Method for continuously preparing alkylaluminoxane based on non-hydrolysis method

Abstract

The invention discloses a method for continuously preparing alkylaluminoxane based on a non-hydrolysis method, and belongs to the field of alkylaluminoxane preparation. According to the method disclosed by the invention, a microreactor and a flow chemical technology are organically combined, so that the mixing, heat transfer and mass transfer efficiencies in the preparation process of alkylaluminoxane are improved, and the problems of low reaction efficiency, poor activity repeatability of different batches of products and the like in a synthesis technology based on a tank reactor are solved. The method is suitable for the reaction of aluminum alkyl and a gas-phase / liquid-phase compound containing carbon-oxygen bonds, the reaction temperature and the reaction time can be accurately controlled, the whole reaction process is safe and efficient, and the produced alkylaluminoxane product has high yield, high catalytic activity and high stability.

Description

Technical Field

[0001] The invention belongs to the technical field of chemistry and chemical engineering, and specifically relates to the preparation of alkylaluminoxane, and in particular to a method for continuously preparing alkylaluminoxane based on a non-hydrolysis method. Background Art

[0002] In 1980, W. Kaminsky discovered that metallocene catalysts formed with metallocene compounds such as zirconocene dichloride as the main catalyst and alkylaluminoxane compounds represented by methylaluminoxane (MAO) as the co-catalyst have the capabilities of a single active center and excellent catalytic copolymerization. They can greatly improve the polymerization activity of ethylene and prepare a variety of high-end polyolefin products with precisely controllable microstructures, playing an important role in the development of the polyolefin industry.

[0003] There are two main methods for preparing alkylaluminoxanes. The first is the hydrolysis method, which is to prepare alkylaluminoxanes through the controlled reaction of alkylaluminum and water, which is further divided into free hydration method and crystal hydration method according to the source of water; the second is the non-hydrolysis method, which is to prepare alkylaluminoxanes through the reaction of alkylaluminum with carbonyl, hydroxyl, carboxyl or boron-containing compounds.

[0004] Patent US 6881695 B2 discloses a route for synthesizing alkylaluminoxane by hydrolysis. Since alkylaluminum reacts violently with water and releases a large amount of heat, it is not conducive to the control of the reaction process. The invention usually uses a static mixer, a membrane disperser, etc. to disperse water in an inert solvent in the form of small droplets, and then reacts with alkylaluminum at a relatively low temperature. Patent CN102190677 B uses an atomizing device to atomize water and then react, and patent CN 115121200A uses a membrane reactor to prepare microscale water droplets for reaction. The hydrolysis method needs to strictly control the reactant ratio. Too high alumina-water molar ratio will cause the raw material alkylaluminum and alkylaluminoxane product to be over-hydrolyzed to generate aluminum hydroxide by-products, and too low alumina-water ratio is not conducive to improving the reaction conversion rate. Both will lead to problems such as low reaction efficiency and poor product activity. Therefore, the hydrolysis method has extremely high requirements for equipment and process control, and product quality is also difficult to control.

[0005] In order to avoid the above-mentioned problems of the hydrolysis method, a number of existing patents (US 5728855, US 5831109, US5777143, etc.) have developed a technical route for synthesizing alkylaluminoxane by non-hydrolysis method. The reaction raw materials that can be adopted by the non-hydrolysis method are abundant, including various compounds such as carbon dioxide, carboxylic acids, ketones, alcohols, etc. Compared with the hydrogen-oxygen bond in the water molecule, the carbon-oxygen bond reacts more slowly with the alkylaluminum, and the reaction is more easily controlled. The above-mentioned patents all utilize intermittent reactors to synthesize alkylaluminoxane. However, the use of intermittent reactors has low reaction efficiency, poor reproducibility of activity of different batches of products, and reaction conditions are difficult to accurately control and generate by-products, which all affect the final activity of the product, bringing difficulties to the actual production of synthesizing alkylaluminoxane by non-hydrolysis method. Summary of the invention

[0006] The present invention aims to overcome the deficiencies of the prior art and provide a method for continuously preparing alkylaluminoxane based on a non-hydrolysis method, which is more conducive to controlling the reaction process, can achieve intrinsically safe preparation of alkylaluminoxane, and the product has high yield, high activity and high stability.

[0007] The method of the present invention is as follows: A method for continuously preparing alkylaluminoxane based on a non-hydrolysis method, the method comprising any one of the following methods (1) to (3):

[0008] Method (1): The injection pump S1 delivers an alkyl aluminum solution, and the injection pump S2 delivers a reactant containing a carbon-oxygen bond or a solution of a reactant containing a carbon-oxygen bond diluted with an inert solvent. The two fluids are fully mixed in a micro mixer M1, and the mixed material is delivered to a micro reactor R1 for heating and reaction to obtain an alkyl aluminum oxane solution.

[0009] Method (2): The injection pump S1 delivers an alkyl aluminum solution, and the injection pump S2 delivers a reactant containing a carbon-oxygen bond or a reactant solution containing a carbon-oxygen bond diluted with an inert solvent. The two fluids are fully mixed in a micro mixer M1, and the mixed material is delivered to a micro reactor R1 for heating and reaction to obtain an alkyl aluminum oxane precursor solution; the alkyl aluminum oxane precursor solution and the activator delivered by the injection pump S3 are fully mixed in a micro mixer M2, and the mixed material is delivered to a micro reactor R2 for heating and reaction to obtain an alkyl aluminum oxane solution;

[0010] Method (3): The injection pump S1 delivers the alkyl aluminum solution, and the gas cylinder G1 delivers the gas phase carbon-oxygen bond-containing reactants or the mixed gas of carbon-oxygen bond-containing reactants diluted with an inert gas. The two fluids are fully mixed in the micro mixer M4, and the gas-liquid mixture is delivered to the micro reactor R3 for heating and reaction to obtain an alkyl aluminum oxane solution.

[0011] In the method of the present invention, methods (1) and (2) are operating methods when liquid phase reactants containing carbon-oxygen bonds are selected, and method (3) is an operating method when gas phase reactants containing carbon-oxygen bonds are selected.

[0012] In particular, for some systems, the method (1) further comprises: arranging a micromixer M2 between the micromixer M1 and the microreactor R1, partially refluxing the alkylaluminoxane solution obtained from the microreactor R1 through the diverter F1, fully mixing the mixed liquid flowing out of the micromixer M1 in the micromixer M2, and then transporting it back to the microreactor R1 for heating and reaction to obtain the alkylaluminoxane solution; the reflux ratio is 0.1-20.

[0013] For some systems, the method (2) further includes: setting a micromixer M3 between the micromixer M2 and the microreactor R2, partially refluxing the alkyl aluminoxane solution obtained from the microreactor R2 through the diverter F1 and fully mixing it with the mixed liquid flowing out of the micromixer M2 in the micromixer M3, and then transporting it back to the microreactor R2 for heating and reaction to obtain the alkyl aluminoxane solution; the reflux ratio is 0.1-20.

[0014] For some systems, the method (3) further includes: setting a micromixer M5 between the micromixer M4 and the microreactor R3, partially refluxing the alkylaluminoxane solution / gas reactant that has not fully reacted in the microreactor R3 through the diverter F1, fully mixing it with the gas-liquid mixture flowing out of the micromixer M4 in the micromixer M5, and then transporting it back to the microreactor R3 for heating and reaction to obtain an alkylaluminoxane solution; the reflux ratio is 0.1-20.

[0015] Preferably, the gas phase / liquid phase carbon-oxygen bond-containing reactant is selected from one or more of carbon dioxide, carboxylic acid organic compounds, ketone organic compounds, aldehyde organic compounds, and alcohol organic compounds, preferably one or more of carbon dioxide, aromatic carboxylic acid organic compounds, and aromatic ketone organic compounds.

[0016] Preferably, the alkylaluminum is selected from one or more of trialkylaluminum, aryl alkylaluminum, alkoxy alkylaluminum, and halogenated alkylaluminum, preferably one or more of C1-C10 trialkylaluminum.

[0017] Preferably, the activator is selected from one or more of trialkylaluminum, arylalkylaluminum, halogenated alkylaluminum, and alkylaluminoxane, preferably one or more of C1-C10 trialkylaluminum and C1-C10 alkylaluminoxane.

[0018] Preferably, the inert solvent is selected from one or more of aliphatic hydrocarbons, aromatic hydrocarbons, and isomeric alkanes.

[0019] Preferably, the inert gas is selected from one or more of helium, argon and nitrogen.

[0020] Preferably, the concentration of the alkyl aluminum solution is 0.1-80wt%, the concentration of the reactant containing carbon-oxygen bonds in the liquid phase is 0.1-80wt%, and the concentration of the reactant containing carbon-oxygen bonds in the reactant mixture is 0.1-100wt%. The molar ratio of the reactant containing carbon-oxygen bonds to the alkyl aluminum is 0.01-10. Preferably, the concentration of the alkyl aluminum solution is 1-40wt%, the concentration of the reactant containing carbon-oxygen bonds in the liquid phase is 1-40wt%, and the concentration of the reactant containing carbon-oxygen bonds in the reactant mixture is 1-100wt%. Preferably, the molar ratio of the reactant containing carbon-oxygen bonds to the alkyl aluminum is 0.01-2;

[0021] Preferably, the concentration of the activator before mixing is 0.1-40wt%, and the molar ratio of the activator to the alkyl aluminum is 0.001-1.

[0022] Preferably, the volume flow rates of the alkyl aluminum solution, the reactant containing carbon-oxygen bonds, and the activator are all 0.001-5000 mL / min.

[0023] Preferably, the micromixers M1 and M2 described in method (1) are T-type or Y-type micromixers with an inner diameter of 50-5000 μm; the microreactor R1 is a tubular reactor with an inner diameter of 0.05-100 mm, a length of 0.1-30 m, a heating temperature T1 of 0-150° C., an average residence time t1 of 0.01-1 h, and an average residence time t2 of 0.01-30 h.

[0024] Preferably, the micromixers M1, M2, and M3 described in method (2) are T-type or Y-type micromixers with an inner diameter of 50-5000 μm; the microreactors R1 and R2 are tubular reactors with an inner diameter of 0.05-100 mm and a length of 0.1-30 m. The heating temperature T1 is 0-150° C., the heating temperature T2 is 30-150° C., the average residence time t1 is 0.01-1 h, the average residence time t2 is 0.01-5 h, and the average residence time t3 is 0.01-100 h.

[0025] Preferably, the micromixers M4 and M5 described in method (3) are T-type or Y-type micromixers with an inner diameter of 10-1000 μm; the microreactor R3 is a tubular reactor with an inner diameter of 0.01-100 mm, a length of 0.1-30 m, a heating temperature T3 of 0-200° C., reaction pressures P1 and P2 of 1.0-50 MPa, an average residence time t4 of 0.01-1 h, and an average residence time t5 of 0.01-30 h.

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] (1) The components such as the micro mixer and micro reactor used in the present invention have a large specific surface area, thus having high mixing, mass transfer and heat transfer efficiency. In addition, the fluid flow rate in the micro reactor used in the present invention is low, and the flow in the tube is laminar. The reaction materials are mixed uniformly and rapidly under the characteristic size of micrometer level, which is conducive to improving the reaction conversion rate and product activity.

[0028] (2) The synthesis reaction of alkylaluminoxane by the non-hydrolysis method is relatively violent. If a kettle reactor is used, it needs to be carried out at a relatively low temperature. A higher reaction temperature can be used in a microreactor to increase the reaction speed, thereby improving the reaction efficiency; alkylaluminoxane requires a higher temperature for activation. The use of a microreactor can avoid uneven local heating, and the resulting product has a higher catalytic activity.

[0029] (3) The reaction of the present invention is continuously operated, and the quality of the obtained product is stable; and the total volume of the reaction system is small, and the liquid holdup is low, which is a design with intrinsic safety characteristics. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 The schematic diagram of the process of continuously synthesizing alkylaluminoxane in a microreactor without reflux is based on the non-hydrolysis method, using liquid phase carbon-oxygen bond reactants, without introducing activating materials.

[0031] Figure 2 The schematic diagram of the process of continuously synthesizing alkylaluminoxane in a microreactor with reflux based on the non-hydrolysis method, using liquid phase carbon-oxygen bond-containing reactants, without introducing activating substances.

[0032] Figure 3 This is a schematic diagram of the process of continuously synthesizing alkylaluminoxane in a microreactor without reflux based on a non-hydrolysis method, selecting liquid phase carbon-oxygen bond reactants, introducing activators, and a reflux-free microreactor.

[0033] Figure 4 The schematic diagram of the process of continuously synthesizing alkylaluminoxane in a microreactor with reflux is based on a non-hydrolysis method, selecting liquid phase carbon-oxygen bond-containing reactants, introducing activators, and a reflux microreactor.

[0034] Figure 5 This is a schematic diagram of the process for continuously synthesizing alkylaluminoxanes based on a non-hydrolysis method using gas-phase carbon-oxygen bond reactants and a reflux-free microreactor.

[0035] Figure 6 The schematic diagram of the process of continuously synthesizing alkylaluminoxane in a microreactor with reflux based on the non-hydrolysis method, using gas-phase carbon-oxygen bond reactants. DETAILED DESCRIPTION

[0036] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments and comparative examples, but the scope of the present invention cannot be limited thereto. That is, all changes and modifications made according to the scope of the patent application of the present invention still fall within the scope covered by the invention patent.

[0037] Considering the problems of industrial hydrolysis and non-hydrolysis methods for synthesizing alkylaluminoxane, the present invention organically combines microreactors and flow chemistry technology, and proposes a new method for organically combining microreactors and flow chemistry technology. The characteristic size of the microreactor used in this method is at the micron level, and its excellent mixing efficiency and mass transfer and heat transfer efficiency can effectively strengthen the chemical reaction process, reduce local hot spots in the reactor, avoid problems such as uneven concentration, thereby accurately controlling process conditions and synthesizing products with specific properties. At the same time, the microreactor can achieve scaled-up production by increasing the number of parallel reactors, and can avoid the traditional chemical "small test-pilot-large production" process when designing new products, so that the operating cost and time cost are greatly reduced, and the economic benefits of the chemical process are improved.

[0038] like Figure 1-Figure 6 As shown, the method of the present invention further includes three optional implementation methods, which are described as follows:

[0039] Method (1): The injection pump S1 delivers the alkyl aluminum solution, and the injection pump S2 delivers the reactant containing carbon-oxygen bonds or the reactant solution containing carbon-oxygen bonds diluted with an inert solvent. The two fluids are fully mixed in the micro mixer M1, and the mixed material is delivered to the micro reactor R1 for heating (heating temperature T1) and reaction. After an average residence time t1, an alkyl aluminumoxane solution ( Figure 1 ). In particular, for some systems, the alkylaluminoxane solution is partially refluxed through the splitter F1 (reflux ratio r1) and the mixed solution flowing out of the micromixer M1 is fully mixed in the micromixer M2, and then transported back to the microreactor R1 for heating (heating temperature T1) and reaction, and the alkylaluminoxane solution ( Figure 2 ).

[0040] Method (2): The injection pump S1 delivers the alkyl aluminum solution, and the injection pump S2 delivers the reactant containing carbon-oxygen bonds or the reactant solution containing carbon-oxygen bonds diluted with an inert solvent. The two fluids are fully mixed in the micro mixer M1, and the mixed material is delivered to the micro reactor R1 for heating (heating temperature T1) and reaction, and the alkyl aluminum oxane precursor solution is obtained after the average residence time t1. The alkyl aluminum oxane precursor and the activated material delivered by the injection pump S3 are fully mixed in the micro mixer M2, and the mixed material is delivered to the micro reactor R2 for heating (heating temperature T2) and reaction, and the alkyl aluminum oxane solution is obtained after the average residence time t2. Figure 3). In particular, for some systems, the alkylaluminoxane solution is partially refluxed through the splitter F1 (reflux ratio r1) and the mixed solution flowing out of the micromixer M2 is fully mixed in the micromixer M3, and then transported back to the microreactor R2 for heating (heating temperature T2) and reaction, and the alkylaluminoxane solution ( Figure 4 ).

[0041] Method (3): The injection pump S1 delivers the alkyl aluminum solution, and the gas cylinder G1 delivers the gas phase carbon-oxygen bond-containing reactant or the mixed gas of the carbon-oxygen bond-containing reactant diluted by an inert gas. The two streams are fully mixed in the micro mixer M4, and the gas-liquid mixture is delivered to the micro reactor R3 for heating (heating temperature T3) and reaction. The reaction pressure is P1, and the alkyl aluminum oxane solution ( Figure 5 ). In particular, for some systems, the alkylaluminoxane solution / gas reactant that has not fully reacted is partially refluxed through the splitter F1 (reflux ratio r2) and the gas-liquid mixture flowing out of the micromixer M4 is fully mixed in the micromixer M5, and then transported back to the microreactor R3 for heating (heating temperature T3) and reaction. The reaction pressure is P2, and the alkylaluminoxane solution ( Figure 6 ).

[0042] The embodiments of the present invention are operated in a Schlenk line (double-row tube) or a glove box. The present invention requires that the reaction system used be vacuumed and replaced with nitrogen more than five times in advance to completely remove moisture and oxygen in the system to avoid deterioration of the reaction raw materials and products. The liquid phase reactant is transported and its flow is controlled by a fluid pump, and the gas phase reactant is transported by a gas pipeline connected to a steel cylinder, and its flow is controlled by a gas flow meter.

[0043] The synthesized alkylaluminoxane was used as a cocatalyst to carry out ethylene polymerization experiments to evaluate its activity.

[0044] The main catalyst used in the ethylene polymerization for evaluating the activity of the co-catalyst in this embodiment is zirconocene dichloride, and the polymerization experimental conditions are 0.1MPa and 70°C. The experiment was carried out in a 150mL three-necked flask that was fully dried and fully vacuum-nitrogen replaced. 50mL toluene was added to the three-necked flask as a solvent. When the oil bath temperature reached 70°C, the main catalyst and the co-catalyst were added, the aluminum-zirconium molar ratio was controlled to be 1000, ethylene was introduced for reaction for 30min, and 5mL acidified ethanol was added to the three-necked flask to quench the reaction. The reaction product was filtered, and the separated solid product was placed in a 60°C vacuum oven after washing and dried to constant weight. The catalyst activity was calculated by the dried polyethylene solid.

[0045] For comparison, methylaluminoxane (PMAO-IP) produced by Nouryon was used as a co-catalyst, and other conditions were kept unchanged to compare the catalyst activity. The catalytic activity test of the comparative example PMAO-IP was 702 kg·(mol Zr) -1 ·h -1 .

[0046] Embodiment 1:

[0047] The schematic diagram of this embodiment is as follows Figure 1 As shown, 6.7 mL of 1.5 mol / L trimethylaluminum toluene solution was taken in the glove box, 0.98 g of benzoic acid was taken, and 12.3 mL of refined toluene was used to prepare a solution, which was respectively transported into the reaction system using injection pumps. The flow rate of injection pump S1 was 2 mL / h, and the flow rate of injection pump S2 was 4 mL / h. M1 used a T-type three-way structure micro mixer with an inner diameter of 1.6 mm, and R1 used a tubular reactor with an inner diameter of 1.6 mm. The heating temperature T1 was 70°C, and the average residence time t1 was 2.25 h. The obtained solution was filtered, and the clear liquid was used for ethylene polymerization. The catalytic activity was 666 kg·(mol Zr) -1 ·h -1 .

[0048] Embodiment 2:

[0049] The schematic diagram of this embodiment is as follows Figure 2 As shown, on the basis of Example 1, a flow divider F1 and a micro mixer M2 are added, M2 is a T-type three-way micro mixer with an inner diameter of 1.6 mm, the reflux ratio r1 is 4.0, and the average residence time t2 is 3.6 h. The obtained solution is filtered, and the clear liquid is used for ethylene polymerization, and the catalytic activity is 864 kg·(mol Zr) -1 ·h -1 .

[0050] Embodiment 3:

[0051] The schematic diagram of this embodiment is as follows Figure 3 As shown:

[0052] Step (1): Take 10 mL of 1.5 mol / L trimethylaluminum toluene solution in a glove box, take 2.19 g of benzophenone, and prepare a solution with 27.3 mL of refined toluene, and use injection pumps to transport them into the reaction system respectively. The flow rate of injection pump S1 is 3 mL / h, and the flow rate of injection pump S2 is 9 mL / h. M1 uses a T-type three-way structure micro mixer with an inner diameter of 1.6 mm, R1 uses a tubular reactor with an inner diameter of 1.6 mm, the heating temperature T1 is 70°C, and the average residence time t1 is 0.2 h.

[0053] Step (2): Take 5 mL of a commercial methylaluminoxane toluene dilute solution prepared in advance to 0.15 mol / L, and use a syringe pump S3 to deliver it into the reaction system (the syringe pump S3 is connected to the micro mixer M2). The flow rate of the syringe pump S3 is 1.5 mL / h. When the mixed solution in step (1) enters the micro mixer M2, the syringe pump S3 is turned on. M2 uses a Y-type three-way structure micro mixer with an inner diameter of 1.6 mm, R2 uses a tubular reactor with an inner diameter of 1.6 mm, the heating temperature T2 is 70°C, and the average residence time t2 is 1.8 h. The obtained solution is filtered, and the clear liquid is used for ethylene polymerization. The catalytic activity is 331 kg·(mol Zr) -1 ·h -1 .

[0054] The flow diagrams used in Examples 4 to 11 are as follows: Figure 4 As shown, on the basis of Example 3, a flow splitter F1 and a micro mixer M3 are added.

[0055] Embodiment 4:

[0056] In Example 4, M3 is a Y-type three-way micro mixer with an inner diameter of 1.6 mm, a reflux ratio of 3.0, and an average residence time t3 of 2.6 h. The obtained solution is filtered and the clear liquid is used for ethylene polymerization. The catalytic activity is 1170 kg·(mol Zr) -1 ·h -1 .

[0057] Embodiment 5:

[0058] R1 and R2 in Example 4 were changed to tubular reactors with an inner diameter of 0.8 mm, the heating temperature remained unchanged, and the average residence time t2 was changed to 0.65 h. The catalytic activity of the obtained alkylaluminoxane was 662 kg·(mol Zr) -1 ·h -1 .

[0059] Embodiment 6:

[0060] In this example, only the heating temperature T1 is changed on the basis of Example 4, and the catalytic activities of the alkylaluminoxanes obtained at different heating temperatures T1 are shown in Table 1.

[0061] Table 1

[0062]

[0063] Embodiment 7:

[0064] In this example, only the heating temperature T2 is changed on the basis of Example 4. The catalytic activities of the alkylaluminoxanes obtained at different heating temperatures T2 are shown in Table 2.

[0065] Table 2

[0066]

[0067] Embodiment 8:

[0068] In this example, other conditions were kept unchanged on the basis of Example 4, and the reflux ratio r1 was changed to 10.0. The activity of the obtained alkylaluminoxane was 997 kg·(mol Zr) -1 ·h -1 .

[0069] Embodiment 9:

[0070] Step (1): Take 14 mL of 1.5 mol / L trimethylaluminum toluene solution in a glove box, take 3.28 g of triphenylmethanol, and prepare a solution with 52.2 mL of refined toluene, and use syringe pumps to transport them into the reaction system respectively, with the flow rate of syringe pump S1 being 10 mL / h and the flow rate of syringe pump S2 being 40 mL / h. M1 uses a T-type three-way structure micro mixer with an inner diameter of 1.6 mm, R1 uses a tubular reactor with an inner diameter of 1.6 mm, the heating temperature T1 is 70°C, and the average residence time t1 is 0.1 h.

[0071] Step (2): Take 10.5 mL of a commercial methylaluminoxane toluene dilute solution prepared in advance to 0.1 mol / L, and use a syringe pump to deliver it into the reaction system. The flow rate of the syringe pump S3 is 7.5 mL / h. When the mixed solution in step (1) enters the micro mixer M2, start the syringe pump S3. M2 and M3 use a Y-type three-way structure micro mixer with an inner diameter of 1.6 mm, R2 uses a tubular reactor with an inner diameter of 1.6 mm, the heating temperature T2 is 65°C, the average residence time t2 is 0.6 h, and the reflux ratio r1 is 1.5. The obtained solution is filtered and the clear liquid is used for ethylene polymerization. The catalytic activity is 1496 kg·(mol Zr) -1 ·h -1 .

[0072] Embodiment 10:

[0073] Step (1): Take 20 mL of 1.5 mol / L trimethylaluminum toluene solution in a glove box, take 4.38 g of benzophenone, and prepare a solution with 35 mL of refined toluene, and use injection pumps to transport them into the reaction system respectively, with the flow rate of injection pump S1 being 4 mL / h and the flow rate of injection pump S2 being 8 mL / h. M1 uses a T-type three-way structure micro mixer with an inner diameter of 1.6 mm, R1 uses a tubular reactor with an inner diameter of 1.6 mm, the heating temperature T1 is 60° C., and the average residence time t1 is 0.2 h.

[0074] Step (2): Take 5 mL of a 0.2 mol / L triisobutylaluminum toluene dilute solution prepared in advance, and use a syringe pump to deliver it into the reaction system. The flow rate of the syringe pump S3 is 1 mL / h. When the mixed solution in step (1) enters the micro mixer M2, start the syringe pump S3. M2 and M3 use a Y-type three-way structure micro mixer with an inner diameter of 1.6 mm, R2 uses a tubular reactor with an inner diameter of 1.6 mm, the heating temperature T2 is 60°C, the average residence time t2 is 2.5 h, and the reflux ratio r1 is 5.0. The obtained solution is filtered and the clear liquid is used for ethylene polymerization. The catalytic activity is 1091 kg·(mol Zr) -1 ·h -1 .

[0075] Embodiment 11:

[0076] Step (1): Take 16 mL of 1.5 mol / L trimethylaluminum toluene solution in a glove box, take 3.50 g of benzophenone, and prepare a solution with 36 mL of refined toluene, and use syringe pumps to deliver them into the reaction system respectively, with the flow rate of syringe pump S1 being 8 mL / h and the flow rate of syringe pump S2 being 16 mL / h. M1 uses a Y-type three-way structure micro mixer with an inner diameter of 1.6 mm, R1 uses a tubular reactor with an inner diameter of 1.6 mm, the heating temperature T1 is 60° C., and the average residence time t1 is 0.1 h.

[0077] Step (2): Take 4 mL of a 0.2 mol / L trioctylaluminum toluene dilute solution prepared in advance, and use a syringe pump to deliver it into the reaction system. The flow rate of the syringe pump S3 is 2 mL / h. When the mixed solution in step (1) enters the micro mixer M2, start the syringe pump S3. M2 and M3 use a Y-type three-way structure micro mixer with an inner diameter of 1.6 mm, R2 uses a tubular reactor with an inner diameter of 1.6 mm, the heating temperature T2 is 60°C, the average residence time t2 is 3.9 h, and the reflux ratio r1 is 3.0. The obtained solution is filtered and the clear liquid is used for ethylene polymerization. The catalytic activity is 775 kg·(mol Zr) -1 ·h -1 .

[0078] Embodiment 12:

[0079] The schematic diagram of this embodiment is as follows Figure 5As shown. Take 6.7mL of 1.5mol / L trimethylaluminum toluene solution in the glove box and use a syringe pump to deliver it into the reaction system. The flow rate of the syringe pump S1 is 10mL / h. Carbon dioxide gas is delivered into the reaction system through a pipeline connected to the gas cylinder. A flow meter is set to control the carbon dioxide delivery rate to 0.53g / h. M4 uses a T-type three-way structure micro mixer with an inner diameter of 0.5mm, R1 uses a tubular reactor with an inner diameter of 0.5mm, the heating temperature T3 is 60℃, the reaction pressure P is 1.5MPa, and the average residence time t4 is 0.5h. The obtained solution is filtered and the clear liquid is used for ethylene polymerization. The catalytic activity is 421kg·(mol Zr) -1 ·h -1 .

[0080] The flow diagrams used in Examples 13 to 15 are as follows: Figure 6 As shown, they are all based on Example 12 with the addition of a splitter F1 and a micro-mixer M5.

[0081] Embodiment 13:

[0082] In this embodiment, based on the embodiment 12, the micro mixer M5 is a Y-type three-way structure micro mixer with an inner diameter of 0.5 mm, the reflux ratio is 1.0, and the average residence time t5 is 2.0 h. The obtained solution is filtered and the clear liquid is used for ethylene polymerization. The catalytic activity is 537 kg·(mol Zr) -1 ·h -1 .

[0083] Embodiment 14:

[0084] By changing the reaction pressure P in Example 13, the catalytic activities obtained are shown in Table 3.

[0085] Table 3

[0086]

[0087] Embodiment 15:

[0088] By changing the heating temperature T3 in Example 13, the catalytic activities obtained are shown in Table 4.

[0089] Table 4

[0090]

[0091] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to 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 words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A method for continuously preparing alkylaluminoxane based on a non-hydrolysis process, the method comprising any one of the following methods (1) to (3): Method (1): The injection pump S1 delivers an alkyl aluminum solution, and the injection pump S2 delivers a reactant containing a carbon-oxygen bond or a solution of a reactant containing a carbon-oxygen bond diluted with an inert solvent. The two fluids are fully mixed in a micro mixer M1, and the mixed material is delivered to a micro reactor R1 for heating and reaction to obtain an alkyl aluminum oxane solution. Method (2): The injection pump S1 delivers an alkyl aluminum solution, and the injection pump S2 delivers a reactant containing a carbon-oxygen bond or a reactant solution containing a carbon-oxygen bond diluted with an inert solvent. The two fluids are fully mixed in a micro mixer M1, and the mixed material is delivered to a micro reactor R1 for heating and reaction to obtain an alkyl aluminum oxane precursor solution; the alkyl aluminum oxane precursor solution and the activator delivered by the injection pump S3 are fully mixed in a micro mixer M2, and the mixed material is delivered to a micro reactor R2 for heating and reaction to obtain an alkyl aluminum oxane solution; Method (3): The injection pump S1 delivers the alkyl aluminum solution, and the gas cylinder G1 delivers the gas phase carbon-oxygen bond-containing reactants or the mixed gas of carbon-oxygen bond-containing reactants diluted with an inert gas. The two fluids are fully mixed in the micro mixer M4, and the gas-liquid mixture is delivered to the micro reactor R3 for heating and reaction to obtain an alkyl aluminum oxane solution.

2. The method for preparing alkylaluminoxane by non-hydrolysis method based on continuous flow mode according to claim 1, The method (1) further comprises: A micromixer M2 is provided between the micromixer M1 and the microreactor R1, and the alkylaluminoxane solution obtained in the microreactor R1 is partially refluxed through the splitter F1 and fully mixed with the mixed solution flowing out of the micromixer M1 in the micromixer M2, and then transported back to the microreactor R1 for heating and reaction to obtain an alkylaluminoxane solution; The reflux ratio is 0.1-20; The method (2) further comprises: arranging a micromixer M3 between the micromixer M2 and the microreactor R2, partially refluxing the alkyl aluminoxane solution obtained in the microreactor R2 through the splitter F1, fully mixing the mixed solution with the mixed solution flowing out of the micromixer M2 in the micromixer M3, and then transporting the mixed solution back to the microreactor R2 for heating and reaction, thereby obtaining the alkyl aluminoxane solution; the reflux ratio is 0.1-20; The method (3) further comprises: arranging a micromixer M5 between the micromixer M4 and the microreactor R3, partially refluxing the alkylaluminoxane solution / gas reactant that has not fully reacted in the microreactor R3 through the splitter F1, fully mixing the gas-liquid mixture flowing out of the micromixer M4 in the micromixer M5, and then transporting it back to the microreactor R3 for heating and reaction to obtain an alkylaluminoxane solution; the reflux ratio is 0.1-20.

3. The method for preparing alkylaluminoxane by non-hydrolysis method based on continuous flow mode according to claim 1, characterized in that: The reactant containing a carbon-oxygen bond is one or more of carbon dioxide, carboxylic acid organic compounds, ketone organic compounds, and alcohol organic compounds.

4. The method for preparing alkylaluminoxane by non-hydrolysis method based on continuous flow mode according to claim 1, characterized in that: The alkyl aluminum is selected from one or more of trialkyl aluminum, alkoxy alkyl aluminum, aryl alkyl aluminum, and halogenated alkyl aluminum.

5. The method for preparing alkylaluminoxane by non-hydrolysis method based on continuous flow mode according to claim 1, characterized in that: The activator described in method (2) is selected from one or more of trialkylaluminum, arylalkylaluminum, halogenated alkylaluminum, and alkylaluminoxane; the concentration of the activator before mixing is 0.1-40wt%, and the molar ratio of the activator to the alkylaluminum is 0.001-1.

6. The method for preparing alkylaluminoxane by non-hydrolysis method based on continuous flow mode according to claim 1, characterized in that: The inert solvent is selected from one or more of aliphatic hydrocarbons, aromatic hydrocarbons, and isomeric alkanes, and the inert gas is selected from one or more of helium, argon, and nitrogen.

7. The method for preparing alkylaluminoxane by non-hydrolysis method based on continuous flow mode according to claim 1, characterized in that: The molar ratio of the reactant containing carbon-oxygen bonds to the alkyl aluminum is 0.01-2; the concentration of the alkyl aluminum solution is 1-40wt%, the concentration of the reactant containing carbon-oxygen bonds in the liquid phase is 1-40wt%, and the concentration of the reactant containing carbon-oxygen bonds in the reactant mixed gas is 1-100wt%.

8. The method for preparing alkylaluminoxane by non-hydrolysis method based on continuous flow mode according to claim 1, characterized in that: The volume flow rates of the alkyl aluminum solution, the reactant containing carbon-oxygen bonds, and the activator are all 0.01-5000 mL / min.

9. The method for preparing alkylaluminoxane by non-hydrolysis method based on continuous flow mode according to claim 1, characterized in that: The micromixer M1 described in method (1) is a T-type or Y-type micromixer with an inner diameter of 50-5000 μm, the microreactor R1 is a tubular reactor with an inner diameter of 0.05-100 mm, a length of 0.1-30 m, a reaction temperature of 0-150° C., and an average residence time of 0.01-30 h; The micromixers M1, M2 and M3 described in method (2) are T-type or Y-type micromixers with an inner diameter of 50-5000 μm; the microreactor R1 is a tubular reactor with an inner diameter of 0.05-100 mm, a length of 0.1-30 m, a reaction temperature of 0-150° C. and an average residence time of 0.1-1 h; the microreactor R2 is a tubular reactor with an inner diameter of 0.05-100 mm, a length of 0.1-30 m, a reaction temperature of 30-150° C. and an average residence time of 0.1-100 h.

10. The method for preparing alkylaluminoxane by non-hydrolysis method based on continuous flow mode according to claim 1, characterized in that: The micromixers M4 and M5 described in method (3) are T-type or Y-type micromixers with an inner diameter of 50-5000 μm, the microreactor R3 is a tubular reactor with an inner diameter of 0.01-100 mm, a length of 0.1-30 m, a reaction pressure of 1.0-50 MPa, a reaction temperature of 0-200° C., and an average residence time of 0.1-30 h.

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