Continuous flow preparation method for metallocene catalyst

Abstract

The present invention relates to the technical field of catalyst synthesis, and in particular, to a continuous flow preparation method for a metallocene catalyst. The method uses a cyclopentadienyl compound or an indenyl compound, organic lithium, organosilane, and chloride as the starting materials for a reaction in a micro-channel continuous flow reactor to give the metallocene catalyst, wherein the temperature of the reaction is -20 °C to 60 °C. By means of using a micro-channel continuous flow reactor, the method can prepare the metallocene catalyst around room temperature with mild reaction conditions, thereby improving the safety of the chemical synthesis process, shortening the reaction time, and improving the production efficiency.

Description

[0003] Polyolefins have the advantages of desirable mechanical properties, excellent processability, and stable thermal and chemical properties, and are widely used in the daily life of humans, medical care and public health, industrial and agricultural industries, aerospace, national defense and military, and other areas of the national economy. In recent years, the output of polyolefin products fabricated by using a metallocene catalyst has rapidly increased and occupied the market by virtue of their excellent material characteristics. Specifically, the metallocene polyolefin products include metallocene polyethylene (mPE), metallocene polypropylene (mPP), metallocene syndiotactic polystyrene, metallocene cycloolefins, polyolefin elastomers (POE), and the like.

[0004] The metallocene catalyst has unique properties and characteristics compared to the other catalysts. Since the metallocene catalyst has a single catalytically active center, it can promote the narrow and uniform distribution of comonomer molecular weight on the polymer backbone during the catalytic synthesis process, it determines that the catalytically synthesized polymer has desirable uniformity. In addition, the metallocene catalyst has superior excellence than other catalysts in the aspect of catalyzing copolymerization of different monomers.

[0005] Metallocenes have a rich structure and can produce different polyolefins depending on the various structures. There are more than 1,000 metallocene catalysts for producing metallocene polypropylene, but the polypropylene produced with each catalyst has different structures. The structures of polypropylenes prepared with the same catalyst under different reaction conditions are not completely identical. As can be seen, the polymerization behaviors of the metallocene catalyst system are much more plentiful than the traditional catalysts, thus the polyolefins with more structural types can be generated.

[0006] At present, a majority of the metallocene catalysts have been prepared through a low-temperature metal-organic reaction. A conventional method for preparing a metallocene catalyst is as follows: a cyclopentadienyl or indenyl compound is used as a precursor, which is subjected to a reaction at a low temperature with butyl lithium to remove an active hydrogen atom and reacts with an excessive amount of dimethyl dichlorosilane to obtain a ligand with silicon bridge; the ligand is subjected to the dianioning with the twice equivalent amount of butyl lithium at a low temperature, then the ligand reacts with a metal chloride salt (e.g., titanium tetrachloride / zirconium tetrachloride / hafnium tetrachloride) at a low temperature to obtain the target metallocene catalyst. In the above reactions, it is necessary to control the reaction to be performed at a low temperature (usually -78°C), to perform slowly during the process of dropwise adding butyl lithium; and to control the reaction with the metal chloride salt to be performed at a low temperature (usually -78°C). The conditions are disadvantageous for the scaled-up process of the catalyst, which requires high energy consumption and a long reaction time. Moreover, there are some risks in the reaction kettle, because a large amount of butyl lithium is added to the reaction kettle. SUMMARY

[0007] The present disclosure aims to overcome the defects in the prior art concerning the low preparation temperatures and safety risks and provides a continuous preparation method for preparing a metallocene catalyst, the method realizes a continuous synthesis of a metallocene catalyst under the more moderate reaction conditions, it has the advantages such as simple operation, safe and controllable synthetic process, and strong universality, thereby exhibiting the desirable industrial production base and broad application prospects.

[0008] To achieve the above object, the present disclosure provides a continuous flow method for preparing a metallocene catalyst, the preparation method uses a cyclopentadienyl compound or an indenyl compound, organic lithium, organosilane, and chloride as the starting materials for a reaction in a micro-channel continuous flow reactor to prepare the metallocene catalyst, wherein the temperature of the reaction is from -20°C to 60°C.

[0009] Due to the technical scheme, the present disclosure produces the favorable technical effects as follows:

[0010] The present disclosure uses continuous flow techniques for the efficient production of the metallocene catalyst. The method in the present disclosure uses a micro-channel continuous flow reactor, on the one hand, the continuous synthesis of the metallocene catalyst is achieved under moderate reaction conditions, and the preparation of the metallocene catalyst is achieved only in the vicinity of room temperature (from -20°C to 60°C), the reaction conditions are milder than those of the low-temperature preparation (e.g., -78°C) of the reaction kettle, thus the safety of the chemical synthesis process is improved, the human involvement is reduced, the reaction time is shortened, and the production efficiency is increased; on the other hand, the leakage risk of organic lithium (butyl lithium), organic solvents, and other flammable and explosive materials is avoided, and the threats of the experiments with an explosion risk on the operation staff are avoided, and the safety of the chemical synthesis process is enhanced. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] FIG. 1 is a flow chart illustrating a continuous flow synthesis of the ligand with silicon bridge provided by an embodiment of the present disclosure;

[0012] FIG. 2 is a flow chart illustrating a continuous flow synthesis of the metallocene catalyst provided by an embodiment of the present disclosure;

[0013] FIG. 3 is a flow chart illustrating a continuous flow synthesis of the ligand with silicon bridge provided by another embodiment of the present disclosure;

[0014] FIG. 4 is a flow chart illustrating a continuous flow synthesis of the metallocene catalyst provided by another embodiment of the present disclosure. DETAILED DESCRIPTION

[0015] The terminals and any value of the ranges disclosed herein are not limited to the precise ranges or values, such ranges or values shall be comprehended as comprising the values adjacent to the ranges or values. As for numerical ranges, the endpoint values of the various ranges, the endpoint values and the individual point values of the various ranges, and the individual point values may be combined with one another to produce one or more new numerical ranges, which should be deemed to have been specifically disclosed herein.

[0016] The present disclosure provides a continuous flow method for preparing a metallocene catalyst comprising using a cyclopentadienyl compound or an indenyl compound, organic lithium, organosilane, and chloride as the starting materials for a reaction in a micro-channel continuous flow reactor to prepare the metallocene catalyst, wherein the temperature of the reaction is from -20°C to 60°C, such as -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 a random value within the range consisting of any two numerical values, preferably from -10°C to 30°C.

[0017] In the present disclosure, the micro-channel continuous flow reactor is a small reaction system with a much smaller pipe size than the conventional reactors, the miniaturization of the reaction channel may significantly increase the contact area between the channels and the heat exchange medium, and improve the heat exchange efficiency. The extremely strong turbulence process inside the micro-channel can exponentially increase the mass transfer efficiency, especially for heterogeneous reactions, where the increased mass transfer efficiency is more obvious. The miniaturization of the reaction channel can also increase the yield by facilitating the direct contact of the reaction media. In addition, the micro-channel continuous flow reactor can be used for the multi-step continuous reaction, thus the mass production can be easily implemented by directly scaling up without the need for pilot scale experiment, thus the reactor has the advantages of high safety, controllable production process, and high reaction selectivity.

[0018] The present disclosure uses the continuous flow techniques for the efficient production of the metallocene catalyst, achieves continuous synthesis of the metallocene catalyst under more moderate reaction conditions, reduces the human involvement, shortens the reaction time, improves the production efficiency, and enhances the safety of the chemical synthesis process.

[0019] In some embodiments of the present disclosure, the number of the micro-channel continuous flow reactors is at least 2; for example 2, 3, or 4.

[0020] In some embodiments of the present disclosure, the micro-channel continuous flow reactor is a channel having a tubular structure, and the channel has a diameter within the range of 0.5-10mm, such as 0.5mm, 0.8mm, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, and a random value within the range consisting of any two numerical values, preferably within the range of l-8mm.

[0021] In some embodiments of the present disclosure, the micro-channel continuous flow reactor has a liquid holdup within the range of 5-200mL, such as 5mL, 10mL, 15mL, 20mL, 30mL, 40mL, 50mL, 60mL, 70mL, 80mL, 100mL, 150mL, 180mL, and a random value within the range consisting of any two numerical values, preferably within the range of 20-150mL.

[0022] In some embodiments of the present disclosure, the flow rate of fluid in the micro-channel reactor is within the range of 5-40mL / min, for example, 5mL / min, 8mL / min, lOmL / min, 15mL / min, 20mL / min, 30mL / min, 40mL / min, and a random value within the range consisting of any two numerical values, preferably within the range of 5-20mL / min.

[0023] In some embodiments of the present disclosure, the reaction time is not greater than 30 min, such as Imin, 2min, 3min, 5min, 8min, lOmin, 15min, 20min, 25min, 30min, and a random value within the range consisting of any two numerical values, preferably within the range of 3-20min.

[0024] According to the present disclosure, the diameter, volume, and fluid flow rate of the micro-channel continuous flow reactor affect the yield of the metallocene catalyst.

[0025] In some embodiments of the present disclosure, a back pressure valve is provided at an outlet of the micro-channel continuous flow reactor, the pressure of the back pressure valve is larger than or equal to 0.5MPa, such as 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, IMPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, and a random value within the range consisting of any two numerical values, preferably within the range of 0.6-2MPa.

[0026] The present disclosure provides a back pressure valve at an outlet of the micro-channel continuous flow reactor and controls that the pressure of the back pressure valve is larger than or equal to 0.5MPa so that a lithium salt having poor fluidity can be smoothly operated.

[0027] In some embodiments of the present disclosure, the number of the micro-channel continuous flow reactors is 2, as shown in FIG. 1 and FIG. 2, the method specifically comprises the following steps:

[0028] Subjecting a cyclopentadienyl compound or an indenyl compound to a first reaction with organic lithium I in a micro-channel continuous flow reactor I to obtain a first product; further adding an organosilane to carry out a second reaction to obtain a second product, separating and purifying the second product to obtain a ligand with silicon bridge; subsequently subjecting the ligand with silicon bridge to a third reaction with an organic lithium II in a micro-channel continuous flow reactor II to obtain a third product; further adding chloride to perform a fourth reaction to obtain a fourth product; concentrating and crystallizing the fourth product to prepare a metallocene catalyst.

[0029] In the present disclosure, each of the micro-channel continuous flow reactor I and the micro-channel continuous flow reactor II is a channel having a tubular structure, and the channel has a diameter within the range of 0.5-10mm, wherein the micro-channel continuous flow reactor has a liquid holdup within the range of 5-200mL, the flow rate of fluid in the micro-channel reactor is within the range of 5-40mL / min.

[0030] The present disclosure adopts continuous flow technology to prepare the metallocene catalyst and uses two micro-channel continuous flow reactors to realize the continuous operation of the micro-channel continuous flow reaction. Compared with the traditional kettle-type synthesis method, the reaction conditions of the present disclosure are milder and can carry out the reaction under conditions close to room temperature, the present disclosure has the advantages such as safe operation, fast and efficient reaction, high yield, and low energy consumption, it is suitable for the scaled-up preparation of the metallocene catalyst.

[0031] In some embodiments of the present disclosure, the number of the micro-channel continuous flow reactors is 4, as shown in FIG. 3 and FIG. 4, the method specifically comprises the following steps:

[0032] SI: subjecting a cyclopentadienyl compound or an indenyl compound to a first reaction with organic lithium I in a first micro-channel continuous flow reactor I to obtain a first product;

[0033] S2: subjecting the first product to a second reaction B with an organosilane in a second micro-channel continuous flow reactor to obtain a second product, separating and purifying the second product to obtain a ligand with silicon bridge;

[0034] S3: subjecting the ligand with silicon bridge to a third reaction with an organic lithium II in a third micro-channel continuous flow reactor C to obtain a third product;

[0035] S4: subjecting the third product to a fourth reaction with chloride in a fourth micro-channel continuous flow reactor D to obtain a fourth product; concentrating and crystallizing the fourth product to prepare a metallocene catalyst.

[0036] According to the present disclosure, the ligand with silicon bridge obtained in step S2 can also be a precursor of the ligand with silicon bridge in some embodiments.

[0037] In the present disclosure, each of the first micro-channel continuous flow reactor A, the second micro-channel continuous flow reactor B, the third micro-channel continuous flow reactor C, and the fourth micro-channel continuous flow reactor D is a channel having a tubular structure, and the channel has a diameter within the range of 0.5-10mm, wherein the micro-channel continuous flow reactor has a liquid holdup within the range of 5-200mL, the flow rate of fluid in the micro-channel reactor is within the range of 5-40mL / min.

[0038] The present disclosure adopts continuous flow technology to prepare the metallocene catalyst and uses four micro-channel continuous flow reactors to realize the continuous operation of the micro-channel continuous flow reaction. Compared with the traditional kettle-type synthesis method, the reaction conditions of the present disclosure are milder and can carry out the reaction under conditions close to room temperature, the present disclosure has the advantages such as safe operation, fast and efficient reaction, high yield, and low energy consumption, it is suitable for the scaled-up preparation of the metallocene catalyst.

[0039] According to the present disclosure, the number of the micro-channel continuous flow reactors can also be 3, for example, the combination of FIG. 1 and FIG. 4, or the combination of FIG. 3 and FIG. 2, can be used for preparing the metallocene catalyst.

[0040] In some embodiments of the present disclosure, the first reaction is performed at a temperature range from -20°C to 60°C, such as -20°C, -15°C, -I0°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 30°C, 40°C, 50°C, 60°C, and a random value within the range consisting of any two numerical values, preferably a temperature range from -10°C to 30°C; the reaction time is within the range of 5-500s, such as 8s, 10s, 20s, 50s, 80s, 100s, 150s, 180s, 200s, 220s, 250s, 280s, and a random value within the range consisting of any two numerical values, preferably within the range of 100-500s.

[0041] In some embodiments of the present disclosure, the second reaction is performed at a temperature range from -20°C to 60°C, such as -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 a random value within the range consisting of any two numerical values, preferably a temperature range from -10°C to 30°C; the reaction time is within the range of 5-500s, such as 8s, 10s, 20s, 50s, 80s, 100s, 150s, 180s, 200s, 220s, 250s, 280s, and a random value within the range consisting of any two numerical values, preferably within the range of 100-500s.

[0042] In some embodiments of the present disclosure, the third reaction is performed at a temperature range from -20°C to 60°C, such as -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 a random value within the range consisting of any two numerical values, preferably a temperature range from -10°C to 30°C; the reaction time is within the range of 5-500s, such as 8s, 10s, 20s, 50s, 80s, 100s, 150s, 180s, 200s, 220s, 250s, 280s, and a random value within the range consisting of any two numerical values, preferably within the range of 100-500S.

[0043] In some embodiments of the present disclosure, the fourth reaction is performed at a temperature range from -20°C to 60°C, such as -20°C, -15°C, -I0°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 30°C, 40°C, 50°C, 60°C, and a random value within the range consisting of any two numerical values, preferably a temperature range from -10°C to 30°C; the reaction time is within the range of 5-500s, such as 8s, 10s, 20s, 50s, 80s, 100s, 150s, 180s, 200s, 220s, 250s, 280s, and a random value within the range consisting of any two numerical values, preferably within the range of 100-500s.

[0044] In some embodiments of the present disclosure, 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 controlled by an external heat exchanger respectively, wherein the heat exchange medium in the external heat exchanger is a heat transfer oil, water, icy wanter, ice brine, or ethanol.

[0045] Preparation of the metallocene catalyst requires the use of organic lithium (e.g., butyl lithium), which is flammable and explosive, and has certain risks during the scaled-up preparation process. Since the micro-channel continuous flow reactor has a small liquid holdup (from 5mL to 200mL), it is easy to control the liquid even if the liquid leakage occurs, thus the reactor has an intrinsic safety. Since the micro-channel continuous flow reactor has a large specific surface area and excellent mass and heat transfer characteristics, the reactor does not need to carry out the reaction at the temperature of -78°C and can be run smoothly at the temperature of around 0°C, especially useful for the scaled-up preparation of the metallocene catalyst. Due to the miniaturization of the channel size of the micro-channel continuous flow reactor, the channel has a diameter within the range of 0.5-10mm, such that the reaction starting materials can contact sufficiently, and completely react in a short time, the reaction has the advantages of short reaction time and high yield.

[0046] The present disclosure allows for the precise control of the reaction process through the control of feed pumps.

[0047] In some embodiments of the present disclosure, the molar ratio of the cyclopentadienyl compound or the indenyl compound to the organic lithium I is 1: (1-3), preferably 1: (1-1.1).

[0048] In some embodiments of the present disclosure, the molar ratio of the first product to the organosilane is 1: (0.5-3), preferably 1: (0.5-1.1).

[0049] In some embodiments of the present disclosure, the molar ratio of the ligand with silicon bridge to the organic lithium II is 1: (2-3), preferably 1: (2-2.2).

[0050] In some embodiments of the present disclosure, the molar ratio of the third product to chloride is 1: (1-1.2), preferably 1: (1-1.1).

[0051] In some embodiments of the present disclosure, the cyclopentadienyl compound is tetramethyl cyclopentadiene and / or cyclopentadiene.

[0052] In some embodiments of the present disclosure, the indenyl compound is one or more selected from the group consisting of indene, 7-(3',5'-dimethylphenyl)-4-m ethoxy-2 -methylindene, and 7-(3',5'-dimethylphenyl)-2-m ethylindene.

[0053] In some embodiments of the present disclosure, the organic lithium is one or more selected from the group consisting of n-butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium, phenyl lithium, hexyl lithium, and di(trimethylsilyl) lithium amide.

[0054] In some embodiments of the present disclosure, the organosilane is dimethyl dichlorosilane and / or diphenyl dichlorosilane.

[0055] In some embodiments of the present disclosure, the chloride is one or more selected from the group consisting of titanium tetrachloride, zirconium tetrachloride, and hafnium tetrachloride.

[0056] In some embodiments of the present disclosure, the cyclopentadienyl compound or indenyl compound in step SI is added in the form of a solution, of which the solvent used is one or more of benzene, toluene, xylene, tetrahydrofuran, diethyl ether, and an aliphatic hydrocarbon, preferably tetrahydrofuran.

[0057] In some embodiments of the present disclosure, the micro-channel continuous flow reactor is made of glass, metal and alloy thereof, ceramic, single-crystal silicon, glass with an anti-corrosion coating on the surface, metal and alloy thereof with an anti-corrosion coating on the surface, ceramic with an anti-corrosion coating on the surface, single-crystal silicon with an anti-corrosion coating on the surface, fluorine-containing resin, or highly cross-linked thermosetting resin, respectively.

[0058] The present disclosure will be described in detail below with reference to examples, but the protection scopes of the present disclosure are not limited by the following description.

[0059] If the specific conditions are not indicated in the following examples and comparative examples, the reactions are performed according to the conventional conditions or the conditions suggested by the manufacturers. If the manufacturers of the reagent or instrument are not specified, both the reagent and the instrument pertain to the commercially available conventional products.

[0060] Constant flow pump: the type P230p constant flow pump manufactured by the Dalian Elite Analytical Instruments Co., Ltd.

[0061] Preparation Example 1

[0062] The method of preparing bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dim ethylsilane, as shown in FIG. 3, comprising the following steps:

[0063] (1) Pre-treatment: 7-(3',5'-dimethylphenyl)-4-m ethoxy-2 -methylindene was dissolved in dry tetrahydrofuran and prepared into a 0.62M solution placed in a starting material bottle; 2.5M butyl lithium solution and dimethyl dichlorosilane were taken and placed in their starting material bottles ready for use. The micro-channel continuous flow reactor A was connected with the micro-channel continuous flow reactor B, both the micro-channel continuous flow reactor A and the micro-channel continuous flow reactor B had a diameter of 3.18 mm (1 / 8 inch) and a volume of 50mL, and the pressure of a back pressure valve provided at an outlet of the micro-channel continuous flow reactor was at least 0.6MPa.

[0064] (2) Operation: the temperature of both micro-channel continuous flow reactors was set to 0°C. After the temperature of the reactors reached the set temperature, the constant flow pump for feeding 7-(3',5'-dimethylphenyl)-4-m ethoxy-2-methylindene was initially powered on for feeding at a flow rate of 5mL / min, the pressure reading of the first back pressure valve was adjusted to 1 .OMPa, the pressure reading of the second back pressure valve was adjusted to 0.6MPa, after the pipeline was washed for 5 min, both the constant flow pump for feeding butyl lithium and the constant flow pump for feeding dimethyl dichlorosilane were switched on, the flow rate of the constant flow pump for feeding butyl lithium was set to 1.3mL / min, the flow rate of the constant flow pump for feeding dimethyl dichlorosilane was set to 0.15mL / min. The residence time of each micro-channel continuous flow reactor can be obtained based on the ratio of the liquid holdup volume to the volume flow rate. The mobile phase used for washing and the initial unstable state product was collected with a nitrogen gas-protected flask.

[0065] (3) Collecting products: the sample outlet was observed, when a continuous and stable liquid mobile phase was formed, and a light yellow product was present, the product was switched to another nitrogen gas-protected flask for collection, and the time was recorded.

[0066] (4) Washing: after collection of the product, the feeding of butyl lithium and dimethyl dichlorosilane was stopped, and the 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene solution was replaced with the pure tetrahydrofuran, a large amount of tetrahydrofuran was pumped into the pipeline for washing for lOmin.

[0067] (5) Post-treatment: the product was collected, the solvent and dimethyl dichlorosilane were removed by distillation, and ether was used for recrystallizing the product to obtain a pale yellow solid with a yield of 76%.

[0068] Preparation Example 2

[0069] The bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dim ethylsilane was prepared according to the preparation method of Preparation Example 1, except that the temperature of the two micro-channel continuous flow reactors was set to -20°C, the yield was 81%.

[0070] Preparation Example 3

[0071] The bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane was prepared according to the preparation method of Preparation Example 1, except that the temperature of the two micro-channel continuous flow reactors was set to 20°C, the yield was 72%.

[0072] Preparation Example 4

[0073] The bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane was prepared according to the preparation method of Preparation Example 1, except that the flow rate of 7-(3',5'-dimethylphenyl)-4-m ethoxy-2 -methylindene was set to lOmL / min, the flow rate of the constant flow pump for feeding butyl lithium was set to 2.6mL / min, and the flow rate of the constant flow pump for feeding dimethyl dichlorosilane was set to 0.3mL / min. The yield was 74%.

[0074] Preparation Example 5

[0075] The bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dim ethylsilane was prepared according to the preparation method of Preparation Example 1, except that the two micro-channel continuous flow reactors both had a diameter of 6.35mm and a volume of 50mL. The yield was 68%.

[0076] Preparation Example 6

[0077] The bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dimethylsilane was prepared according to the preparation method of Preparation Example 1, except that the two micro-channel continuous flow reactors both had a diameter of 1.59mm and a volume of 50mL. The yield was 78%.

[0078] Preparation Example 7

[0079] The bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dim ethylsilane was prepared according to the preparation method of Preparation Example 1, except that the two micro-channel continuous flow reactors both had a diameter of 3.18mm and a volume of 25mL. The yield was 75%.

[0080] Preparation Example 8

[0081] The method of preparing bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dim ethylsilane, as shown in FIG. 1, comprising the following steps:

[0082] (1) Pre-treatment: 7-(3',5'-dimethylphenyl)-4-m ethoxy-2 -methylindene was dissolved in dry tetrahydrofuran and prepared into a 0.62M solution placed in a starting material bottle; 2.5M butyl lithium solution and dimethyl dichlorosilane were taken and placed in their starting material bottles ready for use. A micro-channel continuous flow reactor I with an intermediate feed inlet was used, the micro-channel continuous flow reactor had a diameter of 3.18 mm (1 / 8 inch) and a volume of 50mL, Dimethyl dichlorosilane was connected to the intermediate feed inlet; both the 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene solution and the butyl lithium solution were connected with the tenninal feed inlet.

[0083] (2) Operation: the temperature of the micro-channel continuous flow reactor I was set to 0°C. After the temperature of the reactor reached the set temperature, the constant flow pump for feeding 7-(3',5'-dimethylphenyl)-4-m ethoxy-2 -methylindene was initially powered on for feeding at a flow rate of 5mL / min, the pressure reading of the first back pressure valve was adjusted to 1 .OMPa, the pressure reading of the second back pressure valve was adjusted to l.OMPa, after the pipeline was washed for 5 min, both the constant flow pump for feeding butyl lithium and the constant flow pump for feeding dimethyl dichlorosilane were switched on, the flow rate of the constant flow pump for feeding butyl lithium was set to 1.3mL / min, the flow rate of the constant flow pump for feeding dimethyl dichlorosilane was set to 0.15mL / min. The residence time of the micro-channel continuous flow reactor 1 can be obtained based on the ratio of the liquid holdup volume to the volume flow rate. The mobile phase used for washing and the initial unstable state product was collected with a nitrogen gas-protected flask.

[0084] (3) Collecting products: the sample outlet was observed, when a continuous and stable liquid mobile phase was formed, and a light yellow product was present, the product was switched to another nitrogen gas-protected flask for collection, and the time was recorded.

[0085] (4) Washing: after collection of the product, the feeding of butyl lithium and dimethyl dichlorosilane was stopped, and the 7-(3',5'-dimethylphenyl)-4-m ethoxy-2 -methylindene solution was replaced with the pure tetrahydrofuran, a large amount of tetrahydrofuran was pumped into the pipeline for washing for lOmin.

[0086] (5) Post-treatment: the product was collected, the solvent and dimethyl dichlorosilane were removed by distillation, and ether was used for recrystallizing the product to obtain a pale yellow solid, the yield was 72%.

[0087] Preparation Comparative Example 1

[0088] The conventional method of preparing bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dim ethylsilane comprising the following steps:

[0089] 100 mL Schlenk reaction flask was taken and the air contained in the flask was replaced with nitrogen gas, 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene (2mmol), and tetrahydrofuran (10mL) were then added, a stirring process was started. n-BuLi hexane solution (2.4M, 2.1mmol) was slowly and dropwise added to the reaction flask at the temperature of -78°C, after the adding process was complete, the flask was heated to room temperature, and the stirring was continued for 2h. The reaction solution was dropwise added to di chlorodimethylsilane (Immol) tetrahydrofuran (10mL) solution at the temperature of -78°C. The flask was heated to room temperature and stirred for 3h, the solvent was removed under vacuum, and the crude residue was recrystallized using ether to produce a pale yellow solid, the yield was 51%.

[0090] Preparation Example 9

[0091] The method of preparing dimethyl-(tetramethyl-r|5-cyclopentadienyl)-monochlorosilane, as shown as shown in FIG. 3, comprising the following steps:

[0092] (1) Pre-treatment: tetramethyl cyclopentadiene was dissolved in dry tetrahydrofuran and prepared into a 0.62M solution placed in a starting material bottle; 2.5M butyl lithium solution and dimethyl dichlorosilane were taken and placed in their starting material bottles ready for use. The micro-channel continuous flow reactor A was connected with the micro-channel continuous flow reactor B, both of the micro-channel continuous flow reactors had a diameter of 3.18 mm and a volume of 50mL

[0093] (2) Operation: the temperature of both micro-channel continuous flow reactors was set to 0°C. After the temperature of the reactors reached the set temperature, the constant flow pump for feeding tetramethyl cyclopentadiene was initially powered on for feeding at a flow rate of 5mL / min, the pressure reading of the first back pressure valve was adjusted to l.OMPa, the pressure reading of the second back pressure valve was adjusted to 0.6MPa, after the pipeline was washed for 5 min, both the constant flow pump for feeding butyl lithium and the constant flow pump for feeding dimethyl dichlorosilane were switched on, the flow rate of the constant flow pump for feeding butyl lithium was set to 1.3mL / min, the flow rate of the constant flow pump for feeding dimethyl di chlorosilane was set to 0.35mL / min. The residence time of each micro-channel continuous flow reactor can be obtained based on the ratio of the liquid holdup volume to the volume flow rate. The mobile phase used for washing and the initial unstable state product was collected with a nitrogen gas-protected flask.

[0094] (3) Collecting products: the sample outlet was observed, when a continuous and stable liquid mobile phase was formed, and a light yellow product was present, the product was switched to another nitrogen gas-protected flask for collection.

[0095] (4) Washing: after collection of the product, the feeding of butyl lithium and dimethyl dichlorosilane was stopped, and the tetramethyl cyclopentadiene solution was replaced with the pure tetrahydrofuran, a large amount of tetrahydrofuran was pumped into the pipeline for washing for lOmin.

[0096] (5) Post-treatment: the product was collected, the solvent and dimethyl dichlorosilane were removed by distillation, and ether was used for recrystallizing the product to obtain a pale yellow solid with a yield of 95%.

[0097] Preparation Example 10

[0098] The dimethyl-(tetramethyl-r|5-cyclopentadienyl) -monochlorosilane was prepared according to the method in Preparation Example 9, except that the temperature of the two micro-channel continuous flow reactors was set to -20°C, the flow rate of the constant flow pump for feeding tetramethyl cyclopentadiene was lOmL / min, the flow rate of the constant flow pump for feeding butyl lithium was 2.5mL / min, and the flow rate of the constant flow pump for feeding dimethyl dichlorosilane was set to 0.7mL / min. The yield was 89%.

[0099] Preparation Example 11

[00100] The dimethyl-(tetramethyl-i]5-cyclopentadienyl)- monochlorosilane was prepared according to the method in Preparation Example 9, except that the temperature of the two micro-channel continuous flow reactors was set to 20°C, the flow rate of the constant flow pump for feeding tetramethyl cyclopentadiene was 5mL / min, the flow rate of the constant flow pump for feeding butyl lithium was L3mL / min. and the flow rate of the constant flow pump for feeding dimethyl dichlorosilane was set to 0.35mL / min. The yield was 84%.

[00101] Preparation Example 12

[00102] The dimethyl-(tetramethyl-T|5-cyclopentadienyl)- monochlorosilane was prepared according to the method in Preparation Example 9, except that the two micro-channel continuous flow reactors both had a diameter of 1.59mm and a volume of 50mL. The yield was 96%.

[00103] Preparation Example 13

[00104] The dimethyl-(tetramethyl-i]5-cyclopentadienyl)- monochlorosilane was prepared according to the method in Preparation Example 9, except that the two micro-channel continuous flow reactors both had a diameter of 6.35mm and a volume of 50mL. The yield was 79%.

[00105] Preparation Example 14

[00106] The dimethyl-(tetramethyl-T|5-cyclopentadienyl)- monochlorosilane was prepared according to the method in Preparation Example 9, except that the two micro-channel continuous flow reactors both had a diameter of 3.18mm and a volume of 25mL. The yield was 80%.

[00107] Preparation Example 15

[00108] The dimethyl-(tetramethyl-r|5-cyclopentadienyl)- monochlorosilane was prepared according to the method in Preparation Example 9, except that the two micro-channel continuous flow reactors both had a diameter of 3.18mm and a volume of 100mL. The yield was 95%.

[00109] Preparation Example 16

[00110] The method of preparing (tert-butylamino)dimethyl-(tetramethyl-r|5-cyclopentadienyl)-silane specifically comprising the following steps:

[00111] 33g of dimethyl-(tetramethyl-r|5-cyclopentadienyl)- monochlorosilane and 300mL of tetrahydrofuran (THF) were added to a clean, dry, and nitrogen-filled three-port bottle, the three-port bottle was cooled to 0°C under the N2 protection, and the temperature was maintained at about 0°C, 34 mL of tBu-NH2 was dropwise added. After the dropwise addition of tertiary butylamine was completed, the solution was heated to room temperature and subjected to the reaction for 6h, the reaction was then complete. The solution exhibited a bluish-yellow color, and a layer of cyan precipitate (tert-butyl hydrochloride) was presented at the bottom. The solution was then filtered under N2 protection. The bluish-yellow filtrate was collected. The residue was rinsed with 50mL THF, and the filtrate was further collected. All the filtrates were placed in an oil bath pan at 55°C to remove the THF and the redundant tert-butyl amine, the bluish-yellow oily substance was obtained, and the output was 32g.

[00112] Preparation Comparative Example 2

[00113] The conventional method of preparing dimethyl-(tetram ethyl -T|5-cyclopentadienyl)-monochlorosilane comprising the following steps:

[00114] 100 mL Schlenk reaction flask was taken and the air contained in the flask was replaced with nitrogen gas, tetramethyl cyclopentadiene (1.83mmol) and tetrahydrofuran (10mL) were then added, and a stirring process was started. n-BuLi hexane solution (2.4M, 1.9mmol) was slowly and drop wise added to the reaction flask at the temperature of -78°C, after the adding process was complete, the flask was heated to room temperature, and the stirring was continued for 2h. The reaction solution was dropwise added to di chlorodimethylsilane (2.5mmol) tetrahydrofuran (10mL) solution at the temperature of -78°C. The flask was heated to room temperature and stirred for 3h, the solvent was removed under vacuum, and the crude residue was extracted by using toluene to remove the solvent, a pale yellow oily substance was produced, and the yield was 68%.

[00115] Example 1

[00116] The method of preparing rac-dimethylsilyl-bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene )]-zirconium dichloride, as shown in FIG. 4, comprising the following steps:

[00117] (1) Pre-treatment: the bis[4-(3',5'-dimethylphenyl)-7- methoxy-2-methylindene)]-dimethylsilane obtained from Preparation Example 1 was dissolved in dry tetrahydrofuran and prepared into a 0.5M solution placed in a starting material bottle; 2.5M butyl lithium solution was taken and placed in its starting material bottle. ZrCU (DME) was dissolved in dry toluene and prepared into a 2M solution placed in a starting material bottle. The micro-channel continuous flow reactor C and the micro-channel continuous flow reactor D were connected, both of the two micro-channel continuous flow reactors had a volume of 50mL.

[00118] (2) Operation: the temperature of both micro-channel continuous flow reactors was set to 0°C. After the temperature of the reactors reached the set temperature, the constant flow pump for feeding bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dim ethylsilane was initially powered on for feeding at a flow rate of 5mL / min, the pressure reading of the first back pressure valve was adjusted to 1 .OMPa, the pressure reading of the second back pressure valve was adjusted to 0.5MPa, after the pipeline was washed for 5 min, both the constant flow pump for feeding butyl lithium and the constant flow pump for feeding zirconium tetrachloride were switched on, the flow rate of the constant flow pump for feeding butyl lithium was set to 2mL / min, the flow rate of the constant flow pump for feeding zirconium tetrachloride was set to 1.25mL / min. The residence time of each micro-channel continuous flow reactor can be obtained based on the ratio of the liquid holdup volume to the volume flow rate. The mobile phase used for washing and the initial unstable state product was collected with a nitrogen gas-protected flask.

[00119] (3) Collecting products: the sample outlet was observed, when a continuous and stable liquid mobile phase was formed, and a dark yellow product was present, the product was switched to another nitrogen gas-protected flask for collection, and the time was recorded.

[00120] (4) Washing: after collection of the product, the feeding of butyl lithium and zirconium tetrachloride was stopped, and the bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dim ethylsilane solution was replaced with the pure tetrahydrofuran, a large amount of tetrahydrofuran was pumped into the pipeline for washing for lOmin.

[00121] (5) Post-treatment: the product was collected, the solvent was removed by distillation, toluene was added for filtering, and the filtrate was concentrated and crystallized to obtain a pale yellow product, the yield was 76%.

[00122] Example 2

[00123] The rac-dimethylsilyl-bis[4-(3',5'-dimethylphenyl)-7- methoxy-2-methylindene)]-zirconium dichloride was prepared according to the method of Example 1, except that the temperature of the two micro-channel continuous flow reactors was set to -20°C, the yield was 82%.

[00124] Example 3

[00125] The rac-dimethylsilyl-bis[4-(3',5'-dimethylphenyl)-7- methoxy-2-methylindene)]-zirconium dichloride was prepared according to the method of Example 1, except that the temperature of the two micro-channel continuous flow reactors was set to 20°C, the yield was 74%.

[00126] Example 4

[00127] The rac-dimethylsilyl-bis[4-(3',5'-dimethylphenyl)-7- methoxy-2-methylindene)]-zirconium dichloride was prepared according to the method of Example 1, except that the two micro-channel continuous flow reactors both had a diameter of 6.35mm and a volume of 50mL. The yield was 68%.

[00128] Example 5

[00129] The rac-dimethylsilyl-bis[4-(3',5'-dimethylphenyl)-7- methoxy-2-methylindene)]-zirconium dichloride was prepared according to the method of Example 1, except that the two micro-channel continuous flow reactors both had a diameter of 1,59mm and a volume of 50mL. The yield was 78%.

[00130] Example 6

[00131] The rac-dimethylsilyl-bis[4-(3',5'-dimethylphenyl)-7- methoxy-2-m ethylindene)]-zirconium dichloride was prepared according to the method of Example 1, except that the two micro-channel continuous flow reactors both had a diameter of 3.18mm and a volume of 25mL. The yield was 75%.

[00132] Example 7

[00133] The rac-dimethylsilyl-bis[4-(3',5'-dimethylphenyl)-7- methoxy-2-m ethylindene)]- titanium di chloride was prepared according to the method of Example 1, except that the zirconium tetrachloride solution was replaced by titanium tetrachloride solution. The yield was 76%.

[00134] Example 8

[00135] The rac-dimethylsilyl-bis[4-(3',5'-dimethylphenyl)-7- methoxy-2-methylindene)]-hafnium di chloride was prepared according to the method of Example 1, except that the zirconium tetrachloride solution was replaced by hafnium tetrachloride solution. The yield was 82%.

[00136] Example 9

[00137] The method of preparing (tert-butylamino)dimethyl-(tetramethyl-r|5-cyclopentadienyl)-silane titanium dichloride, as shown in FIG. 4, comprising the following steps:

[00138] (1) Pre-treatment: the (tert-butylamino)dimethyl- (tetramethyl-i]5-cyclopentadienyl)-silane produced with the method of Preparation Example 16 was dissolved in dry tetrahydrofuran and prepared into a 0.5M solution placed in a starting material bottle; 2.5M butyl lithium solution was taken and placed in its starting material bottle. Titanium tetrachloride was dissolved in dry toluene and prepared into a 2M solution placed in a starting material bottle. The micro-channel continuous flow reactor C and the micro-channel continuous flow reactor D were connected, both of the two micro-channel continuous flow reactors had a diameter of 3.18mm and a volume of 50mL.

[00139] (2) Operation: the temperature of both micro-channel continuous flow reactors was set to 0°C. After the temperature of the reactors reached the set temperature, the constant flow pump for feeding (tert-butylamino)dimethyl-(tetramethyl-r|5-cyclopentadienyl)-silane was initially powered on for feeding at a flow rate of 5mL / min, the pressure reading of the first back pressure valve was adjusted to l.OMPa, the pressure reading of the second back pressure valve was adjusted to 0.5MPa, after the pipeline was washed for 5 min, both the constant flow pump for feeding butyl lithium and the constant flow pump for feeding titanium tetrachloride were switched on, the flow rate of the constant flow pump for feeding butyl lithium was set to 2mL / min, the flow rate of the constant flow pump for feeding titanium tetrachloride was set to 1.25mL / min. The residence time of each micro-channel continuous flow reactor can be obtained based on the ratio of the liquid holdup volume to the volume flow rate. The mobile phase used for washing and the initial unstable state product was collected with a nitrogen gas-protected flask.

[00140] (3) Collecting products: the sample outlet was observed, when a continuous and stable liquid mobile phase was formed, and a dark yellow product was present, the product was switched to another nitrogen gas-protected flask for collection, and the time was recorded.

[00141] (4) Washing: after collection of the product, the feeding of the butyl lithium solution and titanium tetrachloride solution was stopped, and the (tert-butylamino)dimethyl-(tetramethyl-r|5- cyclopentadienyl)-silane solution was replaced with the pure tetrahydrofuran, a large amount of tetrahydrofuran was pumped into the pipeline for washing for lOmin.

[00142] (5) Post-treatment: the product was collected, the solvent was removed by distillation, toluene was added for filtering, the filtrate was concentrated and crystallized to obtain a yellow product, the yield was 75%.

[00143] Example 10

[00144] The (tert-butylamino)dimethyl-(tetramethyl-r|5- cyclopentadienyl)-silane titanium dichloride was prepared with the method according to Example 9, except that the temperature of both micro-channel continuous flow reactors was set to -20°C, the flow rate for feeding (tert-butylamino)dimethyl-(tetramethyl-r|5- cyclopentadienyl)-silane was lOmL / min, the flow rate of the constant flow pump for feeding butyl lithium feed flow rate was set to 4mL / min, the flow rate of the constant flow pump for feeding titanium tetrachloride was set to 2.5mL / min. The yield was 82%.

[00145] Example 11

[00146] The (tert-butylamino)dimethyl- (tetramethyl-r|5-cyclopentadienyl)-silane titanium dichloride was prepared with the method according to Example 9, except that the temperature of the first micro-channel continuous flow reactors was set to -20°C, the temperature of the second micro-channel continuous flow reactors was set to 20°C, the flow rate for feeding (tert-butylamino)dimethyl-(tetramethyl-r|5-cyclopentadienyl)-silane was lOmL / min, the flow rate of the constant flow pump for feeding butyl lithium feed flow rate was set to 4mL / min, the flow rate of the constant flow pump for feeding titanium tetrachloride was set to 2.5mL / min. The yield was 85%.

[00147] Example 12

[00148] The (tert-butylamino)dimethyl- (tetramethyl-i]5-cyclopentadienyl)-silane titanium dichloride was prepared with the method according to Example 9, except that the temperature of the first micro-channel continuous flow reactors was set to -20°C, the temperature of the second micro-channel continuous flow reactors was set to 40 °C, the flow rate for feeding (tert-butylamino)dimethyl-(tetramethyl-r|5-cyclopentadienyl)-silane was lOmL / min, the flow rate of the constant flow pump for feeding butyl lithium feed flow rate was set to 4mL / min, the flow rate of the constant flow pump for feeding titanium tetrachloride was set to 2.5mL / min. The yield was 81%.

[00149] Example 13

[00150] The (tert-butylamino)dimethyl- (tetramethyl-i|5-cyclopentadienyl)-silane titanium dichloride was prepared with the method according to Example 9, except that the two micro-channel continuous flow reactors both had a diameter of 1.59mm and a volume of 50mL. The yield was 76%.

[00151] Example 14

[00152] The (tert-butylamino)dimethyl- (tetramethyl-i]5-cyclopentadienyl)-silane titanium dichloride was prepared with the method according to Example 9, except that the two micro-channel continuous flow reactors both had a diameter of 6.35mm and a volume of 50mL. The yield was 71%.

[00153] Example 15

[00154] The (tert-butyl amino)dimethyl- (tetramethyl-T|5-cyclopentadienyl)-silane titanium dichloride was prepared with the method according to Example 9, except that the two micro-channel continuous flow reactors both had a diameter of 3.18mm and a volume of 25mL. The yield was 69%.

[00155] Example 16

[00156] The (tert-butylamino)dimethyl- (tetramethyl-r|5-cyclopentadienyl)-silane titanium dichloride was prepared with the method according to Example 9, except that the two micro-channel continuous flow reactors both had a diameter of 3.18mm and a volume of 75mL. The yield was 75%.

[00157] Example 17

[00158] The method of preparing rac-dimethylsilyl-bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene )]-zirconium dichloride, as shown in FIG. 2, comprising the following steps:

[00159] (1) Pre-treatment: the bis[4-(3',5'-dimethylphenyl)-7- methoxy-2-methylindene)]-dimethylsilane obtained from Preparation Example 8 was dissolved in dry tetrahydrofuran and prepared into a 0.5M solution placed in a starting material bottle; 2.5M butyl lithium solution was taken and placed in its starting material bottle. ZrCl^DME) was dissolved in dry toluene and prepared into a 2M solution placed in a starting material bottle. A micro-channel continuous flow reactor II with an intermediate feed inlet was used, the micro-channel continuous flow reactor II had a volume of 50mL, ZrCU (DME) was connected to the intermediate feed inlet; both the bis[4-(3',5'-dimethylphenyl)-7- methoxy-2-methylindene)] dimethylsilane solution and the butyl lithium solution were connected with the terminal feed inlet.

[00160] (2) Operation: the temperature of the micro-channel continuous flow reactor II was set to 0°C. After the temperature of the reactor reached the set temperature, the constant flow pump for feeding bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dim ethylsilane was initially powered on for feeding at a flow rate of 5mL / min, the pressure reading of the back pressure valve was adjusted to 1 .OMPa, after the pipeline was washed for 5 min, both the constant flow pump for feeding butyl lithium and the constant flow pump for feeding zirconium tetrachloride were switched on, the flow rate of the constant flow pump for feeding butyl lithium was set to 2mL / min, the flow rate of the constant flow pump for feeding zirconium tetrachloride was set to 1.25mL / min. The residence time of each micro-channel continuous flow reactor can be obtained based on the ratio of the liquid holdup volume to the volume flow rate. The mobile phase used for washing and the initial unstable state product was collected with a nitrogen gas-protected flask.

[00161] (3) Collecting products: the sample outlet was observed, when a continuous and stable liquid mobile phase was formed, and a dark yellow product was present, the product was switched to another nitrogen gas-protected flask for collection, and the time was recorded.

[00162] (4) Washing: after collection of the product, the feeding of butyl lithium and zirconium tetrachloride was stopped, and the bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dim ethylsilane solution was replaced with the pure tetrahydrofuran, a large amount of tetrahydrofuran was pumped into the pipeline for washing for lOmin.

[00163] (5) Post-treatment: the product was collected, the solvent was removed by distillation, toluene was added for filtering, and the filtrate was concentrated and crystallized to obtain a pale yellow product, the yield was 76%.

[00164] Comparative Example 1

[00165] The method of preparing rac-dimethylsilyl-bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene )]-zirconium dichloride comprising the following steps:

[00166] 100 mL Schlenk reaction flask was taken and the air contained in the flask was replaced with nitrogen gas, bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-dim ethylsilane (2mmol) obtained from the Preparation Comparative Example 1 and tetrahydrofuran (10mL) were then added, a stirring process was started. »-BuLi hexane solution (2.4M, 4.4mmol) was slowly and dropwise added to the reaction flask at the temperature of -78°C, after the adding process was complete, the flask was heated to room temperature, and the stirring was continued for 2h. The reaction system was again cooled to -78°C, ZrCk (2mmol) was added, the flask was heated to room temperature and stirred for 2h, the solvent was removed by distillation, toluene was added for filtering, the filtrate was concentrated and crystallized to obtain a yellow product, the yield was 41%.

[00167] As can be seen from the above results, the embodiments of the present disclosure has characteristics such as mild reaction conditions, short time and high safety, and obviously better effects.

[00168] Application Example 1

[00169] The application example provided a method for the catalytic preparation of propylene-ethylene copolymer using the catalyst rac-dimethylsilyl-bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene )]-zirconium di chloride prepared in Example 1, the method comprised the following steps:

[00170] Under anhydrous and anaerobic conditions, 1,000mL of toluene and 1,000 pmol of methylaluminoxane (Zr: Al=l: 500) were added to a reaction kettle, and the kettle was heated to 150°C, 2 pmol of the catalyst rac-dimethylsilyl-bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene)]-zirconium dichloride was dissolved in 10mL of toluene, a mixed gas of propylene and ethylene (with a propylene content of 93% by mass) was pressurized into the reaction kettle, the pressure of the mixed gas was adjusted to be 1 MPa. Propylene-ethylene copolymerization reaction was performed at 150°C for 30 min. After the reaction was stopped, the hydrochloric acid acidified ethanol with a mass fraction of 5% was used for terminating the polymerization, a stirring process was implemented for 0.5h, the reactant was filtered, the filtered material was washed with ethanol three times, then subjected to drying under vacuum at 70°C for 12h, the propylene-ethylene polymer was obtained.

[00171] In the application example, the catalyst rac-dimethylsilyl-bis[4-(3',5'-dimethylphenyl)-7-methoxy-2-methylindene )]-zirconium dichloride had a catalytic activity of 2.1 xl07g / [mol(Zr) h], the produced propylene-ethylene polymer had a weight average molecular weight of 63kg / mol, a molecular weight distribution index of 2.7, an ethylene content (by mass) of 15%; the copolymer had a glass transition temperature of -31°C and a melting temperature of 97°C.

[00172] Application Example 2

[00173] The application example provided a method for the catalytic preparation of a copolymer of ethylene and octene by using the catalyst (tert-butylamino)dimethyl-(tetramethyl-r|5-cyclopentadienyl)-silane titanium dichloride prepared in Example 9 under the condition of high temperature 150°C, the method specifically comprised the following steps:

[00174] Under anhydrous and anaerobic conditions, 1,000mL of toluene, 300 mL of 1-octene, and 1,000 pmol of methylaluminoxane (Zr: Al=l: 500) were added to a reaction kettle, and the kettle was heated to 150°C, 2 pmol of the catalyst (tert-butyl aminoj-dimethyl- (tetramethyl-r|5-cyclopentadienyl)-silane titanium dichloride was dissolved in 10mL of toluene, and ethylene was pressurized into the reaction kettle, the ethylene pressure was adjusted to 2MPa, the copolymerization reaction of ethylene and 1-octene was performed at 150°C for 30min, after the reaction was stopped, the hydrochloric acid acidified ethanol with a mass fraction of 5% was used for terminating the polymerization, a stirring process was implemented for 0.5h, the reactant was filtered, the filtered material was washed with ethanol for three times, then subjected to drying under vacuum at 70°C for 12h, the ethyleneoctene polymer was obtained.

[00175] In the application example, the catalyst (tert-butylamino)dimethyl-(tetramethyl-r|5-cyclopentadienyl)-silane titanium dichloride had a catalytic activity of 2.4 107g / [mol(Ti)h], the produced ethylene-octene copolymer had a weight average molecular weight of 63kg / mol, a molecular weight distribution index of 2.5; the copolymer had a glass transition temperature of -52°C and a melting temperature of 65°C.

[00176] The above content describes in detail the preferred embodiments of the present disclosure, but the present disclosure is not limited thereto. A variety of simple modifications can be made in regard to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, including a combination of individual technical features in any other suitable manner, such simple modifications and combinations thereof shall also be regarded as the content disclosed by the present disclosure, each of them falls into the protection scope of the present disclosure.

Claims

1. A continuous flow method for preparing a metallocene catalyst, is characterized in that the method uses a cyclopentadienyl compound or an indenyl compound, organic lithium, organosilane, and chloride as the starting materials for a reaction in a micro-channel continuous flow reactor to prepare the metallocene catalyst, wherein the temperature of the reaction is from -20°C to 60°C.

2. The method of claim 1, wherein the number of the micro-channel continuous flow reactors is at least two;preferably, the micro-channel continuous flow reactor is a channel having a tubular structure, and the channel has a diameter within the range of 0.5-10mm.

3. The method of claim 1 or 2, wherein the micro-channel continuous flow reactor has a liquid holdup within the range of 5-200mL.

4. The method of any one of claims 1-3, wherein the flow rate of fluid in the micro-channel reactor is within the range of 5-40mL / min.

5. The method of any one of claims 1-4, wherein the reaction time is notgreater than 30 min.

6. The method of any one of claims 1-5, wherein a back pressure valve is provided at an outlet of the micro-channel continuous flow reactor, the pressure of the back pressure valve is larger than or equal to 0.5MPa, preferably within the range of 0.6-2MPa.

7. The method of any one of claims 1-6, wherein the number of the micro-channel continuous flow reactors is two, the method specifically comprises the following steps:Subjecting a cyclopentadienyl compound or an indenyl compound to a first reaction with organic lithium I in a micro-channel continuous flow reactor I to obtain a first product; further adding an organosilane to carry out a second reaction to obtain a second product, separating and purifying the second product to obtain a ligand with silicon bridge; subsequently subjecting the ligand with silicon bridge to a third reaction with an organic lithium II in a micro-channel continuous flow reactor II to obtain a third product; further adding chloride to perform a fourth reaction to obtain a fourth product; concentrating and crystallizing the fourth product to prepare a metallocene catalyst.

8. The method of any one of claims 1-6, wherein the number of themicro-channel continuous flow reactors is four, the method specifically comprises the following steps:SI: subjecting a cyclopentadienyl compound or an indeny 1 compound to a first reaction with organic lithium I in a first micro-channel continuous flow reactor I to obtain a first product;S2: subjecting the first product to a second reaction with an organosilane in a second micro-channel continuous flow reactor to obtain a second product, separating and purifying the second product to obtain a ligand with silicon bridge;S3: subjecting the ligand with silicon bridge to a third reaction with an organic lithium II in a third micro-channel continuous flow reactor to obtain a third product;S4: subjecting the third product to a fourth reaction with chloride in a fourth micro-channel continuous flow reactor to obtain a fourth product; concentrating and crystallizing the fourth product to prepare a metallocene catalyst.

9. The method of claim 7 or 8, wherein the first reaction is performed at a temperature range from -20°C to 60°C for a time of 5-500s;and / or, the second reaction is performed at a temperature range from-20°C to 60°C for a time of 5-500s;and / or, the third reaction is performed at a temperature range from -20°Cto 60°C for a time of 5-500s;and / or, the fourth reaction is performed at a temperature range from -20°C to 60°C for a time of 5-500s.

10. The method of any one of claims 7-9, wherein the molar ratio of the cyclopentadienyl compound or the indenyl compound to the organic lithium I is 1: (1-3), preferably 1: (1-1.1);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 method of any one of claims 7-10, wherein the molar ratio of the ligand with silicon bridge to the organic lithium 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 method of any one of claims 1-11, wherein the cyclopentadienyl compound is tetramethyl cyclopentadiene and / or cyclopentadiene;and / or, the indenyl compound is one or more selected from the group consisting of indene, 7-(3',5'-dimethylphenyl)-4-methoxy-2-methylindene, and 7-(3',5'-dimethylphenyl)-2-methylindene;and / or, the organic lithium is one or more selected from the groupconsisting of n-butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium, phenyl lithium, hexyl lithium, and di(trimethylsilyl) lithium amide.

13. The method of any one of claims 1-12, wherein the organosilane is dimethyl di chlorosilane and / or diphenyl dichlorosilane;and / or, the chloride is one or more selected from the group consisting of titanium tetrachloride, zirconium tetrachloride, and hafnium tetrachloride.

14. The method of any one of claims 1-13, wherein the cyclopentadienyl compound or indenyl compound is added in the form of a solution, of which the solvent used is one or more of benzene, toluene, xylene, tetrahydrofuran, diethyl ether, and an aliphatic hydrocarbon, preferably tetrahydrofuran.

15. The method of any one of claims 1-14, wherein the micro-channel continuous flow reactor is made of glass, metal and alloy thereof, ceramic, single-crystal silicon, glass with an anti-corrosion coating on the surface, metal and alloy thereof with an anti-corrosion coating on the surface, ceramic with an anti-corrosion coating on the surface, single-crystal silicon with an anti-corrosion coating on the surface, fluorine-containing resin, or highly crosslinked thermosetting resin, respectively.PCT / CN2023 / 114394A. CLASSIFICATION OF SUBJECT MATTER C07F17 / 00(2006.01)i; C08F10 / 02(2006.01)i; C08F10 / 06(2006.01)i; C08F10 / 14(2006.01)i; C08F4 / 6592(2006.01)i According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) C07F, C08F Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) CNTXT, CNABS, ENTXTC, WPABSC. CNKI, STN, ^S, SMlt, WSS, ¢, (W-t, 8, 41 H ¢(, Li, Zr, Hf, Si, catal+, metall, ocene, lithium, olefin, micro, channel C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. Y CN 103772443 A (CHINA PETROLEUM &CHEMICAL CORP, et al.) 07 May 2014 (2014-05-07) claim 1, and embodiments 1 and 2 1-15 Y Y CN 114195920 A (QINGDAO UNIVERSITY OF SCIENCE AND TECHNOLOGY) 18 March 2022 (2022-03-18) description, paragraphs 136-140, and embodiment 4 CN 108456235 A (XI'AN MODERN CHEMISTRY RESEARCH INSTITUTE) 28 August 2018 (2018-08-28) description, paragraphs 6-20 1-15 1-15 Y MACHAT, M. R. et al. "Ultrarigid Indenyl-based Hafnocene Complexes for the Highly Isoselective Polymerization of Propene: Tunable Polymerization Performance Adopting Various Sterically Demanding 4-Aryl Substituents" ORGANOMETALLICS, Vol. 36, 17 December 2016 (2016-12-17), 399-408 1-15 | | Further documents are listed in the continuation of Box C. | J | See patent family annex. * Special categories of cited documents: “T” later document published after the international filing date or priority “A” document defining the general state of the art which is not considered date and not in conflict with the application but cited to understand the to be of particular relevance principle or theory underlying the invention “D” document cited by the applicant in die international application “X” document of particular relevance; the claimed invention cannot be “E" earlier application orpatent but published on or after the international considered novel or cannot be considered to involve an inventive step filing date when the document is taken alone •SL” document which may throw doubts on priority claim(s) or which is “Y” document of particular relevance; the claimed invention cannot be cited to establish the publication date of another citation or other considered to involve an inventive step when the document is special reason (as specified) combined with one or more other such documents, such combination “O” document referring to an oral disclosure, use, exhibition or other being obvious to a person skilled in the art means document member of the same patent family “P” document published prior to the international filing date but later than the priority date claimed Date of the actual completion of the international search 06 November 2023 Date of mailing of the international search report 23 November 2023 Name and mailing address of the ISA / CN China National Intellectual Property Administration (ISA / CN) China No. 6, Xitucheng Road, Jimenqiao, Haidian District, Beijing 100088 Authorized officer Telephone No.PCT / CN2023 / 114394C. DOCUMENTS CONSIDERED TO BE RELEVANTCategory* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. Y WO 03002583 A2 (EXXONMOBIL CHEMICAL PATENTS INC. et al.) 09 January 2003 (2003-01-09) claim 1, and description, embodiments 1-22 1-15 A CN 106478707 A (DALIAN JOIN KING FINE CHEMICAL CO., LTD.) 08 March 2017 (2017-03-08) entire document 1-15 A CN 107488242 A (SHANGHAI NACO LUBRICATION CO., LTD.) 19 December 2017 (2017-12-19) entire document 1-15INTERNATIONAL SEARCH REPORT Information on patent family membersPCT / CN2023 / 114394Patent document cited in search report Publication date (day / month / year) Patent family member)s) Publication date (day / month / year) CN 103772443 A 07 May 2014 None CN 114195920 A 18 March 2022 None CN 108456235 A 28 August 2018 None WO 03002583 A2 09 January 2003 WO 03002583 A3 04 March 2004 JP 2005522406 A 28 July 2005 EP 1421090 A2 26 May 2004 EP 1421090 Bl 26 March 2014 CN 106478707 A 08 March 2017 None CN 107488242 A 19 December 2017 None

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