurities in the reaction system. It is also reported that the aluminum alkyl of alkylaluminoxane is easy to undergo group exchange with polymerization chains in the main catalyst, which can affect the molecular weight and molecular weight distribution of the polymerization product.

[0003] Alkylaluminoxane is synthesized by the reaction of alkylaluminum with water or water-containing substances, or by a method capable of forming RAlO or R2AlOAlR2 (R is an alkyl group) structural fragments. The synthesis of alkylaluminoxane for laboratory and industrial use is carried out in an inert organic solvent, and the obtained is usually a mixture of an alkylaluminoxane and an alkylaluminum organic solution, so when the alkylaluminoxane is directly used as a solution, its structural formula needs to be considered as (RAIO) n ·(AlR3) m or (R2AlOAlR2) n ·(AlR3) m The former is the reaction of one molecule of AlR3 with the removal of two molecules of RH, and the latter is the reaction of two molecules of AlR3 with the removal of two molecules of RH. When both of the two reactions exist, the structural formula of the generated alkylaluminoxane and alkylaluminum mixture can be represented as (RAIO) n ·(R2AlOAlR2) l ·(AlR3) m When the volatile substances in the alkylaluminoxane solution are removed by the method of evaporation under reduced pressure or volatilization, the structural formula of the remaining solid-state alkylaluminoxane is usually considered to be (RAIO) n or (R2AlOAlR2) n or (RAIO) n ·(R2AlOAlR2) l However, aluminum hydroxyl compounds or aluminum trioxide can also be generated when alkylaluminum reacts with water or water-containing substances, and the aluminum hydroxyl compounds or aluminum trioxide are non-active species. At the same time, the reaction of alkylaluminum with water is very violent, and it is easy to form non-active aluminum hydroxyl compounds or aluminum trioxide. Therefore, the reaction of alkylaluminum with water or water-containing substances needs to be controlled in terms of metering and reaction conditions, so as to obtain effective alkylaluminoxane (RAIO) n ·(AlR3) mOr (R2AlOAlR2) n ·(AlR3) m Or (RAlO) n ·(R2AlOAlR2) l ·(AlR3) m Or (RAlO) n Or (R2AlOAlR2) n Or (RAlO) n ·(R2AlOAlR2) l Those skilled in the art know that metering control and reaction condition control require a combination of specific device design and operating techniques.

[0004] The method of reacting alkylaluminum with aqueous substances such as crystalline hydrates to produce alkylaluminoxanes is generally referred to by those in the art as the indirect method. Patents such as DE3240383A1, EP0208561A2, EP0513808A2, US4544762A, US4404744, US4665208, US5041583, US5099050, CN03104815.3, CN97104192.X, CN200410029717.5, CN200910090468.3, and CN201010215018.5 report the use of metal salt hydrates for the synthesis of alkylaluminoxanes. However, the metal ions in these compounds can easily introduce colored impurities into the product and affect the reactivity of the alkylaluminoxanes. Furthermore, this synthesis method has a weakness: a large amount of inorganic salt reaction residue can adsorb onto the product and alkylaluminum, resulting in significant losses and low reaction yields. There are also reports of using porous materials that adsorb a certain amount of water, such as silica gel, molecular sieves, alumina, and cyclodextrin (CN88106834.9, CN1039587C, CN94119050.1, CN97104192.X, CN201010576012.0, CN201210239141.X), to react with alkylaluminum to synthesize alkylaluminoxanes. The reaction characteristics and weaknesses are similar to those described above, and the adsorption of alkylaluminoxanes and alkylaluminum by reaction residues is also unavoidable.

[0005] The direct reaction of alkylaluminum with water to produce alkylaluminoxanes is commonly referred to in the art as the direct method. However, the highly vigorous reaction between alkylaluminum and water is well-known. Therefore, the control of techniques such as the ratio and stoichiometry of alkylaluminum to H₂O, the concentration adjustment of the inert organic solvent, the reaction temperature, the degree of stirring, and the extent of alkane byproduct removal is crucial for the synthesis of high-quality, high-yield alkylaluminoxanes. These factors place extremely high demands on the corresponding synthetic reaction process control, accident prevention of the reaction apparatus, and safety protection of operators.

[0006] US4924018 uses a static mixer to thoroughly mix water and toluene to form an emulsion, which is then injected into a reactor through a conduit to react with an alkylaluminum toluene solution. US4908436 uses a T-type reactor to react this emulsion and solution. US4772736 uses a syringe pump to inject water through a stainless steel conduit, with three conditions: first, the outlet of the stainless steel pipe is designed to atomize the outflowing water; second, a low-pressure nitrogen system is installed at the inlet of the pipe to promote water atomization; and third, the atomized water is directly introduced below the liquid surface and rapidly dispersed in the alkylaluminum toluene solution under high shear and vigorous stirring by the blades of a propeller-type agitator for reaction. US5041585 also mentions a method for synthesizing atomized water. US4937363 directs the use of an inert gas containing water vapor, i.e., a moist inert gas, introduced from the bottom of a hollow column and rising along the column wall to react with the alkylaluminum solution falling from the top via a membrane process. US5087713 describes the reaction of ice at -80°C and a dilute solution of alkylaluminum in an inert solvent under mechanical force or vigorous stirring to generate fluid impact, producing alkylaluminoxanes. Sinn et al. (Sinn, H.; Bliemeister, J.; et al. In Ziegler catalyst recent innovations and technological improvements, 1995, p58) further synthesized alkylaluminoxanes using a frozen ice pan at -40°C and a toluene solution of alkylaluminum. US4730072 and ER257695A utilize ultrasonic vibration to uniformly disperse immiscible water and organic solvents, particularly toluene, before reacting them with an alkylaluminum solution.

[0007] Compared to the indirect method, the direct method can avoid the adsorption of alkylaluminoxanes and alkylaluminum by reaction residues. However, regardless of whether it is the direct or indirect method, the reaction between alkylaluminum and water molecules is very vigorous. Controlling the reaction to produce alkylaluminoxanes instead of aluminum hydroxyl compounds or aluminum oxide still places very high demands on the synthesis process and technology. Summary of the Invention

[0008] This invention addresses the shortcomings of existing technologies by providing a novel method for preparing alkylaluminoxanes. This method utilizes packed column technology, where the column can hold a specific amount of water. This ensures that the amount of water, relative to the amount of alkylaluminum in the inert organic solvent solution, maximizes the formation of alkylaluminoxanes rather than aluminum hydroxyl compounds or aluminum oxide. By combining relevant configuration and operational techniques in the experimental process, the reaction proceeds smoothly and controllably, achieving high yields of alkylaluminoxanes.

[0009] Therefore, the first aspect of the present invention provides a method for preparing alkylaluminoxanes using a packed column water-carrying method, comprising: metering water using a packed column, and injecting the water into a solution formed by alkylaluminum and a first inert organic solvent under the drive of a mobile phase to react, thereby obtaining a mixture containing alkylaluminoxanes.

[0010] In some embodiments of the present invention, the water loading of the packed column is 0.1 mL to 1000 mL. In this invention, the water loading of the packed column is such that the amount of water relative to the amount of alkylaluminum in the inert organic solvent solution maximizes the formation of alkylaluminoxanes rather than aluminum hydroxyl compounds or aluminum oxide.

[0011] In this invention, the water can be injected into the packed column using a micro-injection pump.

[0012] In some embodiments of the present invention, the column packing material in the packed column is selected from inorganic materials that do not react with water or form gels with water, or organic polymers that do not react with water or form gels with water.

[0013] The column packing material in this invention does not undergo a chemical reaction with water molecules, and the interaction between the two is preferably a van der Waals force or a weak hydrogen bond.

[0014] In some embodiments of the present invention, the inorganic material is selected from at least one of silica, alumina, molecular sieves, kaolin, attapulgite, ceramics, metal oxide ceramics, and glass fibers. Furthermore, other inorganic materials that do not strongly interact with water and can be carried by the mobile phase are also selected fillers. It is worth noting that experiments show that silica, alumina, molecular sieves, kaolin, and attapulgite that have not been calcined at high temperatures easily form gels with water, hindering water transport. Therefore, the selected silica, alumina, molecular sieves, kaolin, and attapulgite need to be calcined at high temperatures and pulverized into particles of a certain size before use. The particle size depends on the flow rate of the mobile phase being within a controlled range. Generally, the particle size can be 4–400 mesh (Note: based on US standard mesh size).

[0015] In other embodiments of the present invention, the organic polymer is selected from at least one of polyethylene, polypropylene, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polyisobutylene, polyisoprene, ethylene propylene rubber resin, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polyacrylamide, polycarbonate, polysulfone, and polyetheretherketone.

[0016] In this invention, the column packing material can also be an inorganic metal framework compound that does not react with water or form a gel with water. Other high-molecular-weight organic compounds and metal-organic framework compounds that do not strongly interact with water and can be transported by the mobile phase are also selected packing materials.

[0017] In some embodiments of the present invention, the alkylaluminum has the structural formula AlR3, wherein R is an alkyl group, limited to alkyl groups that can currently be prepared. In some specific embodiments of the present invention, R is an alkyl group having 1 to 20 carbon atoms.

[0018] In some preferred embodiments of the present invention, the alkylaluminum is selected from at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, and tri-n-octylaluminum.

[0019] When the alkyl aluminum is a single alkyl aluminum, the method is used to prepare a single alkyl aluminum oxane; when the alkyl aluminum is a mixture of two alkyl aluminums, the method is used to prepare a mixed dialkyl aluminum oxane; when the alkyl aluminum is a mixture of three or more alkyl aluminums, the method is used to prepare a poly-mixed alkyl aluminum oxane.

[0020] In some embodiments of the present invention, the first inert organic solvent is selected from any one of straight-chain hydrocarbons, branched hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons; preferably, the first inert organic solvent is selected from any one of toluene, xylene, trimethylbenzene, n-pentane, isopentane, neopentane, cyclopentane, methylcyclopentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, petroleum ether, isoheptane, neoheptane, Isopar E, and Isopar F.

[0021] In other embodiments of the invention, the mobile phase is selected from a second inert organic solvent or a gaseous substance that does not react with water and alkylaluminum.

[0022] In some specific embodiments of the present invention, the second inert organic solvent is selected from any one of straight-chain hydrocarbons, branched hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons; more preferably, the second inert organic solvent is selected from any one of toluene, xylene, trimethylbenzene, n-pentane, isopentane, neopentane, cyclopentane, methylcyclopentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, petroleum ether, isoheptane, neoheptane, Isopar E, and Isopar F.

[0023] In some preferred embodiments of the present invention, the second inert organic solvent is the same as the first inert organic solvent. That is, the inert organic solvent used for the mobile phase is consistent with the inert organic solvent used to dissolve the alkyl aluminum.

[0024] In some other embodiments of the present invention, the gaseous substance is selected from any one of nitrogen, argon and methane.

[0025] In some embodiments of the present invention, the molar ratio of water to alkylaluminum is not higher than 1:1. The minimum molar ratio of water to alkylaluminum depends on the optimal activity of the alkylaluminoxane obtained after the reaction for a specific co-catalytic reaction or catalytic reaction. In some preferred embodiments of the present invention, the molar ratio of water to alkylaluminum is 1:(1 to 10), preferably 1:(1 to 5).

[0026] In other embodiments of the present invention, the content of alkyl aluminum in the solution is 0.4 to 80 wt%.

[0027] The amount of inert organic solvent in this invention is determined by the following aspects: (1) to make the reaction stable, (2) to avoid the formation of insoluble solid aluminum hydroxyl compounds or aluminum oxide to the greatest extent, and (3) to make the generated alkylaluminoxane solution of a certain concentration have the best activity for specific co-catalytic or catalytic reactions.

[0028] In some specific embodiments of the present invention, the aluminum content in the mixture containing alkylaluminoxane is 0.1 to 40.0 wt%; wherein, when the mobile phase is a gaseous substance, the aluminum content in the mixture containing alkylaluminoxane is controlled by adjusting the amount of the first inert organic solvent; when the mobile phase is a second inert organic solvent, the aluminum content in the mixture containing alkylaluminoxane is controlled by adjusting the sum of the amounts of the first and second inert organic solvents.

[0029] In some embodiments of the present invention, the reaction temperature is -50 to 110°C, preferably -20 to 90°C, and more preferably -10 to 80°C. In the present invention, the control of the reaction temperature is preferably carried out in steps. The process from the addition of water in a gaseous mobile phase or water in a liquid inert organic solvent mobile phase to the complete reaction of the solution containing alkylaluminum is controlled at the lower temperature limit; subsequently, the aging process needs to be controlled at the upper temperature limit. The temperature limits given for these two steps refer to certain temperature ranges, and the specific temperature for each step is determined based on the optimal performance of the subsequent catalytic activity test. The reaction times for these two steps should also be determined based on the optimal performance of the subsequent catalytic activity test.

[0030] In some embodiments of the present invention, the reaction time is 4 to 15 hours; preferably 8 to 12 hours.

[0031] For those skilled in the art, this control is not merely a two-step process; one-step or multi-step control is also permissible to achieve optimal co-catalytic or catalytic performance of the synthesized alkylaluminoxane solution. The aging process following the addition of water and reaction with the solution containing alkylaluminum can be understood in a sense as the formation of a stable alkylaluminoxane with the structural formula (RA1O) as described above. n ·(AlR3) m Or (R2AlOAlR2) n ·(AlR3) m Or (RAlO) n ·(R2AlOAlR2) l ·(AlR3) m Or (RAlO) n Or (R2AlOAlR2) n Or (RAlO) n ·(R2AlOAlR2) l .

[0032] In this invention, the final mixture containing alkylaluminoxane is injected into a sealed container under an inert atmosphere for later use. The sealed container is selected from pressure-resistant glass bottles or stainless steel bottles.

[0033] The alkylaluminoxanes prepared by this invention preferably include methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, isobutylaluminoxane, tert-butylaluminoxane, and n-octylaluminoxane. Limited to currently available R-alkyl groups, other alkylaluminoxanes that can be synthesized do not exclude those generated by controlled hydrolysis of other alkylaluminum groups.

[0034] It should be noted that these specific alkylaluminoxanes are just a general term, and the structural formulas should include the following types: among them, the structural formula of methylaluminoxane is (MeAlO). n ·(AlMe3) m (Me2AlOAlMe2) n ·(AlMe3) m (MeAlO) n ·(Me2AlOAlMe2) l ·(AlMe3) m (MeAlO) n (Me2AlOAlMe2) n (MeAlO) n ·(Me2AlOAlMe2) l The structural formula for ethylaluminoxane is (EtAlO). n ·(AlEt3) m (Et2AlOAlEt2)n ·(AlEt3) m (EtAlO) n ·(Et2AlOAlEt2) l ·(AlEt3) m (EtAlO) n (Et2AlOAlEt2) n (EtAlO) n ·(Et2AlOAlEt2) l The structural formula for n-propylaluminoxane is (nPrAlO). n ·(AlnPr3) m (nPr2AlOAlnPr2) n ·(AlnPr3) m (nPrAlO) n ·(nPr2AlOAlnPr2) l ·(AlnPr3) m (nPrAlO) n (nPr2AlOAlnPr2) n (nPrAlO) n ·(nPr2AlOAlnPr2) l The structural formula for n-butylaluminoxane is (nBuAlO). n ·(AlnBu3) m (nBu2AlOAlnBu2) n ·(AlnBu3) m (nBuAlO) n ·(nBu2AlOAlnBu2) l ·(AlnBu3) m (nBuAlO) n (nBu2AlOAlnBu2) n (nBuAlO) n ·(nBu2AlOAlnBu2) l The structural formula for isobutylaluminoxane is (iBuAlO). n (AliBu3) m (iBu2AlOAliBu2) n (AliBu3) m (iBuAlO) n ·(iBu2AlOAliBu2) l (AliBu3) m (iBuAlO) n (iBu2AlOAliBu2) n (iBuAlO)n ·(iBu2AlOAliBu2) l The structural formula for n-octylaluminoxane is (n-OctylAlO). n ·(Aln-Octyl3) m (n-Octyl2AlOAln-Octyl2) n ·(Aln-Octyl3) m (n-OctylAlO) n ·(n-Octyl2AlOAln-Octyl2) l ·(Aln-Octyl3) m (n-OctylAlO) n (n-Octyl2AlOAln-Octyl2) n (n-OctylAlO) n ·(n-Octyl2AlOAln-Octyl2) l Other alkylaluminoxanes also have structural formulas that basically include these, where the alkyl groups need to be replaced accordingly.

[0035] The quantitative concentration of alkylaluminoxanes is determined by the mass percentage of metallic aluminum in the mixture containing alkylaluminoxanes. The specific determination method is as follows: A certain amount of the mixture containing alkylaluminoxanes is taken, hydrolyzed to produce aluminum ions, which react with an excess of the complexing agent disodium ethylenediaminetetraacetate (EDTA) at a low acidity to form a water-soluble complex. Using xylenol orange as an indicator, the excess EDTA is back-titrated with a zinc salt solution. Once the zinc ions have fully complexed with the EDTA, a trace excess of zinc ions forms a colored complex with the indicator, which is the titration endpoint. Finally, the mass percentage of metallic aluminum in the mixture containing alkylaluminoxanes can be calculated.

[0036] The determination of the alkyl content in alkylaluminoxanes can be made by assessing the amount of methane or ethane gas produced by the hydrolysis or acidolysis of a certain amount of alkylaluminoxane solution for methylaluminoxane and ethylaluminoxane. However, the alkanes produced by the hydrolysis or acidolysis of other alkylaluminoxanes are readily miscible with organic solvents, making accurate determination relatively difficult.

[0037] A mixture containing alkylaluminoxanes was purified by removing volatile alkylaluminum and inert organic solvents to obtain solid alkylaluminoxanes, which were then analyzed by nuclear magnetic resonance spectroscopy, such as... 1 H, 13 C and 27 Al spectra can detect the presence of alkyl groups and metallic aluminum, but precise measurement is not sufficient.

[0038] Solid methylaluminoxanes can be detected by UV-vis spectroscopy and compared with spectra reported in the literature to obtain qualitative information.

[0039] The specific method for calculating the conversion yield of alkylaluminum reacting with water in an inert organic solvent to produce alkylaluminoxanes is as follows: After the reaction is complete, the mixture is filtered to collect as much solid as possible and weighed. Based on the premise that the molar ratio of water to alkylaluminum is no higher than 1:1, the solid produced should be aluminum oxide. The conversion yield can then be calculated.

[0040] The determination of the mass percentage of aluminum in the above-mentioned mixture containing alkylaluminoxanes can also be used to calculate the conversion yield of the reaction.

[0041] For alkylaluminum compounds such as trimethylaluminum and triethylaluminum, another measurement method is the methane or ethane gas metric method. This involves collecting and measuring the methane or ethane released during the reaction, and then calculating the conversion yield. This method is applicable only if an inert organic solvent is used as the water-carrying mobile phase. If a gas is used as the water-carrying mobile phase, metric measurement is not possible.

[0042] In some specific embodiments of the present invention, the method of the present invention specifically includes the following steps:

[0043] S1, the reactor is replaced with an inert gas, and the water and oxygen content in the reactor after replacement is less than 1000 ppm, preferably less than 100 ppm;

[0044] S2, Weigh alkyl aluminum and a first inert organic solvent to prepare a solution (reaction solution), inject it into the reactor, and turn on the stirring device; The amount of reaction solution in the reactor is 1 / 10 to 9 / 10 of the reactor volume, preferably 1 / 2 to 2 / 3;

[0045] S3, set the reactor to a certain temperature; control the reaction temperature between -50 and 110°C, preferably between -20 and 90°C, and even more preferably between -10 and 80°C;

[0046] S4, fill the packed column with water, introduce the mobile phase, and let the water in the packing enter the solution formed by alkyl aluminum and the first inert organic solvent in the reactor, and react under stirring;

[0047] S5, the alkane gas produced in the reaction partially dissolves in the resulting mixture containing alkylaluminoxanes and is partially released; when no more gas is released, the reactor temperature is increased (by 50-70°C) and the reaction continues for a period of time until no more gas is produced, at which point the reaction is terminated;

[0048] S6. Collect the mixture containing alkylaluminoxanes under an inert atmosphere, seal and store for later use.

[0049] The method described in this invention can be used for: (1) the controlled hydrolysis of a single alkyl aluminum to prepare a single alkyl aluminum oxane; (2) the controlled hydrolysis of a mixture of two alkyl aluminums to prepare a mixed dialkyl aluminum oxane; (3) the controlled hydrolysis of a mixture of three or more alkyl aluminums to prepare a poly-mixed alkyl aluminum oxane; and (4) the preparation of modified alkyl aluminum oxanes.

[0050] When the method of the present invention is used for the controlled hydrolysis of a single alkyl aluminum to prepare a single alkyl aluminum oxane, the method specifically includes the following steps:

[0051] (1) The reactor is replaced with an inert gas so that the reactor contains the lowest possible amount of water, oxygen and other impurities; specifically, the water and oxygen content in the reactor after replacement is less than 1000 ppm, preferably less than 100 ppm.

[0052] (2) Weigh a certain amount of alkyl aluminum A and a certain amount of the first inert organic solvent to prepare a solution (reaction solution), inject it into the reactor, and turn on the stirring device; the amount of reaction solution in the reactor is 1 / 10 to 9 / 10 of the reactor volume, preferably 1 / 2 to 2 / 3;

[0053] (3) Set the reactor to a certain temperature; control the reaction temperature between -50 and 110°C, preferably between -20 and 90°C, and even more preferably between -10 and 80°C;

[0054] (4) A certain amount of water-carrying column packing is filled into the column, and then a certain amount of water is injected. Then, a mobile phase that is inert to water, column packing and alkyl aluminum is introduced, carrying the water in the packing into the reactor formed by alkyl aluminum and the first inert organic solvent, and the reaction is carried out under stirring.

[0055] (5) The alkane gas produced in the reaction partially dissolves in the mixture containing alkylaluminoxane and is partially released; when the reaction stops releasing gas, the reactor temperature is increased (by 50-70°C) and the reaction continues for a period of time until no more gas is produced, at which point the reaction ends.

[0056] (6) Collect the mixture containing alkylaluminoxane under an inert atmosphere, seal and store for later use.

[0057] When the method of the present invention is used for the controlled hydrolysis of a mixture of two alkyl aluminum compounds to prepare mixed dialkyl aluminum oxanes, the method specifically includes the following steps:

[0058] (1) The reactor is replaced with an inert gas so that the reactor contains the lowest possible amount of water, oxygen and other impurities; specifically, the water and oxygen content in the reactor after replacement is less than 1000 ppm, preferably less than 100 ppm.

[0059] (2) Weigh a certain amount of alkyl aluminum A, a certain amount of alkyl aluminum B and a certain amount of the first inert organic solvent to prepare a solution (reaction solution), inject it into the reactor, and turn on the stirring device; the amount of reaction solution in the reactor is 1 / 10 to 9 / 10 of the reactor volume, preferably 1 / 2 to 2 / 3;

[0060] (3) Set the reactor to a certain temperature; control the reaction temperature between -50 and 110°C, preferably between -20 and 90°C, and even more preferably between -10 and 80°C;

[0061] (4) A certain amount of water-carrying column packing is filled into the column, and then a certain amount of water is injected. Then, a mobile phase that is inert to water, column packing and alkyl aluminum is introduced, carrying the water in the packing into the reactor formed by alkyl aluminum and the first inert organic solvent, and the reaction is carried out under stirring.

[0062] (5) The alkane gas produced in the reaction partially dissolves in the mixed liquid containing mixed dialkylaluminoxane and is partially released; when the reaction stops releasing gas, the reactor temperature is increased (increased by 50-70°C) and the reaction continues for a period of time until no more gas is produced, and the reaction is terminated.

[0063] (6) Collect the mixture containing dialkylaluminoxane under an inert atmosphere, seal and store for later use.

[0064] The proportions of alkylaluminum A and B, and the first inert organic solvent, and the resulting concentrations of A and B, depend on the optimal catalytic or co-catalytic performance achieved by the synthesized mixed alkylaluminoxanes. The quantitative concentration of the alkylaluminoxanes is determined using the mass percentage of metallic aluminum, consistent with the method described above for preparing alkylaluminoxanes from a single alkylaluminum; however, this quantitative concentration cannot be used to calculate the reaction conversion or yield.

[0065] A mixture containing mixed dialkylaluminoxanes was purified by removing volatile alkylaluminum compounds and organic solvents to obtain solid mixed dialkylaluminoxanes. Nuclear magnetic resonance spectroscopy was performed, as shown in... 1 H, 13 C and 27 Al spectra can detect the presence of alkyl groups and metallic aluminum, but precise measurement is not sufficient.

[0066] The two mixed alkyl aluminum compounds A and B are preferably derived from trimethylaluminum and triethylaluminum, trimethylaluminum and tri-n-propylaluminum, trimethylaluminum and tri-n-butylaluminum, trimethylaluminum and triisobutylaluminum, triethylaluminum and tri-n-propylaluminum, triethylaluminum and tri-n-butylaluminum, triethylaluminum and triisobutylaluminum, tri-n-propylaluminum and tri-n-butylaluminum, tri-n-propylaluminum and triisobutylaluminum, tri-n-propylaluminum and triisobutylaluminum.

[0067] The structural formula of the mixed dialkylaluminoxanes prepared using this method can be represented as follows:

[0068] For methyl ethyl aluminoxane: (MeAlO) m ·(EtAlO) n ·(AlMe3) o ·(AlEt3) p 、(Me2AlOAlMe2) m ·(Et2AlOAlEt2) n ·(AlMe3) o ·(AlEt3) p 、(MeAlO) m ·(Et2AlOAlEt2) n ·(AlMe3) o ·(AlEt3) p 、(EtAlO) m ·(Me2AlOAlMe2) n ·(AlMe3) o ·(AlEt3) p 、(MeAlO) m ·(Me2AlOAlMe2) n ·(Et2AlOAlEt2) o ·(AlMe3) p ·(AlEt3) q 、(EtAlO) m ·(Me2AlOAlMe2) n ·(Et2AlOAlEt2) o ·(AlMe3) p ·(AlEt3) q 、(MeAlO) m ·(EtAlO) n ·(Me2AlOAlMe2) o ·(Et2AlOAlEt2) p ·(AlMe3) q ·(AlEt3) r 、(MeAlO) m ·(EtAlO) n 、(Me2AlOAlMe2) m ·(Et2AlOAlEt2) n 、(MeAlO) m ·(Et2AlOAlEt2) n 、(EtAlO) m ·(Me2AlOAlMe2) n 、(MeAlO) m ·(Me2AlOAlMe2)n ·(Et2AlOAlEt2) o 、(EtAlO) m ·(Me2AlOAlMe2) n ·(Et2AlOAlEt2) o 、(MeAlO) m ·(EtAlO) n ·(Me2AlOAlMe2) o ·(Et2AlOAlEt2) p ;

[0069] For the mixed methyl-n-propylaluminoxane: (MeAlO) m ·(nPrAlO) n ·(AlMe3) o ·(AlnPr3) p 、(Me2AlOAlMe2) m ·(nPr2AlOAlnPr2) n ·(AlMe3) o ·(AlnPr3) p 、(MeAlO) m ·(nPr2AlOAlnPr2) n ·(AlMe3) o ·(AlnPr3) p 、(nPrAlO) m ·(Me2AlOAlMe2) n ·(AlMe3) o ·(AlnPr3) p 、(MeAlO) m ·(Me2AlOAlMe2) n ·(nPr2AlOAlnPr2) o ·(AlMe3) p ·(AlnPr3) q 、(nPrAlO) m ·(Me2AlOAlMe2) n ·(nPr2AlOAlnPr2) o ·(AlMe3) p ·(AlnPr3) q 、(MeAlO) m ·(nPrAlO) n ·(Me2AlOAlMe2) o ·(nPr2AlOAlnPr2) p ·(AlMe3) q ·(AlnPr3) r, (MeAlO) m ·(nPrAlO) n , (Me2AlOAlMe2) m ·(nPr2AlOAlnPr2) n , (MeAlO) m ·(nPr2AlOAlnPr2) n , (nPrAlO) m ·(Me2AlOAlMe2) n , (MeAlO) m ·(Me2AlOAlMe2) n ·(nPr2AlOAlnPr2) o , (nPrAlO) m ·(Me2AlOAlMe2) n ·(nPr2AlOAlnPr2) o , (MeAlO) m ·(nPrAlO) n ·(Me2AlOAlMe2) o ·(nPr2AlOAlnPr2) p ;

[0070] For the mixed methyl n-butyl aluminoxane: (MeAlO) m ·(nBuAlO) n ·(AlMe3) o ·(AlnBu3) p , (Me2AlOAlMe2) m ·(nBu2AlOAlnBu2) n ·(AlMe3) o ·(AlnBu3) p , (MeAlO) m ·(nBu2AlOAlnBu2) n ·(AlMe3) o ·(AlnBu3) p , (nBuAlO)<​​​​​​​​​​​​​​​​​​·(Me2AlOAlMe2) n ·(nBu2AlOAlnBu2) o ·(AlMe3) p ·(AlnBu3) q ,(MeAlO) m ·(nBuAlO) n ·(Me2AlOAlMe2) o ·(nBu2AlOAlnBu2) p ·(AlMe3) q ·(AlnBu3) r ,(MeAlO) m ·(nBuAlO) n ,(Me2AlOAlMe2) m ·(nBu2AlOAlnBu2) n ,(MeAlO) m ·(nBu2AlOAlnBu2) n ,(nBuAlO) m ·(Me2AlOAlMe2) n ,(MeAlO) m ·(Me2AlOAlMe2) n ·(nBu2AlOAlnBu2) o ,(nBuAlO) m ·(Me2AlOAlMe2) n ·(nBu2AlOAlnBu2) o ,(MeAlO) m ·(nBuAlO) n ·(Me2AlOAlMe2) o ·(nBu2AlOAlnBu2) p ;

[0071] For the mixed methyl isobutyl aluminoxane: (MeAlO) m ·(iBuAlO) n ·(AlMe3) o ·(AliBu3)<000​​​​​​​​​​​​​​​p 、(iBuAlO) m ·(Me2AlOAlMe2) n ·(AlMe3) o ·(AliBu3) p 、(MeAlO) m ·(Me2AlOAlMe2) n ·(iBu2AlOAliBu2) o ·(AlMe3) p ·(AliBu3) q 、(iBuAlO) m ·(Me2AlOAlMe2) n ·(iBu2AlOAliBu2) o ·(AlMe3) p ·(AliBu3) q 、(MeAlO) m ·(iBuAlO) n ·(Me2AlOAlMe2) o ·(iBu2AlOAliBu2) p ·(AlMe3) q ·(AliBu3) r 、(MeAlO) m ·(iBuAlO) n 、(Me2AlOAlMe2) m ·(iBu2AlOAliBu2) n 、(MeAlO) m ·(iBu2AlOAliBu2) n 、(iBuAlO) m ·(Me2AlOAlMe2) n 、(MeAlO) m ·(Me2AlOAlMe2) n ·(iBu2AlOAliBu2) o 、(iBuAlO) m ·(Me2AlOAlMe2) n ·(iBu2AlOAliBu2) o 、(MeAlO) m ·(iBuAlO) n ·(Me2AlOAlMe2) o ·(iBu2AlOAliBu2) p ;

[0072] For the mixed ethyl-n-propylaluminoxane: (EtAlO) m·(nPrAlO) n ·(AlEt3) o ·(AlnPr3) p 、(Et2AlOAlEt2) m ·(nPr2AlOAlnPr2) n ·(AlEt3) o ·(AlnPr3) p 、(EtAlO) m ·(nPr2AlOAlnPr2) n ·(AlEt3) o ·(AlnPr3) p 、(nPrAlO) m ·(Et2AlOAlEt2) n ·(AlEt3) o ·(AlnPr3) p 、(EtAlO) m ·(Et2AlOAlEt2) n ·(nPr2AlOAlnPr2) o ·(AlEt3) p ·(AlnPr3) q 、(nPrAlO) m ·(Et2AlOAlEt2) n ·(nPr2AlOAlnPr2) o ·(AlEt3) p ·(AlnPr3) q 、(EtAlO) m ·(nPrAlO) n ·(Et2AlOAlEt2) o ·(nPr2AlOAlnPr2) p ·(AlEt3) q ·(AlnPr3) r 、(EtAlO) m ·(nPrAlO) n 、(Et2AlOAlEt2) m ·(nPr2AlOAlnPr2) n 、(EtAlO) m ·(nPr2AlOAlnPr2) n 、(nPrAlO) m ·(Et2AlOAlEt2) n 、(EtAlO) m ·(Et2AlOAlEt2) n ·(nPr2AlOAlnPr2)o , (nPrAlO) m ·(Et2AlOAlEt2) n ·(nPr2AlOAlnPr2) o , (EtAlO) m ·(nPrAlO) n ·(Et2AlOAlEt2) o ·(nPr2AlOAlnPr2) p ;

[0073] For the mixed ethyl n-butyl aluminoxane: (EtAlO) m ·(nBuAlO) n ·(AlEt3) o ·(AlnBu3) p , (Et2AlOAlEt2) m ·(nBu2AlOAlnBu2) n ·(AlEt3) o ·(AlnBu3) p , (EtAlO) m ·(nBu2AlOAlnBu2) n ·(AlEt3) o ·(AlnBu3) p , (nBuAlO) m ·(Et2AlOAlEt2) n ·(AlEt3) o ·(AlnBu3) p , (EtAlO) m ·(Et2AlOAlEt2) n ·(nBu2AlOAlnBu2) o ·(AlEt3) p ·(AlnBu3) q , (nBuAlO) m ·(Et2AlOAlEt2) n ·(nBu2AlOAlnBu2) o ·(AlEt3) p ·(AlnBu3) q , (EtAlO) m ·(nBuAlO) n ·(Et2AlOAlEt2) o ·(nBu2AlOAlnBu2) p ·(AlEt3) q ·(AlnBu3) r , (EtAlO) m·(nBuAlO) n 、(Et2AlOAlMe2) m ·(nBu2AlOAlnBu2) n 、(EtAlO) m ·(nBu2AlOAlnBu2) n 、(nBuAlO) m ·(Et2AlOAlEt2) n 、(EtAlO) m ·(Et2AlOAlEt2) n ·(nBu2AlOAlnBu2) o 、(nBuAlO) m ·(Et2AlOAlEt2) n ·(nBu2AlOAlnBu2) o 、(EtAlO) m ·(nBuAlO) n ·(Et2AlOAlEt2) o ·(nBu2AlOAlnBu2) p ;

[0074] For the mixed ethyl isobutyl aluminoxane: (EtAlO) m ·(iBuAlO) n ·(AlEt3) o ·(AliBu3) p 、(Et2AlOAlEt2) m ·(iBu2AlOAliBu2) n ·(AlEt3) o ·(AliBu3) p 、(EtAlO) m ·(iBu2AlOAliBu2) n ·(AlEt3) o ·(AliBu3) p 、(iBuAlO) m ·(Et2AlOAlEt2) n ·(AlEt3) o ·(AliBu3) p 、(EtAlO) m ·(Et2AlOAlEt2) n ·(iBu2AlOAliBu2) o ·(AlEt3) p ·(AliBu3) q 、(iBuAlO) m ·(Et2AlOAlEt2)n ·(Diisobutylaluminum oxide) o ·(Triethylaluminum) p ·(Triisobutylaluminum) q 、(Ethylaluminum oxide) m ·(Isobutylaluminum oxide) n ·(Diethylaluminum oxide) o ·(Diisobutylaluminum oxide) p ·(Triethylaluminum) q ·(Triisobutylaluminum) r 、(Ethylaluminum oxide) m ·(Isobutylaluminum oxide) n 、(Dimethylaluminum oxide) m ·(Diisobutylaluminum oxide) n 、(Ethylaluminum oxide) m ·(Diisobutylaluminum oxide) n 、(Isobutylaluminum oxide) m ·(Diethylaluminum oxide) n 、(Ethylaluminum oxide) m ·(Diethylaluminum oxide) n ·(Diisobutylaluminum oxide) o 、(Isobutylaluminum oxide) m ·(Diethylaluminum oxide) n ·(Diisobutylaluminum oxide) o 、(Ethylaluminum oxide) m ·(Isobutylaluminum oxide) n ·(Diethylaluminum oxide) o ·(Diisobutylaluminum oxide) p ;

[0075] For the mixed n-propyl n-butylaluminum oxide: (n-Butylaluminum oxide) m ·(n-Propylaluminum oxide) n ·(Tri-n-butylaluminum) o ·(Tri-n-propylaluminum) p 、(Di-n-butylaluminum oxide) m ·(Di-n-propylaluminum oxide) n ·(Tri-n-butylaluminum) o ·(Tri-n-propylaluminum) p 、(n-Butylaluminum oxide) m ·(Di-n-propylaluminum oxide) n ·(Tri-n-butylaluminum) o ·(Tri-n-propylaluminum) p、(nPrAlO) m ·(nBu2AlOAlnBu2) n ·(AlnBu3) o ·(AlnPr3) p 、(nBuAlO) m ·(nBu2AlOAlnBu2) n ·(nPr2AlOAlnPr2) o ·(AlnBu3) p ·(AlnPr3) q 、(nPrAlO) m ·(nBu2AlOAlnBu2) n ·(nPr2AlOAlnPr2) o ·(AlnBu3) p ·(AlnPr3) q 、(nBuAlO) m ·(nPrAlO) n ·(nBu2AlOAlnBu2) o ·(nPr2AlOAlnPr2) p ·(AlnBu3) q ·(AlnPr3) r 、(nBuAlO) m ·(nPrAlO) n 、(nBu2AlOAlnBu2) m ·(nPr2AlOAlnPr2) n 、(nBuAlO) m ·(nPr2AlOAlnPr2) n 、(nPrAlO) m ·(nBu2AlOAlnBu2) n 、(nBuAlO) m ·(nBu2AlOAlnBu2) n ·(nPr2AlOAlnPr2) o 、(nPrAlO) m ·(nBu2AlOAlnBu2) n ·(nPr2AlOAlnPr2) o 、(nBuAlO) m ·(nPrAlO) n ·(nBu2AlOAlnBu2) o ·(nPr2AlOAlnPr2) p ;

[0076] The mixed n-butylisobutylaluminoxane is: (nBuAlO) m ·(iBuAlO) n ·(AlnBu3) o (AliBu3) p (nBu2AlOAlnBu2) m ·(iBu2AlOAliBu2) n ·(AlnBu3) o (AliBu3) p (nBuAlO) m ·(iBu2AlOAliBu2) n ·(AlnBu3) o (AliBu3) p (iBuAlO) m ·(nBu2AlOAlnBu2) n ·(AlnBu3) o (AliBu3) p (nBuAlO) m ·(nBu2AlOAlnBu2) n ·(iBu2AlOAliBu2) o ·(AlnBu3) p (AliBu3) q (iBuAlO) m ·(nBu2AlOAlnBu2) n ·(iBu2AlOAliBu2) o ·(AlnBu3) p (AliBu3) q (nBuAlO) m ·(iBuAlO) n ·(nBu2AlOAlnBu2) o ·(iBu2AlOAliBu2) p ·(AlnBu3) q (AliBu3) r (nBuAlO) m ·(iBuAlO) n (nBu2AlOAlnBu2) m ·(iBu2AlOAliBu2) n (nBuAlO) m ·(iBu2AlOAliBu2) n (iBuAlO) m ·(nBu2AlOAlnBu2) n (nBuAlO)m ·(nBu2AlOAlnBu2) n ·(iBu2AlOAliBu2) o (iBuAlO) m ·(nBu2AlOAlnBu2) n ·(iBu2AlOAliBu2) o (nBuAlO) m ·(iBuAlO) n ·(nBu2AlOAlnBu2) o ·(iBu2AlOAliBu2) p .

[0077] The method described in this invention is also applicable to mixtures of three or more alkylaluminum compounds, and obviously the resulting polyalkyl aluminum oxanes have a more complex composition and structure. The significance of preparing polyalkyl aluminum oxanes still depends on their performance as co-catalysts or catalysts. This is something those skilled in the art will recognize.

[0078] The proportions of alkylaluminum A, B, C (or more components) and the first inert organic solvent, and the resulting concentrations of A, B, C (or more components), are still determined based on the optimal co-catalytic or catalytic performance achieved by the prepared poly-alkylaluminoxane mixture. Specifically, the following steps are included:

[0079] (1) The reactor is replaced with an inert gas so that the reactor contains the lowest possible amount of water, oxygen and other impurities; specifically, the water and oxygen content in the reactor after replacement is less than 1000 ppm, preferably less than 100 ppm.

[0080] (2) Weigh a certain amount of alkyl aluminum A, a certain amount of alkyl aluminum B, a certain amount of C, and a certain amount of the first inert organic solvent to prepare a solution (reaction solution), inject it into the reactor, and turn on the stirring device; the amount of reaction solution in the reactor accounts for 1 / 10 to 9 / 10 of the reactor volume, preferably 1 / 2 to 2 / 3;

[0081] (3) Set the reactor to a certain temperature; control the reaction temperature between -50 and 110°C, preferably between -20 and 90°C, and even more preferably between -10 and 80°C;

[0082] (4) A certain amount of water-carrying column packing is filled into the column, and then a certain amount of water is injected. Then, a mobile phase that is inert to water, column packing and alkyl aluminum is introduced, carrying the water in the packing into the reactor formed by alkyl aluminum and the first inert organic solvent, and the reaction is carried out under stirring.

[0083] (5) The alkane gas produced in the reaction partially dissolves in the mixed liquid containing polyalkylaluminoxanes and is partially released; when no gas is released, the reactor temperature is increased (increased by 50-70°C) and the reaction continues for a period of time until no more gas is produced, and the reaction is terminated.

[0084] (6) Collect the mixture containing polyalkylaluminoxanes under an inert atmosphere, seal and store for later use.

[0085] The quantitative concentration of polyalkylaluminoxanes is determined using the mass percentage of metallic aluminum, consistent with the method described above for synthesizing alkylaluminoxanes from single alkylaluminum. However, this quantitative concentration cannot be used to calculate the reaction conversion or yield. After removing volatile alkylaluminum and organic solvents from the mixture containing polyalkylaluminoxanes, solid polyalkylaluminoxanes are obtained. Nuclear magnetic resonance spectroscopy is performed as follows... 1 H, 13 C and 27 Al spectroscopy can detect the presence of polyalkyl groups and metallic aluminum, but its precise measurement is insufficient.

[0086] The three mixed alkylaluminum compounds A, B, and C are preferably selected from trimethylaluminum, triethylaluminum, and tri-n-propylaluminum; trimethylaluminum, triethylaluminum, and tri-n-butylaluminum; trimethylaluminum, triethylaluminum, and triisobutylaluminum; trimethylaluminum, tri-n-propylaluminum, and tri-n-butylaluminum; trimethylaluminum, tri-n-propylaluminum, and tri-n-butylaluminum; triethylaluminum, tri-n-propylaluminum, and triisobutylaluminum; tri-n-propylaluminum, tri-n-butylaluminum, and triisobutylaluminum. The structural formulas of these polyalkylaluminoxanes are complex, as will be apparent to those skilled in the art.

[0087] The method described in this invention yields a single alkylaluminoxane. Further addition of other alkylaluminum compounds and reaction with the synthesized single alkylaluminoxane allows for the preparation of modified alkylaluminoxanes. Specifically, the method includes the following steps:

[0088] (1) The reactor is replaced with an inert gas so that the reactor contains the lowest possible amount of water, oxygen and other impurities; specifically, the water and oxygen content in the reactor after replacement is less than 1000 ppm, preferably less than 100 ppm.

[0089] (2) Weigh a certain amount of alkyl aluminum A and a certain amount of the first inert organic solvent to prepare a solution (reaction solution), inject it into the reactor, and turn on the stirring device; the amount of reaction solution in the reactor is 1 / 10 to 9 / 10 of the reactor volume, preferably 1 / 2 to 2 / 3;

[0090] (3) Set the reactor to a certain temperature; control the reaction temperature between -50 and 110°C, preferably between -20 and 90°C, and even more preferably between -10 and 80°C;

[0091] (4) A certain amount of water-carrying column packing is filled into the column, and then a certain amount of water is injected. Then, a mobile phase that is inert to water, column packing and alkyl aluminum is introduced, carrying the water in the packing into the reactor formed by alkyl aluminum and the first inert organic solvent, and the reaction is carried out under stirring.

[0092] (5) The alkane gas produced in the reaction partially dissolves in the mixed liquid containing polyalkylaluminoxanes and is partially released; when no gas is released, the reactor temperature is increased (increased by 50-70°C) and the reaction continues for a period of time until no more gas is produced, and the reaction is terminated.

[0093] (6) Weigh a certain amount of alkylaluminum B and inject it into the reactor, and turn on the stirring device; set the reactor to a certain temperature (the reaction temperature is controlled at -50 to 110°C, preferably at -20 to 90°C, and even more preferably at -10 to 80°C), and stir for a certain time to obtain a mixture containing modified alkylaluminoxane.

[0094] (7) Collect the mixture containing the modified alkylaluminoxane under an inert atmosphere, seal and store for later use.

[0095] The ratio of alkylaluminum A to the first inert organic solvent, and the resulting concentration of A, as well as the amount of alkylaluminum B added, still depend on the optimal catalytic or co-catalytic performance achieved by the modified alkylaluminoxane prepared.

[0096] The quantitative concentration of the modified alkylaluminoxane is determined using the mass percentage of metallic aluminum, consistent with the method described above for synthesizing alkylaluminoxanes from a single alkylaluminum. This quantitative concentration can also be used to calculate the reaction conversion or yield. The first step, controlled hydrolysis, is the control step in the calculation, and the exchange reaction between the two aluminum alkyl groups in the second step can be considered a complete conversion reaction. After removing volatile alkylaluminum and organic solvents from the mixture containing the modified alkylaluminoxane, a solid modified alkylaluminoxane is obtained. This is then analyzed by nuclear magnetic resonance spectroscopy, as shown in... 1 H, 13 C and 27 Al spectroscopy can detect the presence of two alkyl groups and metallic aluminum, but precise measurement is insufficient.

[0097] Alkyl aluminum A and B are preferably selected from trimethylaluminum and triethylaluminum, trimethylaluminum and tri-n-propylaluminum, trimethylaluminum and tri-n-butylaluminum, trimethylaluminum and triisobutylaluminum, triethylaluminum and tri-n-propylaluminum, triethylaluminum and tri-n-butylaluminum, triethylaluminum and triisobutylaluminum, tri-n-propylaluminum and tri-n-butylaluminum, tri-n-propylaluminum and triisobutylaluminum. Alkyl aluminum A and B can be further preferred from trimethylaluminum and triethylaluminum, trimethylaluminum and tri-n-propylaluminum, trimethylaluminum and tri-n-butylaluminum, and trimethylaluminum and triisobutylaluminum.

[0098] The modified alkylaluminoxanes prepared have complex structures, possibly due to the continuous change in the ratio of A to B. More importantly, when the groups in A and B change, it is difficult to quantify the amount of groups exchanged during the exchange reaction.

[0099] For example, when alkylaluminum A and B are preferably selected from trimethylaluminum and triethylaluminum, the result is an ethyl-modified methylaluminoxane. By analogy, other modified aluminum oxanes can be named.

[0100] A second aspect of the present invention provides an apparatus for preparing alkylaluminoxanes as described in the method of the first aspect of the present invention, comprising a reactor with a stirring device and a packed column connected to a first feed inlet at the top of the reactor.

[0101] In some embodiments of the present invention, a second feed inlet is provided at the top of the reactor, the second feed inlet being connected to the inlet pipeline of the solution formed by the alkylaluminum and the first inert organic solvent;

[0102] The reactor is also equipped with a gas outlet at the top for discharging the gases generated during the reaction.

[0103] In this invention, the inlet pipeline of the solution formed by the alkyl aluminum and the first inert organic solvent can be further connected to a first micro-injection pump, which is used to pump the solution formed by the alkyl aluminum and the first inert organic solvent into the reactor.

[0104] Furthermore, due to the generation of heat and the overflow of gaseous products during the reaction, alkylaluminum, alkylaluminoxanes, and inert organic solvents, especially low-boiling-point methane, ethane, propane, and butane gaseous phases, will inevitably be carried out of the reaction system. Therefore, a condenser and collector need to be installed at the gas outlet to collect the condensed alkylaluminum or alkylaluminum solution or alkylaluminoxane solution or solvent carried out. This collected liquid can be returned to the reaction system through a second inlet for mixing and metering.

[0105] In some embodiments of the present invention, the bottom of the reactor is further provided with a discharge port for discharging the reaction products out of the reactor.

[0106] In some other embodiments of the invention, the reactor is further provided with an inert gas inlet connected to an inert gas inlet pipeline for introducing inert gas into the reactor to collect a mixture containing alkylaluminoxanes under an inert atmosphere.

[0107] In the present invention, a safety relief port may also be provided on the reactor. In addition, other devices such as pressure gauges or meters, temperature gauges or meters, a constant temperature controller for the reactor (note: a device for maintaining the reactor at a set temperature), a visual window, a random sampling port, etc. also need to be configured.

[0108] The reactor is capable of allowing the reaction temperature to be in the range of -80 to 150 °C and the pressure to be in the range of 0 to 150 atm. The facilities, configurations, etc. equipped with the reactor also need to withstand the same temperature and pressure. The stirring device equipped with the reactor can ensure smooth stirring of the reaction materials, and a blade-type stirring device is preferred.

[0109] In the present invention, the shape and filling volume of the packing column are determined by calculating the amount of the synthesized alkylaluminoxane, and a cylindrical shape with a certain length is preferred. The packing column can be placed horizontally, vertically, or at any angle within the range between these two placement forms (i.e., within 0 to 90°).

[0110] In the present invention, the filling volume of the packing column is such that the water-carrying capacity of the packing column is within the range of 0.1 mL to 1000 mL.

[0111] In some embodiments of the present invention, a first interface and a second interface are provided at the top of the packing column; the first interface and the second interface are respectively used to connect to a water (such as pure water) inlet pipeline and a mobile phase inlet pipeline.

[0112] In the present invention, the mobile phase inlet pipeline includes two lines, namely an inlet pipeline for a gaseous substance that does not react with water and alkylaluminum and a second inert organic solvent inlet pipeline.

[0113] In some other embodiments of the present invention, a third interface may also be provided at the top of the packing column, and the third interface is used to connect to a first pressure gauge.

[0114] In the present invention, the water inlet pipeline and the second inert organic solvent inlet pipeline can be further connected to a second micro-syringe pump and a third micro-syringe pump respectively, for pumping water and the second inert organic solvent into the packing column respectively.

[0115] In some embodiments of the present invention, an outlet is provided at the lower part of the packing column, and the outlet is connected to the first feed port of the reactor through a conduit. The conduit can enable the water-containing mobile phase passing through the column packing to enter the solution formed by alkylaluminum and the first inert organic solvent homogeneously and uniformly for reaction. It is particularly noted that if the conduit cannot or cannot well enable the water-containing mobile phase passing through the column packing to enter the solution formed by alkylaluminum and the first inert organic solvent homogeneously and uniformly, it is necessary to consider equipping certain configurations such as a static mixer or an atomizer to achieve this functional purpose.

[0116] Among alkylaluminum compounds, trimethylaluminum reacts most vigorously with water, exhibiting high exothermic activity and releasing a large amount of methane gas; triethylaluminum shows a similar pattern, also highly exothermic and releasing a large amount of ethane gas. Other alkylaluminum compounds also exhibit high exothermic activity, but the resulting alkanes show progressively better solubility in solution as the number of carbon atoms increases. The heat generated in the reaction system can be controlled by a thermostat in the reactor to stabilize the reaction. Some of the generated alkane gas dissolves in the resulting mixture containing alkylaluminoxanes, some is released through the reactor's gas outlet, and some affects the effluent phase of the packed column. Therefore, regarding the effluent phase of the packed column, when it is a gaseous mobile phase, the gas pressure in the packed column needs to be adjusted to be slightly higher than the pressure of the reaction system to prevent effluent phase blockage; when it is a liquid mobile phase, a micro-injection pump is required, similarly to prevent effluent phase blockage. Attached Figure Description

[0117] The invention will now be further described with reference to the accompanying drawings.

[0118] Figure 1 The apparatus used in the method described in the embodiments of the present invention for preparing alkylaluminoxanes; wherein the reference numerals in the drawings have the following meanings:

[0119] 1-Inert gas inlet line; 2-First micro-injection pump; 3-Inlet line for the solution formed by alkylaluminum and the first inert organic solvent; 4-Second micro-injection pump; 5-Water (e.g., pure water) inlet line; 6-Packed column; 7-Inlet line for gaseous substances that do not react with water and alkylaluminum; 8-Second inert organic solvent inlet line; 9-Third micro-injection pump; 10-First pressure gauge; 11-Nebulizer; 12-Stirring device; 13-Second pressure gauge; 14-Condensate inlet; 15-Condensate outlet; 16-Reflux condenser; 17-Collector; 18-Vent line; 19-Reactor; 20-Thermostat; 21-Discharge port; 22-First feed inlet; 23-Second feed inlet; 24-Inert gas inlet; 25-Gas outlet; 26-First interface; 27-Second interface. Detailed Implementation

[0120] To make the present invention easier to understand, the present invention will be further described in detail below with reference to embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of application of the present invention. Unless otherwise specified, the raw materials or components used in the present invention can be obtained commercially or by conventional methods.

[0121] The apparatus used in the following examples for preparing alkylaluminoxanes is as follows: Figure 1 As shown. The device includes a reactor 19 with a stirring device 12 and a packing column 6 connected to a first feed inlet 22 at the top of the reactor 19;

[0122] The reactor 19 is also provided with a second feed inlet 23 at the top, which is connected to the inlet pipeline 3 of the solution formed by the alkyl aluminum and the first inert organic solvent; the inlet pipeline 3 of the solution formed by the alkyl aluminum and the first inert organic solvent is further connected to a first micro-injection pump 2; the reactor 19 is also provided with a gas outlet 25 at the top for discharging the gas generated during the reaction, and a reflux condenser 16 and a collector 17 are configured at the gas outlet 25. The bottom and top of the reflux condenser 16 are respectively provided with a condensate inlet 14 and a condensate outlet 15, and the collector 17 is also provided with a vent pipeline 18; the reactor 19 is also provided with a discharge port 21 at the bottom for discharging the reaction products from the reactor; the reactor 19 is also provided with an inert gas inlet 24, which is connected to an inert gas inlet pipeline 1; the reactor 19 may also be provided with a second pressure gauge 13 and a thermostat 20.

[0123] The top of the packed column 6 is provided with a first interface 26 and a second interface 27; the first interface 26 and the second interface 27 are respectively connected to a water (e.g., pure water) inlet line 5 and a mobile phase inlet line; the mobile phase inlet line includes an inlet line 7 for gaseous substances that do not react with water and alkyl aluminum and a second inert organic solvent inlet line 8; the water inlet line 5 and the second inert organic solvent inlet line 8 are further connected to a second micro-injection pump 4 and a third micro-injection pump 9, respectively; the top of the packed column is also provided with a third interface, which is connected to a first pressure gauge 10; the lower part of the packed column is provided with an outlet, which is connected to the first feed port 22 of the reactor through a conduit; an atomizer 11 is provided at the bottom of the conduit.

[0124] Example 1

[0125] The reactor was purged with N2 atmosphere five times. 24 g of trimethylaluminum and 100 mL of toluene were weighed and mixed to prepare a solution (21.7 wt% trimethylaluminum content). This solution was injected into the reactor, the stirrer was turned on, and the reaction temperature was set to 0°C. 15-mesh silica ceramic powder was packed into the column, compacted, and pure water was injected until the entire column was uniformly wetted. Then, pure water was pumped in at a rate of 0.01 mL / min using a metering pump, controlling the molar ratio of water to trimethylaluminum to be 1:1. The N2 valve was opened, and the flow rate was adjusted to 15 mL / min, allowing the water from the column packing to enter the alkylaluminum solution in the reactor for reaction. The reaction lasted 10 hours. The reaction temperature was further increased to 50°C, and the reaction was allowed to proceed for 10 minutes. N2 and methane gas generated during the reaction were vented through a -50°C condenser, and the condensate was recovered back into the reactor. After the reaction was complete, the mixture was cooled to room temperature, and the product solution was collected under an inert atmosphere. Samples were taken for analysis and then sealed for later use.

[0126] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.2% by mass, and the yield of methylaluminoxane was 87%.

[0127] Example 2

[0128] The reaction time at 0°C in Example 1 was adjusted to 8 hours. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0129] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.0% by mass, and the yield of methylaluminoxane was 92%.

[0130] Example 3

[0131] The reaction time at 0°C in Example 1 was adjusted to 6 hours. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0132] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 7.7% by mass, and the yield of methylaluminoxane was 87%.

[0133] Example 4

[0134] The reaction time at 0°C in Example 1 was adjusted to 4 hours. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0135] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 7.7% by mass, and the yield of methylaluminoxane was 87%.

[0136] Example 5

[0137] The reactor was purged with N2 atmosphere five times. 30g of trimethylaluminum and 100mL of toluene were weighed and mixed to prepare a solution (25.7wt% trimethylaluminum content). This solution was injected into the reactor, the stirrer was turned on, and the reaction temperature was set to 0℃. 15-mesh silica ceramic powder was packed into the column, compacted, and pure water was injected until the entire column was uniformly wetted. Then, pure water was pumped in at a rate of 0.01mL / min using a metering pump, controlling the molar ratio of water to trimethylaluminum to be 1:2. The N2 valve was opened, and the flow rate was adjusted to 15mL / min, allowing the water from the column packing to enter the alkylaluminum solution in the reactor for reaction. The reaction lasted 10 hours. The reaction temperature was further increased to 50℃, and the reaction was allowed to proceed for 10 minutes. N2 and methane gas generated during the reaction were vented through a -50℃ condenser, and the condensate was recovered back into the reactor. After cooling to room temperature, the product solution was collected under an inert atmosphere, sampled for analysis, and then sealed and stored for later use.

[0138] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 11.6% by mass, and the yield of methylaluminoxane was 88%.

[0139] Example 6

[0140] The amount of trimethylaluminum in Example 5 was adjusted to 36g, and the content of trimethylaluminum in the prepared solution was 29.4wt%. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0141] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 13.1% by mass, and the yield of methylaluminoxane was 86%.

[0142] Example 7

[0143] The amount of trimethylaluminum in Example 5 was adjusted to 42g, and the content of trimethylaluminum in the prepared solution was 32.7wt%. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0144] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 15.7% by mass, and the yield of methylaluminoxane was 84%.

[0145] Example 8

[0146] The amount of trimethylaluminum in Example 5 was adjusted to 48g, and the content of trimethylaluminum in the prepared solution was 35.7wt%. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0147] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 18.3% by mass, and the yield of methylaluminoxane was 88%.

[0148] Example 9

[0149] The reactor was purged with N2 atmosphere five times. 24g of trimethylaluminum and 20mL of toluene were weighed and dissolved, then injected into the reactor. The stirrer was turned on, and the reaction temperature was set to -20℃. 15-mesh silica ceramic powder was packed into the column, compacted, and then pure water was injected until the entire column was uniformly wetted. Pure water was then pumped in at a rate of 0.01mL / min using a metering pump, controlling the molar ratio of water to trimethylaluminum to be 1:2. Toluene, carrying the water from the column packing, was then pumped in at a rate of 0.20mL / min using another metering pump into the alkylaluminum solution in the reactor for reaction. The reaction lasted 6 hours. The reaction temperature was further increased to 50℃, and the reaction was allowed to proceed for 10 minutes. The methane gas produced during the reaction was vented through a -50℃ condenser, and the condensate was recovered back into the reactor. The mixture was cooled to room temperature, and the product solution was collected under an inert atmosphere. Samples were taken for analysis and then sealed for later use.

[0150] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 9.3% by mass, and the yield of methylaluminoxane was 92%.

[0151] Example 10

[0152] The reactor was purged with N2 atmosphere five times. 24g of trimethylaluminum and 20mL of heptane were weighed and dissolved, then injected into the reactor. The stirrer was turned on, and the reaction temperature was set to -20℃. 15-mesh silica ceramic powder was packed into the column, compacted, and then pure water was injected until the entire column was uniformly wetted. Pure water was then pumped in at a rate of 0.01mL / min using a metering pump, controlling the molar ratio of water to trimethylaluminum to be 1:2. Heptane, carrying the water from the packing material, was then pumped in at a rate of 0.20mL / min using another metering pump into the alkylaluminum solution in the reactor for reaction. The reaction lasted 6 hours. The reaction temperature was further increased to 50℃, and the reaction was allowed to proceed for 10 minutes. The methane gas produced during the reaction was vented through a -50℃ condenser, and the condensate was recovered back into the reactor. The mixture was cooled to room temperature, and the product solution was collected under an inert atmosphere. Samples were taken for analysis and then sealed for later use.

[0153] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.7% by mass, and the yield of methylaluminoxane was 89%.

[0154] Example 11

[0155] The reactor was purged with N2 atmosphere five times. 24g of trimethylaluminum and 20mL of methylcyclohexane were weighed and dissolved, then injected into the reactor. The stirrer was turned on, and the reaction temperature was set to -20℃. 15-mesh silica ceramic powder was packed into the column, compacted, and then pure water was injected until the entire column was uniformly wetted. Pure water was then pumped in at a rate of 0.01mL / min using a metering pump, controlling the molar ratio of water to trimethylaluminum to be 1:2. Methylcyclohexane was then pumped in at a rate of 0.20mL / min using another metering pump, carrying the water from the column packing into the alkylaluminum solution in the reactor for reaction. The reaction lasted 6 hours. The reaction temperature was further increased to 50℃, and the reaction was allowed to proceed for 10 minutes. The methane gas produced during the reaction was vented through a -50℃ condenser, and the condensate was recovered back into the reactor. The mixture was cooled to room temperature, and the product solution was collected under an inert atmosphere. Samples were taken for analysis and then sealed for later use.

[0156] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.5% by mass, and the yield of methylaluminoxane was 86%.

[0157] Example 12

[0158] The reactor was purged with N2 atmosphere five times. 24g of trimethylaluminum and 20mL of Isopar E were weighed and dissolved, then injected into the reactor. The stirrer was turned on, and the reaction temperature was set to -20℃. 15-mesh silica powder was packed into the column, compacted, and then pure water was injected until the entire column was uniformly wetted. Pure water was then pumped in at a rate of 0.01mL / min using a metering pump, controlling the molar ratio of water to trimethylaluminum to be 1:2. Isopar E, carrying the water from the column packing, was then pumped in at a rate of 0.20mL / min using another metering pump into the alkylaluminum solution in the reactor for reaction. The reaction lasted 6 hours. The reaction temperature was further increased to 50℃, and the reaction was allowed to proceed for 10 minutes. The methane gas produced during the reaction was vented through a -50℃ condenser, and the condensate was recovered back into the reactor. The mixture was cooled to room temperature, and the product solution was collected under an inert atmosphere. Samples were taken for analysis and then sealed for later use.

[0159] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.6% by mass, and the yield of methylaluminoxane was 87%.

[0160] Example 13

[0161] The reactor was purged with N2 atmosphere five times. 24g of trimethylaluminum and 6g of triethylaluminum were weighed, and 100mL of toluene was measured to prepare a solution. This solution was injected into the reactor, the stirrer was turned on, and the reaction temperature was set to 0℃. 15-mesh silica ceramic powder was packed into the column, compacted, and then pure water was injected until the entire column was uniformly wetted. Then, pure water was pumped in at a rate of 0.01mL / min using a metering pump, controlling the molar ratio of water to alkylaluminum to be 1:2. The N2 valve was opened, and the flow rate was adjusted to 15mL / min, allowing the water from the column packing to enter the alkylaluminum solution in the reactor for reaction. The reaction lasted 10 hours. The reaction temperature was further increased to 50℃, and the reaction was allowed to proceed for 10 minutes. N2 and the methane gas produced during the reaction were vented through a -50℃ condenser, and the condensate was recovered back into the reactor. After cooling to room temperature, the product solution was collected under an inert atmosphere, sampled for analysis, and then sealed and stored for later use.

[0162] Hydrolysis and titration analysis revealed that the mass percentage of aluminum in the methylethylaluminoxane solution was 11.4%, and the yield of methylethylaluminoxane was 92%.

[0163] Example 14

[0164] The reactor was purged with N2 atmosphere five times. 24g of trimethylaluminum and 6g of triisobutylaluminum were weighed, and 100mL of toluene was measured to prepare a solution. This solution was injected into the reactor, the stirrer was turned on, and the reaction temperature was set to 0℃. 15-mesh silica ceramic powder was packed into the column, compacted, and then pure water was injected until the entire column was uniformly wetted. Then, pure water was pumped in at a rate of 0.01mL / min using a metering pump, controlling the molar ratio of water to alkylaluminum to be 1:2. The N2 valve was opened, and the flow rate was adjusted to 15mL / min, allowing the water from the column packing to enter the alkylaluminum solution in the reactor for reaction. The reaction lasted 10 hours. The reaction temperature was further increased to 50℃, and the reaction was allowed to proceed for 10 minutes. N2 and the methane gas produced during the reaction were vented through a -50℃ condenser, and the condensate was recovered back into the reactor. After cooling to room temperature, the product solution was collected under an inert atmosphere, sampled for analysis, and then sealed and stored for later use.

[0165] Hydrolysis and titration analysis revealed that the aluminum content in the methyl isobutylaluminoxane solution was 11.8% by mass, and the yield of methyl isobutylaluminoxane was 93%.

[0166] Example 15

[0167] The reactor was purged with N2 atmosphere five times. 24g of trimethylaluminum, 3g of triethylaluminum, and 3g of triisobutylaluminum were weighed, and 100mL of toluene was measured to prepare a solution. This solution was injected into the reactor, the stirrer was turned on, and the reaction temperature was set to 0℃. 15-mesh silica ceramic powder was packed into the column, compacted, and then pure water was injected until the entire column was uniformly wetted. Pure water was then pumped in at a rate of 0.01mL / min using a metering pump, controlling the molar ratio of water to alkylaluminum to be 1:2. The N2 valve was opened, and the flow rate was adjusted to 15mL / min, allowing the water from the column packing to enter the alkylaluminum solution in the reactor for reaction. The reaction lasted 10 hours. The reaction temperature was further increased to 50℃, and the reaction was allowed to proceed for 10 minutes. N2 and the methane gas produced during the reaction were vented through a -50℃ condenser, and the condensate was recovered back into the reactor. After cooling to room temperature, the product solution was collected under an inert atmosphere, sampled for analysis, and then sealed and stored for later use.

[0168] Hydrolysis and titration analysis revealed that the mass percentage of aluminum in the methyl ethyl isobutyl aluminum oxane solution was 11.6%, and the yield of methyl ethyl isobutyl aluminum oxane was 90%.

[0169] Example 16

[0170] The reactor was purged with N2 atmosphere five times. 24g of trimethylaluminum and 100mL of toluene were weighed and dissolved, then injected into the reactor. The stirrer was turned on, and the reaction temperature was set to 0℃. 15-mesh silica ceramic powder was packed into the column, compacted, and then pure water was injected until the entire column was uniformly wetted. Then, pure water was pumped in at a rate of 0.01mL / min using a metering pump, controlling the molar ratio of water to trimethylaluminum to be 1:2. The N2 valve was opened, and the flow rate was adjusted to 15mL / min, allowing the water from the column packing to enter the alkylaluminum solution in the reactor for the reaction. The reaction lasted 10 hours.

[0171] Add 6 g of triethylaluminum and stir for 1 h. Further raise the reaction temperature to 50 °C and react for 10 min. N2 and methane gas produced during the reaction are vented through a -50 °C condenser, and the condensate is recovered back into the reactor. Cool to room temperature, collect the product solution under an inert atmosphere, sample for analysis, and then seal and store for later use.

[0172] Hydrolysis and titration analysis revealed that the aluminum content in the ethyl-modified methylaluminoxane solution was 12.5% ​​by mass, and the yield of ethyl-modified methylaluminoxane was 90%.

[0173] Example 17

[0174] The reactor was purged with N2 atmosphere five times. 24g of trimethylaluminum and 100mL of toluene were weighed and dissolved, then injected into the reactor. The stirrer was turned on, and the reaction temperature was set to 0℃. 15-mesh silica ceramic powder was packed into the column, compacted, and then pure water was injected until the entire column was uniformly wetted. Then, pure water was pumped in at a rate of 0.01mL / min using a metering pump, controlling the molar ratio of water to trimethylaluminum to be 1:2. The N2 valve was opened, and the flow rate was adjusted to 15mL / min, allowing the water from the column packing to enter the alkylaluminum solution in the reactor for the reaction. The reaction lasted 10 hours.

[0175] Add 6 g of triisobutylaluminum and stir for 1 h. Further raise the reaction temperature to 50 °C and react for 10 min. N2 and methane gas produced during the reaction are vented through a -50 °C condenser, and the condensate is recovered back into the reactor. Cool to room temperature, collect the product solution under an inert atmosphere, sample for analysis, and then seal and store for later use.

[0176] Hydrolysis and titration analysis revealed that the aluminum content in the isobutyl-modified methylaluminoxane solution was 11.7% by mass, and the yield of isobutyl-modified methylaluminoxane was 87%.

[0177] Example 18

[0178] The reactor was purged with N2 atmosphere five times. 24g of trimethylaluminum and 100mL of toluene were weighed and dissolved, then injected into the reactor. The stirrer was turned on, and the reaction temperature was set to 0℃. 15-mesh alumina ceramic powder was packed into the column, compacted, and then pure water was injected until the entire column was uniformly wetted. Pure water was then pumped in at a rate of 0.01mL / min using a metering pump, controlling the molar ratio of water to trimethylaluminum to be 1:2. The N2 valve was opened, and the flow rate was adjusted to 15mL / min, allowing the water from the column packing to enter the alkylaluminum solution in the reactor for reaction. The reaction lasted 10 hours. The reaction temperature was further increased to 50℃, and the reaction was allowed to proceed for 10 minutes. N2 and methane gas generated during the reaction were vented through a -50℃ condenser, and the condensate was recovered back into the reactor. After cooling to room temperature, the product solution was collected under an inert atmosphere, sampled for analysis, and then sealed and stored for later use.

[0179] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.3% by mass, and the yield of methylaluminoxane was 88%.

[0180] Example 19

[0181] The column packing material in Example 18 was replaced with 15-mesh kaolin porcelain powder. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0182] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.4% by mass, and the yield of methylaluminoxane was 90%.

[0183] Example 20

[0184] The column packing material in Example 18 was replaced with 15-mesh attapulgite porcelain powder. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0185] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.4% by mass, and the yield of methylaluminoxane was 90%.

[0186] Example 21

[0187] The column packing material in Example 18 was replaced with particulate polyethylene resin. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0188] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.7% by mass, and the yield of methylaluminoxane was 91%.

[0189] Example 22

[0190] The column packing material in Example 18 was replaced with particulate polypropylene resin. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0191] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.6% by mass, and the yield of methylaluminoxane was 90%.

[0192] Example 23

[0193] The column packing material in Example 18 was replaced with particulate polystyrene resin. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0194] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.6% by mass, and the yield of methylaluminoxane was 90%.

[0195] Example 24

[0196] The column packing material in Example 18 was replaced with particulate polymethyl methacrylate resin. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0197] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.5% by mass, and the yield of methylaluminoxane was 90%.

[0198] Example 25

[0199] The column packing material in Example 18 was replaced with particulate polyvinyl chloride resin. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0200] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.4% by mass, and the yield of methylaluminoxane was 86%.

[0201] Example 26

[0202] The column packing material in Example 18 was replaced with particulate polycarbonate resin. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0203] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.5% by mass, and the yield of methylaluminoxane was 88%.

[0204] Example 27

[0205] The column packing material in Example 18 was replaced with particulate polyetheretherketone resin. Finally, the product solution was collected under an inert atmosphere, sampled and analyzed, and then sealed and stored for later use.

[0206] Hydrolysis and titration analysis revealed that the aluminum content in the methylaluminoxane solution was 8.5% by mass, and the yield of methylaluminoxane was 88%.

[0207] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A method for preparing alkylaluminoxanes using a packed column water-carrying method, comprising: Water is metered using a packed column and injected into a solution formed by alkylaluminum and a first inert organic solvent under the drive of a mobile phase to react and obtain a mixture containing alkylaluminoxane. The reaction temperature is 0~110℃; The water is injected into the packed column via a micro-injection pump; The mobile phase is selected from gaseous substances that do not react with water and alkyl aluminum; The water loading capacity of the packed column is 0.1 mL to 1000 mL; The molar ratio of water to alkyl aluminum is not higher than 1:1; The alkyl aluminum content in the solution is 0.4~80 wt%; The aluminum content in the mixture containing alkylaluminoxane is 0.1~40.0 wt%; wherein, the aluminum content in the mixture containing alkylaluminoxane is controlled by adjusting the amount of the first inert organic solvent. The column packing material in the packed column is selected from inorganic materials that do not react with water or form gels with water, or organic polymers that do not react with water or form gels with water. The inorganic material is selected from at least one of silicon dioxide, alumina, molecular sieve, kaolin, attapulgite, ceramics, metal oxide ceramics and glass fiber; The organic polymer is selected from at least one of polyethylene, polypropylene, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polyisobutylene, polyisoprene, ethylene propylene rubber resin, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polyacrylamide, polycarbonate, polysulfone, and polyetheretherketone.

2. The method according to claim 1, characterized in that, The alkylaluminum has the structural formula AlR3, where R is an alkyl group with 1 to 20 carbon atoms.

3. The method according to claim 1 or 2, characterized in that, The first inert organic solvent is selected from any one of straight-chain hydrocarbons, branched hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons; Alternatively, the alkylaluminum is selected from at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, and tri-n-octylaluminum.

4. The method according to claim 3, characterized in that, The first inert organic solvent is selected from any one of toluene, xylene, trimethylbenzene, n-pentane, isopentane, neopentane, cyclopentane, methylcyclopentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, petroleum ether, isoheptane, neoheptane, Isopar E, and Isopar F.

5. The method according to claim 1, characterized in that, The gaseous substance is selected from any one of nitrogen, argon, and methane.

6. The method according to claim 1 or 2, characterized in that, The molar ratio of water to alkyl aluminum is 1:(1~10).

7. The method according to claim 6, characterized in that, The molar ratio of water to alkyl aluminum is 1:(1~5).

8. The method according to claim 1 or 2, characterized in that, The reaction time is 4 to 15 hours.

9. The method according to claim 8, characterized in that, The reaction temperature is 0~90℃; And / or, the reaction time is 8 to 12 hours.

10. The method according to claim 9, characterized in that, The reaction temperature is 0~80℃.

11. An apparatus for preparing alkylaluminoxanes using the method of any one of claims 1-10, comprising a reactor with a stirring device and a packed column connected to a first feed inlet at the top of the reactor.

12. The apparatus according to claim 11, characterized in that, The reactor is also provided with a second feed inlet at the top, which is used to connect to the inlet pipeline of the solution formed by the alkylaluminum and the first inert organic solvent. The reactor is also equipped with a gas outlet at the top for discharging the gases generated during the reaction.

13. The apparatus according to claim 12, characterized in that, A condenser and a collector are provided at the gas outlet.

14. The apparatus according to any one of claims 11 to 13, characterized in that, The bottom of the reactor is also provided with a discharge port for discharging the reaction products out of the reactor.

15. The apparatus according to any one of claims 11 to 13, characterized in that, The top of the filling column is provided with a first interface and a second interface; the first interface and the second interface are respectively used to connect to the water inlet pipeline and the mobile phase inlet pipeline.

16. The apparatus according to any one of claims 11 to 13, characterized in that, The lower part of the packed column is provided with an outlet, which is connected to the first feed port of the reactor via a conduit.

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