Continuous flow process for producing metallocene catalysts

Abstract

The present invention relates to the technical field of catalyst synthesis and discloses a continuous flow production method for metallocene catalysts. The production method involves reacting a cyclopentadienyl compound or an indenyl compound, an organolithium compound, an organosilane, and a chloride as raw materials in a microchannel continuous flow reactor to obtain a metallocene catalyst, and the reaction temperature is -20°C to 60°C. The use of a microchannel continuous flow reactor in the method of the present invention allows the metallocene catalyst to be produced at around room temperature, resulting in mild reaction conditions, improved safety in the chemical synthesis process, shorter reaction times, and improved production efficiency.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of Chinese Patent Application No. 202211610955.X, filed on December 14, 2022, the contents of which are incorporated herein by reference. [Technical Field]

[0002] The present invention relates to the technical field of catalyst synthesis, and in particular to a continuous flow process for the production of metallocene catalysts. [Background technology]

[0003] Polyolefins have the advantages of good mechanical properties, excellent processing characteristics, and stable thermal and chemical properties, and are widely used in various sectors of the national economy, including human daily life, medical hygiene, industry, agriculture, aerospace, and national defense and military. In recent years, the production volume of polyolefin products produced using metallocene catalysts has rapidly increased, and their excellent material properties have dominated the market. Specifically, metallocene polyolefin products include metallocene polyethylene (mPE), metallocene polypropylene (mPP), metallocene syndiotactic polystyrene, metallocene cycloolefin, and polyolefin elastomer (POE).

[0004] Compared with other catalysts, metallocene catalysts have unique properties. Because metallocene catalysts have a single catalytic active center, they can catalyze polymerization, promoting a narrow and uniform molecular weight distribution of the comonomers on the polymer backbone, resulting in uniform polymers synthesized by metallocene catalysts. Furthermore, metallocene catalysts are superior to other catalysts in catalyzing the copolymerization of different monomers.

[0005] Metallocenes have a wide variety of structures, and can produce a variety of polyolefins depending on their structure. Thousands of metallocene catalysts are used to produce metallocene polypropylene, but the structure of the polypropylene produced by each catalyst is different. Even with the same catalyst, different reaction conditions can produce different polypropylene structures. It has been found that the polymerization behavior of metallocene catalyst systems is far richer than that of conventional catalysts, and can produce polyolefins with a greater number of structural types.

[0006] Currently, most metallocene catalysts are obtained by organometallic reactions at low temperatures. The commonly used method for producing metallocene catalysts is as follows: A cyclopentadienyl or indenyl compound is used as a precursor. It is reacted with butyllithium at low temperatures to remove one active hydrogen, followed by reaction with excess dimethyldichlorosilane to obtain a silicon-bridged ligand. The ligand is then dianionized with two equivalents of butyllithium at low temperatures. The desired metallocene catalyst is then reacted with a metal chloride salt, such as titanium tetrachloride, zirconium tetrachloride, or hafnium tetrachloride, at low temperatures. The reaction temperature must be kept low (typically -78°C), and the butyllithium must be added slowly and dropwise. The reaction with the metal chloride salt must also be carried out at a low temperature (typically -78°C). These conditions are not conducive to catalyst scalability, requiring increased energy consumption and longer reaction times. Furthermore, the addition of a large amount of butyllithium to the reaction vessel poses certain risks. Summary of the Invention [Problem to be solved by the invention]

[0007] The objective of the present invention is to solve the problems of the prior art, such as the low production temperature and the safety risks, by realizing the continuous synthesis of metallocene catalysts under milder conditions, and to provide a continuous flow method for producing metallocene catalysts, which is simple to operate, has a safe and controllable synthesis process, is highly versatile, has a good industrial production base, and has promising future applications. [Means for solving the problem]

[0008] In order to achieve the above object, the present invention provides a continuous flow method for producing a metallocene catalyst, comprising reacting a cyclopentadienyl compound or an indenyl compound, an organolithium compound, an organosilane, and a chloride as raw materials in a microchannel continuous flow reactor to obtain a metallocene catalyst, and the reaction temperature is -20°C to 60°C. [Effects of the Invention]

[0009] According to the above technical solutions, the beneficial technical effects obtained by the present invention are as follows:

[0010] The present invention utilizes continuous flow technology to efficiently produce metallocene catalysts. The method of the present invention utilizes a microchannel continuous flow reactor to achieve continuous synthesis of metallocene catalysts under milder conditions, enabling production of metallocene catalysts at near room temperature (-20°C to 60°C). Compared to low-temperature production using a kettle reactor (e.g., -78°C), these milder reaction conditions improve the safety of the chemical synthesis process, reduce manual labor, shorten reaction times, and improve production efficiency. Furthermore, the risk of leakage of flammable or explosive substances such as organolithium (e.g., butyllithium) and organic solvents is avoided, and operator harm due to experiments involving explosives is avoided, improving the safety of the chemical synthesis process. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a flow diagram of a continuous flow synthesis of a silicon-bridged compound ligand according to one embodiment of the present invention. [Figure 2] 1 is a flow diagram of a continuous flow synthesis of a metallocene catalyst according to one embodiment of the present invention. [Figure 3] 1 is a flow diagram of a continuous flow synthesis of silicon-bridged compound ligands according to another embodiment of the present invention. [Figure 4] 2 is a flow diagram of a continuous flow synthesis of a metallocene catalyst according to another embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] The endpoints of ranges and any values disclosed herein are not intended to be limiting to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. In the case of numerical ranges, values between the individual range endpoints, between the individual range endpoints and the individual point values, and between the individual point values can be combined with each other to form one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed herein.

[0013] The present invention provides a continuous flow method for producing a metallocene catalyst, in which a cyclopentadienyl compound or an indenyl compound, an organolithium compound, an organosilane, and a chloride are reacted using a microchannel continuous flow reactor to obtain a metallocene catalyst, and the reaction temperature is -20°C to 60°C, for example, -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 30°C, 40°C, 50°C, 60°C, or any value within a range consisting of any two values, preferably -10 to 30°C.

[0014] In the present invention, a microchannel continuous flow reactor is a compact reaction system, and its piping size is much smaller than that of conventional reactors. The miniaturization of the reaction channel significantly increases the contact area between the channel and the heat exchange medium, improving heat exchange efficiency. The extremely strong turbulence in the microchannel can exponentially increase mass transfer, and the mass transfer enhancement effect is particularly pronounced in heterogeneous reactions. The miniaturization of the reaction channel also benefits direct contact between the reaction media, improving yields. Furthermore, a microchannel continuous flow reactor can realize multi-stage continuous reactions and can be directly scaled up to mass production without pilot testing, offering high safety, controllable production processes, and high reaction selectivity.

[0015] The present invention uses continuous flow technology to achieve efficient production of metallocene catalysts, realize continuous synthesis of metallocene catalysts under milder conditions, reduce manual labor, shorten reaction times, improve production efficiency, and improve the safety of chemical synthesis processes.

[0016] In some embodiments of the present invention, the number of microchannel continuous flow reactors is at least two, for example, two, three, or four.

[0017] In some embodiments of the present invention, the microchannel continuous flow reactor has a channel having a tubular structure, and the diameter of the channel is 0.5 to 10 mm, for example, 0.5 mm, 0.8 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, and any value within a range consisting of any two numerical values, preferably 1 to 8 mm.

[0018] In some embodiments of the present invention, the liquid retention capacity of the microchannel continuous flow reactor is 5 to 200 mL, for example, 5 mL, 10 mL, 15 mL, 20 mL, 30 mL, 40 mL, 50 mL, 60 mL, 70 mL, 80 mL, 100 mL, 150 mL, 180 mL, and any value within a range consisting of any two numerical values, preferably 20 to 150 mL.

[0019] In some embodiments of the present invention, the fluid flow rate in the microchannel reactor is 5 to 40 mL / min, for example, 5 mL / min, 8 mL / min, 10 mL / min, 15 mL / min, 20 mL / min, 30 mL / min, 40 mL / min, and any value within a range consisting of any two numbers, preferably 5 to 20 mL / min.

[0020] In some embodiments of the present invention, the reaction time is less than 30 minutes, for example, 1 minute, 2 minutes, 3 minutes, 5 minutes, 8 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, and any value within a range consisting of any two numbers, preferably 3 to 20 minutes.

[0021] According to the present invention, the diameter, volume and fluid flow rate of the microchannel continuous flow reactor all affect the yield of the metallocene catalyst.

[0022] In some embodiments of the present invention, a backpressure valve is provided at the outlet of the microchannel continuous flow reactor, and the pressure of the backpressure valve is 0.5 MPa or more, for example, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, 3 MPa, or any value within a range consisting of any two numerical values, preferably 0.6 to 2 MPa.

[0023] In the present invention, a back pressure valve is provided at the outlet of the microchannel continuous flow reactor, and the pressure of the back pressure valve is controlled to 0.5 MPa or more, thereby enabling smooth operation even when a lithium salt with poor fluidity is contained.

[0024] In some embodiments of the present invention, there are two microchannel continuous flow reactors, for example, as shown in FIGS. 1 and 2, and the production method specifically includes: The method includes the steps of: carrying out a first reaction between a cyclopentadienyl compound or an indenyl compound and an organolithium I in a microchannel continuous flow reactor I to obtain a first product; further adding an organosilane to carry out a second reaction to obtain a second product, which is separated and purified to obtain a silicon-bridged compound ligand; then carrying out a third reaction between the silicon-bridged compound ligand and an organolithium II in a microchannel continuous flow reactor II to obtain a third product; further adding a chloride to carry out a fourth reaction to obtain a fourth product; and concentrating and crystallizing the fourth product to obtain a metallocene catalyst.

[0025] In the present invention, both the microchannel continuous flow reactor I and the microchannel continuous flow reactor II are channels having a tubular structure, and the diameter of the channel is 0.5 to 10 mm. The liquid retention capacity of the microchannel continuous flow reactor is 5 to 200 mL. The fluid flow rate in the microchannel reactor is 5 to 40 mL / min.

[0026] In the present invention, continuous flow technology is used to produce metallocene catalysts. The use of two microchannel continuous flow reactors allows for continuous microchannel continuous flow reactions. Compared with traditional kettle-type synthesis methods, the present invention has the advantages of milder reaction conditions, near room temperature, safer, faster, more efficient, higher yields, and lower energy consumption, making it suitable for the scale-up of metallocene catalysts.

[0027] In some embodiments of the present invention, the number of microchannel continuous flow reactors is four, and as shown in FIGS. 3 and 4, the manufacturing method specifically includes: Step S1: carrying out a first reaction between a cyclopentadienyl compound or an indenyl compound and an organolithium I in a first microchannel continuous flow reactor A to obtain a first product; Step S2: carrying out a second reaction between the first product and an organosilane in a second microchannel continuous flow reactor B to obtain a second product, which is separated and purified to obtain a silicon-bridged compound ligand; Step S3: carrying out a third reaction between the silicon-bridged compound ligand and organolithium II in a third microchannel continuous flow reactor C to obtain a third product; and step S4 of carrying out a fourth reaction between the third product and chloride in a fourth microchannel continuous flow reactor D to obtain a fourth product, which is concentrated and crystallized to obtain a metallocene catalyst.

[0028] According to the present invention, the silicon bridge compound ligand obtained in step S2 may, in some embodiments, be a precursor of the silicon bridge compound ligand.

[0029] In the present invention, the first microchannel continuous flow reactor A, the second microchannel continuous flow reactor B, the third microchannel continuous flow reactor C, and the fourth microchannel continuous flow reactor D are each a channel having a tubular structure, and the diameter of the channel is 0.5 to 10 mm. The liquid retention capacity of the microchannel continuous flow reactor is 5 to 200 mL. The fluid flow rate in the microchannel reactor is 5 to 40 mL / min.

[0030] In this invention, continuous flow technology is used to produce metallocene catalysts. The use of four microchannel continuous flow reactors allows for continuous microchannel continuous flow reactions. Compared with traditional kettle-type synthesis methods, this invention has the advantages of milder reaction conditions, allowing reactions to be carried out at near room temperature, being safer, faster, and more efficient, with higher yields and lower energy consumption, making it suitable for the scale-up of metallocene catalysts.

[0031] According to the present invention, the number of the microchannel continuous flow reactors may be three, and the production of metallocene catalysts can be achieved by either a combination of Figures 1 and 4 or a combination of Figures 3 and 2.

[0032] In some embodiments of the present invention, the first reaction is carried out at a temperature of -20°C to 60°C, for example, -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 30°C, 40°C, 50°C, 60°C, and any value within a range consisting of any two numerical values, preferably -10 to 30°C, and for a time of 5 to 500 seconds, for example, 8 seconds, 10 seconds, 20 seconds, 50 seconds, 80 seconds, 100 seconds, 150 seconds, 180 seconds, 200 seconds, 220 seconds, 250 seconds, 280 seconds, and any value within a range consisting of any two numerical values, preferably 100 to 500 seconds.

[0033] In some embodiments of the present invention, the second reaction is carried out at a temperature of -20°C to 60°C, for example, -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 30°C, 40°C, 50°C, 60°C, and any value within a range consisting of any two numerical values, preferably -10 to 30°C, and for a time of 5 to 500 seconds, for example, 8 seconds, 10 seconds, 20 seconds, 50 seconds, 80 seconds, 100 seconds, 150 seconds, 180 seconds, 200 seconds, 220 seconds, 250 seconds, 280 seconds, and any value within a range consisting of any two numerical values, preferably 100 to 500 seconds.

[0034] In some embodiments of the present invention, the third reaction is carried out at a temperature of -20°C to 60°C, for example, -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 30°C, 40°C, 50°C, 60°C, and any value within a range consisting of any two numerical values, preferably -10 to 30°C, and for a time of 5 to 500 seconds, for example, 8 seconds, 10 seconds, 20 seconds, 50 seconds, 80 seconds, 100 seconds, 150 seconds, 180 seconds, 200 seconds, 220 seconds, 250 seconds, 280 seconds, and any value within a range consisting of any two numerical values, preferably 100 to 500 seconds.

[0035] In some embodiments of the present invention, the fourth reaction is carried out at a temperature of -20°C to 60°C, for example, -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 30°C, 40°C, 50°C, 60°C, and any value within a range consisting of any two numerical values, preferably -10 to 30°C, and for a time of 5 to 500 seconds, for example, 8 seconds, 10 seconds, 20 seconds, 50 seconds, 80 seconds, 100 seconds, 150 seconds, 180 seconds, 200 seconds, 220 seconds, 250 seconds, 280 seconds, and any value within a range consisting of any two numerical values, preferably 100 to 500 seconds.

[0036] In some embodiments of the present invention, the temperature of the first reaction, the temperature of the second reaction, the temperature of the third reaction, and the temperature of the fourth reaction are each controlled by an external heat exchanger, and a heat exchange medium in the external heat exchanger is thermal oil, water, ice water, ice-brine water, or ethanol.

[0037] Metallocene catalyst production requires the use of flammable and explosive organolithium compounds (e.g., butyllithium), which poses certain risks during scale-up. Microchannel continuous flow reactors have small holding volumes (5 mL to 200 mL), making leaks easy to control and inherently safe. Microchannel continuous flow reactors have large specific surface areas and excellent mass and heat transfer properties, eliminating the need for reactions at -78°C and allowing reactions to proceed smoothly even at temperatures near 0°C, making them particularly suitable for scaling up metallocene catalysts. The small channel size of microchannel continuous flow reactors (0.5 to 10 mm in diameter) allows for sufficient contact between reactants, allowing reactions to be completed in a short time, resulting in high rates and high yields.

[0038] In the present invention, precise control can be achieved by controlling the supply pump.

[0039] In some embodiments of the present invention, the molar ratio of the cyclopentadienyl compound or indenyl compound to the organolithium I is 1:1-3, preferably 1:1-1.1.

[0040] In some embodiments of the present invention, the molar ratio of the first product to the organosilane is 1:0.5-3, preferably 1:0.5-1.1.

[0041] In some embodiments of the present invention, the molar ratio of the silicon-bridged compound ligand to the organolithium II is 1:2-3, preferably 1:2-2.2.

[0042] In some embodiments of the present invention, the molar ratio of the third product to chloride is 1:1 to 1.2, preferably 1:1 to 1.1.

[0043] In some embodiments of the present invention, the cyclopentadienyl compound is tetramethylcyclopentadiene and / or cyclopentadiene.

[0044] In some embodiments of the present invention, the indenyl compound is one or more selected from indene, 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene, and 7-(3',5'-dimethylphenyl)-2-methylindene.

[0045] In some embodiments of the present invention, the organolithium is one or more selected from n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, phenyllithium, hexyllithium, and lithium bis(trimethylsilyl)amide.

[0046] In some embodiments of the present invention, the organosilane is dimethyldichlorosilane and / or diphenyldichlorosilane.

[0047] In some embodiments of the present invention, the chloride is one or more selected from titanium tetrachloride, zirconium tetrachloride, and hafnium tetrachloride.

[0048] In some embodiments of the present invention, in step S1, the cyclopentadienyl compound or indenyl compound is added in the form of a solution, and the solvent used is one or more of benzene, toluene, xylene, tetrahydrofuran, ethyl ether, and an aliphatic hydrocarbon, preferably tetrahydrofuran.

[0049] In some embodiments of the present invention, the material of the microchannel continuous flow reactor is glass, metal and its alloy, ceramic, single crystal silicon, glass coated with an anticorrosion layer on its surface, metal and its alloy coated with an anticorrosion layer on its surface, ceramic coated with an anticorrosion layer on its surface, single crystal silicon coated with an anticorrosion layer on its surface, fluorine-containing resin, or highly crosslinked thermosetting resin.

[0050] The present invention will be described in detail below using examples, but the scope of protection of the present invention is not limited to the following description.

[0051] Unless specific conditions are specified in the following examples and comparative examples, they are carried out according to standard conditions or those suggested by the manufacturer. Unless the manufacturer is specified, the reagents or equipment used are all commercially available standard products.

[0052] Constant flow pump: P230p constant flow pump manufactured by Dalian Yilite Analytical Instrument Co., Ltd. Manufacturing Example 1

[0053] The method for preparing bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane includes the following steps, as shown in FIG. (1) Pretreatment: 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene was dissolved in dry tetrahydrofuran to prepare a 0.62 M solution, which was then placed in a feed bottle. A 2.5 M butyllithium solution and dimethyldichlorosilane were placed in the respective feed bottles for use. Microchannel continuous flow reactor A and microchannel continuous flow reactor B were connected. Both microchannel continuous flow reactors had a diameter of 3.18 mm (1 / 8 inch) and a volume of 50 mL. The backpressure valves at the outlets of the microchannel continuous flow reactors were set to a pressure of at least 0.6 MPa. (2) Operation: The temperatures of both microchannel continuous flow reactors were set to 0°C. Once the reactor temperatures reached the set temperature, the constant flow pump supplying 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene was started at a flow rate of 5 mL / min. The pressure of the first backpressure valve was adjusted to 1.0 MPa, and the pressure of the second backpressure valve was adjusted to 0.6 MPa. After rinsing the lines for 5 minutes, the constant flow pump supplying butyllithium and the constant flow pump supplying dimethyldichlorosilane were started. The flow rates of the constant flow pump supplying butyllithium were set to 1.3 mL / min, and those of the constant flow pump supplying dimethyldichlorosilane were set to 0.15 mL / min. The residence time in each microchannel continuous flow reactor was calculated from the ratio of the retained liquid volume to the volumetric flow rate. The rinsing fluid phase and the initial unstable products were collected in flasks protected by nitrogen gas. (3) Collection of the product: The sample outlet was observed, and when a continuous and stable liquid flow phase was formed and a pale yellow product was observed, the product was collected in another flask protected with nitrogen gas, and the time was recorded. (4) Washing: After collecting the product, the supply of butyllithium and dimethyldichlorosilane was stopped, and the 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene solution was replaced with pure tetrahydrofuran. A large amount of tetrahydrofuran was pumped in to wash the lines for 10 minutes. (5) Work-up: The product was collected, and the solvent and dimethyldichlorosilane were distilled off. The product was recrystallized using ethyl ether to obtain a pale yellow solid. The yield was 76%. Manufacturing Example 2

[0054] Bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane was produced in 81% yield according to the production method of Production Example 1, except that the temperatures of both microchannel continuous flow reactors were set to -20°C. Manufacturing Example 3

[0055] Bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane was produced in 72% yield according to the production method of Production Example 1, except that the temperatures of both microchannel continuous flow reactors were set to 20°C. Production Example 4

[0056] Bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane was produced in 74% yield by following the production method of Production Example 1, except that the flow rate of 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene was set to 10 mL / min, the flow rate of the constant flow pump supplying butyllithium was set to 2.6 mL / min, and the flow rate of the constant flow pump supplying dimethyldichlorosilane was set to 0.3 mL / min. Manufacturing Example 5

[0057] Bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane was produced in two microchannel continuous flow reactors according to the production method of Production Example 1, except that both had a diameter of 6.35 mm and a volume of 50 mL. The yield was 68%. Manufacturing Example 6

[0058] The two microchannel continuous flow reactors each had a diameter of 1.59 mm and a volume of 50 mL, and bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane was produced in a 78% yield according to the production method of Production Example 1. Manufacturing Example 7

[0059] Bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane was produced in two microchannel continuous flow reactors according to the production method of Production Example 1, except that both had a diameter of 3.18 mm and a volume of 25 mL. The yield was 75%. Manufacturing Example 8

[0060] The method for preparing bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane includes the following steps, as shown in FIG. (1) Pretreatment: 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene was dissolved in dry tetrahydrofuran to prepare a 0.62 M solution, which was then placed in a feed bottle. A 2.5 M butyllithium solution and dimethyldichlorosilane were placed in separate feed bottles for use. A 50 mL volume, 3.18 mm (1 / 8 inch) diameter microchannel continuous flow reactor I with an intermediate feed port was used. Dimethyldichlorosilane was continuously fed to the intermediate feed port, and 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene and the butyllithium solution were connected to the end feed ports. (2) Operation: The temperature of microchannel continuous flow reactor I was set to 0°C. Once the reactor temperature reached the set temperature, the constant flow pump supplying 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene was started at a flow rate of 5 mL / min. The backpressure valve was adjusted to 1.0 MPa. After rinsing the lines for 5 minutes, the constant flow pumps supplying butyllithium and dimethyldichlorosilane were started. The flow rates of the constant flow pump supplying butyllithium were set to 1.3 mL / min and 0.15 mL / min, respectively. The residence time in microchannel continuous flow reactor I was determined from the ratio of the retained liquid volume to the volumetric flow rate. The rinsing fluid phase and the initial unstable products were collected in flasks protected with nitrogen gas. (3) Collection of the product: The sample outlet was observed, and when a continuous and stable liquid flow phase was formed and a pale yellow product was observed, the product was collected in another flask protected with nitrogen gas, and the time was recorded. (4) Washing: After collecting the product, the supply of butyllithium and dimethyldichlorosilane was stopped, and the 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene solution was replaced with pure tetrahydrofuran. A large amount of tetrahydrofuran was pumped in to wash the lines for 10 minutes. (5) Work-up: The product was collected, and the solvent and dimethyldichlorosilane were distilled off. The product was recrystallized using ethyl ether to obtain a pale yellow solid. The yield was 72%. Comparative Manufacturing Example 1

[0061] A conventional method for producing bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane includes the following steps: A 100 mL Schlenk reaction flask was prepared, and after replacing the atmosphere with nitrogen gas, 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene (2 mmol) and tetrahydrofuran (10 mL) were added, and stirring was started. n A hexane solution of BuLi (2.4 M, 2.1 mmol) was slowly added dropwise to the reaction flask. After the addition was complete, the mixture was warmed to room temperature and stirred for 2 h. The reaction mixture was then added dropwise to a solution of dichlorodimethylsilane (1 mmol) in tetrahydrofuran (10 mL) at -78 °C. The mixture was warmed to room temperature and stirred for 3 h. The solvent was removed under vacuum, and the crude residue was recrystallized using ethyl ether to give a pale yellow solid. The yield was 51%. Manufacturing Example 9

[0062] The method for producing dimethyl-(tetramethyl-η5-cyclopentadienyl)-monochlorosilane includes the following steps, as shown in FIG. (1) Pretreatment: Tetramethylcyclopentadiene was dissolved in dry tetrahydrofuran to prepare a 0.62 M solution, which was then placed in a raw material bottle. A 2.5 M butyllithium solution and dimethyldichlorosilane were placed in the respective raw material bottles for use. Microchannel continuous flow reactor A and microchannel continuous flow reactor B were connected. Both microchannel continuous flow reactors had a diameter of 3.18 mm and a volume of 50 mL. (2) Operation: The temperatures of both microchannel continuous flow reactors were set to 0°C. Once the reactor temperatures reached the set temperature, the constant flow pump supplying tetramethylcyclopentadiene was started at a flow rate of 5 mL / min. The pressure of the first backpressure valve was adjusted to 1.0 MPa, and the pressure of the second backpressure valve was adjusted to 0.6 MPa. After rinsing the lines for 5 minutes, the constant flow pumps supplying butyllithium and dimethyldichlorosilane were started. The flow rate of the constant flow pump supplying butyllithium was set to 1.3 mL / min, and the flow rate of the constant flow pump supplying dimethyldichlorosilane was set to 0.35 mL / min. The residence time in each microchannel continuous flow reactor was calculated from the ratio of the retained liquid volume to the volumetric flow rate. The rinsing fluid phase and the initial unstable products were collected in flasks protected by nitrogen gas. (3) Collection of the product: The sample outlet was observed, and when a continuous and stable liquid flow phase was formed and a pale yellow product was observed, the product was collected in another flask protected with nitrogen gas. (4) Cleaning: After collecting the product, the supply of butyllithium and dimethyldichlorosilane was stopped, the tetramethylcyclopentadiene solution was replaced with pure tetrahydrofuran, and a large amount of tetrahydrofuran was pumped in to clean the lines for 10 minutes. (5) Post-treatment: The product was collected, and the solvent and dimethyldichlorosilane were distilled off to obtain a pale yellow oily product in 95% yield. Manufacturing Example 10

[0063] Dimethyl-(tetramethyl-η-cyclopentadienyl)-monochlorosilane was produced according to the production method of Production Example 9, except that the temperatures of both microchannel continuous flow reactors were set to -20°C, the flow rate of tetramethylcyclopentadiene was 10 mL / min, the flow rate of the constant flow pump for butyllithium was set to 2.5 mL / min, and the flow rate of the constant flow pump for dimethyldichlorosilane was set to 0.7 mL / min. The yield was 89%. Manufacturing Example 11

[0064] Dimethyl-(tetramethyl-η5-cyclopentadienyl)-monochlorosilane was produced according to the production method of Production Example 9, except that the temperatures of both microchannel continuous flow reactors were set to 20°C, the flow rate of tetramethylcyclopentadiene was 5 mL / min, the flow rate of the constant flow pump for butyllithium was set to 1.3 mL / min, and the flow rate of the constant flow pump for dimethyldichlorosilane was set to 0.35 mL / min. The yield was 84%. Manufacturing Example 12

[0065] Dimethyl-(tetramethyl-η-cyclopentadienyl)-monochlorosilane was produced in two microchannel continuous flow reactors according to the production method of Production Example 9, except that both had a diameter of 1.59 mm and a volume of 50 mL. The yield was 96%. Manufacturing Example 13

[0066] Dimethyl-(tetramethyl-η-cyclopentadienyl)-monochlorosilane was produced in two microchannel continuous flow reactors according to the production method of Production Example 9, except that both had a diameter of 6.35 mm and a volume of 50 mL. The yield was 79%. Manufacturing Example 14

[0067] Dimethyl-(tetramethyl-η-cyclopentadienyl)-monochlorosilane was produced in two microchannel continuous flow reactors according to the production method of Production Example 9, except that both reactors had a diameter of 3.18 mm and a volume of 25 mL. The yield was 80%. Manufacturing Example 15

[0068] Dimethyl-(tetramethyl-η-cyclopentadienyl)-monochlorosilane was produced in two microchannel continuous flow reactors according to the production method of Production Example 9, except that both reactors had a diameter of 3.18 mm and a volume of 100 mL. The yield was 95%. Manufacturing Example 16

[0069] Specifically, the method for producing (tert-butylamino)dimethyl-(tetramethyl-η5-cyclopentadienyl)-silane includes the following steps: A clean, dry, nitrogen-filled three-neck flask was charged with 33 g of dimethyl-(tetramethyl-η5-cyclopentadienyl)-monochlorosilane and 300 mL of THF. Under N2 protection, the flask was cooled to 0 °C. While maintaining the temperature at approximately 0 °C, 34 mL of tBu-NH2 was added dropwise. After the addition of tert-butylamine was complete, the solution was warmed to room temperature and allowed to react for 6 h. The solution turned blue-yellow, and a blue precipitate (tert-butyl hydrochloride) was observed at the bottom. The solution was then filtered under N2 protection, and the blue-yellow filtrate was collected. The filter cake was rinsed with 50 mL of THF, and the filtrate was collected. The remaining THF and excess tert-butylamine were removed from the filtrate in an oil bath at 55 °C, yielding 32 g of a blue-yellow oil. Comparative Manufacturing Example 2

[0070] The conventional method for producing dimethyl-(tetramethyl-η5-cyclopentadienyl)-monochlorosilane includes the following steps: A 100 mL Schlenk reaction flask was prepared. After purging with nitrogen gas, tetramethylcyclopentadiene (1.83 mmol) and tetrahydrofuran (10 mL) were added and stirring was initiated. At -78 °C, a hexane solution of nBuLi (2.4 M, 1.9 mmol) was slowly added dropwise to the reaction flask. After the addition was complete, the temperature was raised to room temperature and stirring was continued for 2 h. The reaction solution was added dropwise to a solution of dichlorodimethylsilane (2.5 mmol) in tetrahydrofuran (10 mL) at -78 °C. The temperature was raised to room temperature and stirring was continued for 3 h. The solvent was removed under vacuum, and the crude residue was extracted with 50 mL of toluene. The solvent was removed, yielding a pale yellow oily product. The yield was 68%. Example 1

[0071] The method for preparing rac-dimethylsilylbis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-zirconium dichloride includes the following steps, as shown in FIG. (1) Pretreatment: Bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane obtained in Production Example 1 was dissolved in dry tetrahydrofuran to prepare a 0.5 M solution, which was then placed in a raw material bottle. A 2.5 M butyllithium solution was placed in a raw material bottle. ZrCl4 (DME) was added to dry toluene to prepare a 2 M solution, which was then placed in a raw material bottle. Microchannel continuous flow reactor C and microchannel continuous flow reactor D were connected. The volume of each of the two microchannel continuous flow reactors was 50 mL. (2) Operation: The temperatures of both microchannel continuous flow reactors were set to 0 °C. Once the reactor temperatures reached the set temperature, the constant flow pump supplying bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane was first started at a flow rate of 5 mL / min. The pressure of the first backpressure valve was adjusted to 1.0 MPa, and the pressure of the second backpressure valve was adjusted to 0.5 MPa. After rinsing the lines for 5 minutes, the constant flow pumps supplying butyllithium and zirconium tetrachloride solution were started. The flow rates of the constant flow pumps supplying butyllithium were set to 2 mL / min, and the flow rate of the constant flow pump supplying zirconium tetrachloride solution was set to 1.25 mL / min. The residence time in each microchannel continuous flow reactor was calculated from the ratio of the retained liquid volume to the volumetric flow rate. The rinsing fluid phase and the initial unstable products were collected in flasks protected by nitrogen gas. (3) Collection of the product: The sample outlet was observed, and when a continuous and stable liquid flow phase was formed and a deep yellow product was observed, the product was collected in another flask protected with nitrogen gas, and the time was recorded. (4) Washing: After collecting the product, the supply of the butyllithium and zirconium tetrachloride solutions was stopped, and the bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane solution was replaced with pure tetrahydrofuran. A large amount of tetrahydrofuran was pumped in to wash the lines for 10 minutes. (5) Work-up: The product was collected, the solvent was distilled off, toluene was added, and the mixture was filtered. The filtrate was concentrated and crystallized to give a pale yellow product in a yield of 79%. Example 2

[0072] rac-Dimethylsilylbis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-zirconium dichloride was produced in 82% yield according to the production method of Example 1, except that the temperatures of both microchannel continuous flow reactors were set to -20°C. Example 3

[0073] rac-Dimethylsilylbis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-zirconium dichloride was produced in 74% yield according to the production method of Example 1, except that the temperatures of both microchannel continuous flow reactors were set at 20°C. Example 4

[0074] The two microchannel continuous flow reactors, each with a diameter of 6.35 mm and a volume of 50 mL, were used to produce rac-dimethylsilylbis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-zirconium dichloride in a 68% yield, according to the method of Example 1. Example 5

[0075] The two microchannel continuous flow reactors, each with a diameter of 1.59 mm and a volume of 50 mL, were used to produce rac-dimethylsilylbis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-zirconium dichloride in accordance with the preparation method of Example 1. The yield was 78%. Example 6

[0076] Two microchannel continuous flow reactors were used to produce rac-dimethylsilylbis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-zirconium dichloride in accordance with the preparation method of Example 1, except that each reactor had a diameter of 3.18 mm and a volume of 25 mL. The yield was 75%. Example 7

[0077] rac-Dimethylsilylbis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-titanium dichloride was produced in 76% yield according to the production method of Example 1, except that the zirconium tetrachloride solution was replaced with a titanium tetrachloride solution. Example 8

[0078] rac-Dimethylsilylbis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-hafnium dichloride was produced in 82% yield according to the production method of Example 1, except that the zirconium tetrachloride solution was replaced with a hafnium tetrachloride solution. Example 9

[0079] The method for producing (tert-butylamino)dimethyl-(tetramethyl-η5-cyclopentadienyl)-silanetitanium dichloride includes the following steps, as shown in FIG. (1) Pretreatment: (tert-Butylamino)dimethyl-(tetramethyl-η5-cyclopentadienyl)-silane produced by the production method of Production Example 16 was dissolved in dry tetrahydrofuran to prepare a 0.5 M solution, which was then placed in the raw material bottle. A 2.5 M butyllithium solution was placed in the raw material bottle. Titanium tetrachloride was dissolved in dry toluene to prepare a 2 M solution, which was then placed in the raw material bottle. Microchannel continuous flow reactor C and microchannel continuous flow reactor D were connected. Both microchannel continuous flow reactors had a diameter of 3.18 mm, and the volume of each of the two microchannel continuous flow reactors was 50 mL. (2) Operation: The temperatures of both microchannel continuous flow reactors were set to 0 °C. Once the reactor temperatures reached the set temperature, the constant flow pump supplying (tert-butylamino)dimethyl-(tetramethyl-η5-cyclopentadienyl)-silane was first started at a flow rate of 5 mL / min. The pressure of the first backpressure valve was adjusted to 1.0 MPa, and the pressure of the second backpressure valve was adjusted to 0.5 MPa. After rinsing the lines for 5 minutes, the constant flow pumps supplying butyllithium and titanium tetrachloride solution were started. The flow rates of the constant flow pumps supplying butyllithium were set to 2 mL / min, and those of the constant flow pumps supplying titanium tetrachloride solution were set to 1.25 mL / min. The residence time in each microchannel continuous flow reactor was calculated from the ratio of the retained liquid volume to the volumetric flow rate. The rinsing fluid phase and the initial unstable products were collected in flasks protected by nitrogen gas. (3) Collection of the product: The sample outlet was observed, and when a continuous and stable liquid flow phase was formed and a deep yellow product was observed, the product was collected in another flask protected with nitrogen gas, and the time was recorded. (4) Cleaning: After collecting the product, the supply of butyllithium and titanium tetrachloride solutions was stopped, and the (tert-butylamino)dimethyl-(tetramethyl-η5-cyclopentadienyl)-silane solution was replaced with pure tetrahydrofuran. A large amount of tetrahydrofuran was pumped in to clean the lines for 10 min. (5) Work-up: The product was collected, the solvent was distilled off, toluene was added, and the mixture was filtered. The filtrate was concentrated and crystallized to obtain a yellow product in a yield of 75%. Example 10

[0080] (tert-Butylamino)dimethyl-(tetramethyl-η-cyclopentadienyl)-silanetitanium dichloride was produced according to the production method of Example 9, except that the temperatures of both microchannel continuous flow reactors were set to -20°C, the flow rate of (tert-butylamino)dimethyl-(tetramethyl-η-cyclopentadienyl)-silane was 10 mL / min, the flow rate of the constant flow pump for supplying butyllithium was set to 4 mL / min, and the flow rate of the constant flow pump for supplying titanium tetrachloride was set to 2.5 mL / min. The yield was 82%. Example 11

[0081] (tert-Butylamino)dimethyl-(tetramethyl-η-cyclopentadienyl)-silanetitanium dichloride was produced in accordance with the production method of Example 9, except that the temperature of the first microchannel continuous flow reactor was set to -20°C, the temperature of the second microchannel continuous flow reactor was set to 20°C, the flow rate of (tert-butylamino)dimethyl-(tetramethyl-η-cyclopentadienyl)-silane was 10 mL / min, the flow rate of the constant flow pump for supplying butyllithium was set to 4 mL / min, and the flow rate of the constant flow pump for supplying titanium tetrachloride was set to 2.5 mL / min. The yield was 85%. Example 12

[0082] (tert-Butylamino)dimethyl-(tetramethyl-η-cyclopentadienyl)-silanetitanium dichloride was produced in 81% yield by the same method as in Example 9, except that the temperature of the first microchannel continuous flow reactor was set to -20°C, the temperature of the second microchannel continuous flow reactor was set to 40°C, the flow rate of (tert-butylamino)dimethyl-(tetramethyl-η-cyclopentadienyl)-silane was 10 mL / min, the flow rate of the constant flow pump for butyllithium was 4 mL / min, and the flow rate of the constant flow pump for titanium tetrachloride was 2.5 mL / min. Example 13

[0083] The two microchannel continuous flow reactors each had a diameter of 1.59 mm and a volume of 50 mL, and were used to produce (tert-butylamino)dimethyl-(tetramethyl-η-cyclopentadienyl)-silanetitanium dichloride in accordance with the preparation method of Example 9. The yield was 76%. Example 14

[0084] (tert-butylamino)dimethyl-(tetramethyl-η-cyclopentadienyl)-silanetitanium dichloride was produced in 71% yield using two microchannel continuous flow reactors, each with a diameter of 6.35 mm and a volume of 50 mL, in accordance with the production method of Example 9. Example 15

[0085] (tert-butylamino)dimethyl-(tetramethyl-η-cyclopentadienyl)-silanetitanium dichloride was produced in 69% yield using two microchannel continuous flow reactors, each with a diameter of 3.18 mm and a volume of 25 mL, in accordance with the production method of Example 9. Example 16

[0086] The two microchannel continuous flow reactors were used to produce (tert-butylamino)dimethyl-(tetramethyl-η-cyclopentadienyl)-silanetitanium dichloride in accordance with the preparation method of Example 9, except that each reactor had a diameter of 3.18 mm and a volume of 75 mL. The yield was 75%. Example 17

[0087] The method for producing rac-dimethylsilylbis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-zirconium dichloride includes the following steps, as shown in FIG. (1) Pretreatment: Bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane obtained in Preparation Example 8 was dissolved in dry tetrahydrofuran to prepare a 0.5 M solution, which was then placed in the feed bottle. A 2.5 M butyllithium solution was placed in the feed bottle. ZrCl4(DME) was added to dry toluene to prepare a 2 M solution, which was then placed in the feed bottle. A 50 mL microchannel continuous flow reactor II with an intermediate feed port was used. ZrCl4(DME) was connected to the intermediate feed port. Bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane and the butyllithium solution were connected to the end feed ports. (2) Operation: The temperature of the microchannel continuous flow reactor II was set to 0°C. Once the reactor temperature reached the set point, the constant flow pump supplying bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane was first started at a flow rate of 5 mL / min. The backpressure valve was adjusted to 1.0 MPa. After rinsing the lines for 5 minutes, the constant flow pumps supplying butyllithium and zirconium tetrachloride solution were started. The flow rates of the constant flow pumps supplying butyllithium were set to 2 mL / min, and those of the constant flow pumps supplying zirconium tetrachloride solution were set to 1.25 mL / min. The residence time in the microchannel continuous flow reactor was determined by the ratio of the retained liquid volume to the volumetric flow rate. The rinsing fluid phase and the initial unstable products were collected in flasks protected by nitrogen gas. (3) Collection of the product: The sample outlet was observed, and when a continuous and stable liquid flow phase was formed and a deep yellow product was observed, the product was collected in another flask protected with nitrogen gas, and the time was recorded. (4) Washing: After collecting the product, the supply of the butyllithium and zirconium tetrachloride solutions was stopped, and the bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane solution was replaced with pure tetrahydrofuran. A large amount of tetrahydrofuran was pumped in to wash the lines for 10 minutes. (5) Work-up: The product was collected, the solvent was distilled off, toluene was added, and the mixture was filtered. The filtrate was concentrated and crystallized to give a pale yellow product in a yield of 76%. Comparative Example 1

[0088] A method for preparing rac-dimethylsilylbis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-zirconium dichloride, comprising the following steps: A 100 mL Schlenk reaction flask was prepared. After purging with nitrogen gas, bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene]-dimethylsilane (2 mmol) obtained in Comparative Example 1 and tetrahydrofuran (10 mL) were added and stirring was initiated. At -78 °C, a 2.4 M n-BuLi hexane solution (4.4 mmol) was slowly added dropwise to the reaction flask. After the addition was complete, the temperature was raised to room temperature and stirring was continued for 2 h. The reaction system was then cooled to -78 °C, ZrCl (2 mmol) was added, the temperature was raised to room temperature and stirring was continued for 2 h. The solvent was then distilled off, toluene was added, and the mixture was filtered. The filtrate was concentrated and crystallized to obtain a yellow product. The yield was 41%. From the above results, it can be seen that the examples of the present invention are characterized by mild reaction conditions, short reaction times, high safety, and obviously superior efficacy. Application example 1

[0089] This application example provides a method for preparing propylene-ethylene copolymerization using the catalyst rac-dimethylsilylbis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-zirconium dichloride prepared in Example 1, which specifically includes the following steps: Under anhydrous and oxygen-free conditions, 1000 mL of toluene and 1000 μmol of methylaluminoxane (Zr:Al = 1:500) were added to a reactor, heated to 150 °C, and 2 μmol of the catalyst rac-dimethylsilylbis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene]-zirconium dichloride was dissolved in 10 mL of toluene. A propylene-ethylene mixed gas (propylene mass content: 93%) was introduced into the reactor, and the mixed gas pressure was adjusted to 1 MPa. The propylene-ethylene copolymerization reaction was carried out at 150 °C for 30 min. After quenching, the polymerization was terminated with 5% by mass of HCl-acidified ethanol. After stirring for 0.5 h, the mixture was filtered, washed three times with ethanol, and vacuum dried at 70 °C for 12 h to obtain a propylene-ethylene polymer. In this application example, the catalytic activity of the catalyst rac-dimethylsilylbis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-zirconium dichloride is 2.1 × 10 7 g / [mol(Zr)·h], and the produced propylene ethylene polymer has a weight average molecular weight of 63 kg / mol, a molecular weight distribution index of 2.7, an ethylene content (mass) of 15%, a glass transition temperature of the copolymer of -31°C, and a melting point of 97°C. Application example 2

[0090] This application example provides a method for preparing copolymerization of ethylene and octene by using the catalyst (tert-butylamino)dimethyl-(tetramethyl-η5-cyclopentadienyl)-silanetitanium dichloride prepared in Example 9 at a high temperature of 150°C, which specifically includes the following steps: Under anhydrous and oxygen-free conditions, 1000 mL of toluene, 300 mL of 1-octene, and 1000 μmol of methylaluminoxane (Ti:Al = 1:500) were added to a reaction vessel, and the temperature was raised to 150°C. 2 μmol of the catalyst (tert-butylamino)dimethyl-(tetramethyl-η5-cyclopentadienyl)-silanetitanium dichloride dissolved in 10 mL of toluene was then pushed into the reaction vessel with ethylene. The ethylene pressure was adjusted to 2 MPa, and the copolymerization reaction of ethylene and 1-octene was carried out at 150°C for 30 min. After quenching the reaction, the polymerization was terminated with 5% by mass of hydrochloric acid-acidified ethanol. After stirring for 0.5 hours, the mixture was filtered, and the filter cake was washed three times with ethanol and dried in vacuo at 70°C for 12 hours to obtain an ethylene-octene copolymer.

[0091] In this application example, the catalytic activity of (tert-butylamino)dimethyl-(tetramethyl-η5-cyclopentadienyl)-silanetitanium dichloride is 2.4 × 10 7 g / [mol(Ti)·h], and the produced ethylene-octene copolymer has a weight average molecular weight of 63 kg / mol, a molecular weight distribution index of 2.5, a glass transition temperature of -52°C, and a melting temperature of 65°C.

[0092] Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including combining each technical feature in other appropriate ways, and these simple modifications and combinations should also be considered as the content disclosed in the present invention, and all fall within the protection scope of the present invention.

Claims

1. 1. A continuous flow process for producing a metallocene catalyst, comprising: A continuous flow production method for a metallocene catalyst, comprising reacting a cyclopentadienyl compound or an indenyl compound, an organolithium compound, an organosilane, and a chloride as raw materials in a microchannel continuous flow reactor to obtain a metallocene catalyst, wherein the reaction temperature is between -20°C and 60°C.

2. the microchannel continuous flow reactor is at least two; The method according to claim 1, wherein the microchannel continuous flow reactor is preferably a channel having a tubular structure, and the diameter of the channel is 0.5 to 10 mm.

3. The method according to claim 1 or 2, wherein the microchannel continuous flow reactor has a liquid retention capacity of 5 to 200 mL.

4. The method according to any one of claims 1 to 3, wherein the fluid flow rate in the microchannel reactor is 5 to 40 mL / min.

5. The method according to any one of claims 1 to 4, wherein the reaction time is less than 30 minutes.

6. The method according to any one of claims 1 to 5, wherein a back pressure valve is provided at an outlet of the microchannel continuous flow reactor, and the pressure of the back pressure valve is 0.5 MPa or more, preferably 0.6 to 2 MPa.

7. The number of microchannel continuous flow reactors is two, and the manufacturing method specifically includes:

7. The method according to claim 1, comprising the steps of: carrying out a first reaction of a cyclopentadienyl compound or an indenyl compound with organolithium I in a microchannel continuous flow reactor I to obtain a first product; adding an organosilane to carry out a second reaction to obtain a second product, which is separated and purified to obtain a silicon-bridged compound ligand; then carrying out a third reaction of the silicon-bridged compound ligand with organolithium II in a microchannel continuous flow reactor II to obtain a third product; adding a chloride to carry out a fourth reaction to obtain a fourth product; and concentrating and crystallizing the fourth product to obtain the metallocene catalyst.

8. The number of the microchannel continuous flow reactors is four, and the production method specifically includes: Step S1: carrying out a first reaction between a cyclopentadienyl compound or an indenyl compound and an organolithium I in a first microchannel continuous flow reactor to obtain a first product; Step S2: carrying out a second reaction between the first product and an organosilane in a second microchannel continuous flow reactor to obtain a second product, which is separated and purified to obtain a silicon-bridged compound ligand; Step S3: carrying out a third reaction between the silicon-bridged compound ligand and organolithium II in a third microchannel continuous flow reactor to obtain a third product; and step S4 of carrying out a fourth reaction between the third product and a chloride in a fourth microchannel continuous flow reactor to obtain a fourth product, which is concentrated and crystallized to obtain a metallocene catalyst.

9. The first reaction is carried out at a temperature of −20° C. to 60° C. for a time of 5 to 500 seconds, and / or the second reaction is carried out at a temperature of −20° C. to 60° C. for a time of 5 to 500 seconds; and / or the third reaction is carried out at a temperature of −20° C. to 60° C. for a time of 5 to 500 seconds; And / or, the fourth reaction is carried out at a temperature of −20° C. to 60° C. for 5 to 500 seconds.

10. the molar ratio of the cyclopentadienyl compound or indenyl compound to the organolithium I is 1:1 to 3, preferably 1:1 to 1.1; And / or the molar ratio of the first product to the organosilane is 1:0.5-3, preferably 1:0.5-1.

1.

11. the molar ratio of the silicon-bridged compound ligand to the organolithium II is 1:2-3, preferably 1:2-2.2; And / or the molar ratio of the third product to chloride is 1:1-1.2, preferably 1:1-1.

1.

12. the cyclopentadienyl compound is tetramethylcyclopentadiene and / or cyclopentadiene; and / or the indenyl compound is one or more selected from indene, 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene, and 7-(3',5'-dimethylphenyl)-2-methylindene; And / or the organolithium is one or more selected from n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, phenyllithium, hexyllithium, and lithium bis(trimethylsilyl)amide.

13. the organosilane is dimethyldichlorosilane and / or diphenyldichlorosilane; And / or the chloride is one or more selected from titanium tetrachloride, zirconium tetrachloride, and hafnium tetrachloride, the manufacturing method according to any one of claims 1 to 12.

14. 14. The process according to any one of claims 1 to 13, wherein the cyclopentadienyl or indenyl compound is added in the form of a solution, and the solvent used is one or more of benzene, toluene, xylene, tetrahydrofuran, ethyl ether, and aliphatic hydrocarbons, preferably tetrahydrofuran.

15. The method according to any one of claims 1 to 14, wherein the material of the microchannel continuous flow reactor is glass, metal and its alloy, ceramic, single crystal silicon, glass coated with an anticorrosion layer on its surface, metal and its alloy coated with an anticorrosion layer on its surface, ceramic coated with an anticorrosion layer on its surface, single crystal silicon coated with an anticorrosion layer on its surface, fluorine-containing resin, or highly crosslinked thermosetting resin.

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