A fluorine aryl borate compound dispersion system, a preparation method and application thereof

Abstract

The application belongs to the technical field of olefin polymerization, and discloses a fluorine aryl borate compound dispersion system, a preparation method and application thereof, the preparation method comprising the following steps: 1) dissolving the fluorine aryl borate compound in a good solvent to prepare a saturated solution; 2) under the action of stirring and ultrasonic, the saturated solution is added into a poor solvent, and after the addition is completed, the stirring and ultrasonic continue for 3-10 minutes; 3) the suspension obtained in the step 2) is filtered to obtain a solid, the solid is dried by blowing hot nitrogen gas under stirring, and then the solid is treated at high temperature under reduced pressure; 4) the solid obtained in the step 3) is dispersed in an alkane solvent to obtain the fluorine aryl borate compound dispersion system. The preparation method has low process cost, and the particle size of the fluorine aryl borate compound in the prepared dispersion system is adjustable and the purity is improved.

Description

A dispersion system of fluoroarylboron salt compounds, its preparation method and application Technical Field

[0001] This invention belongs to the field of olefin polymerization technology, specifically relating to a fluoroarylboron salt compound dispersion system, its preparation method, and its application. Background Technology

[0002] Arylboron compounds are important fine chemicals used in catalysts such as metallocene polyolefin catalysts and hydrogen storage materials. In particular, they have important applications as core co-catalysts in metallocene catalyst systems. By ionizing metallocene compounds, they exhibit excellent catalytic performance in olefin polymerization.

[0003] Tetra(pentafluoroaryl)borate exhibits highly efficient catalytic performance in olefin polymerization by ionizing metallocene compounds. It is a new generation of cocatalyst for metallocene catalysts and one of the best alternatives to conventional cocatalysts such as methylaluminoxane (MAO).

[0004] Long-chain ammonium tetra(pentafluoroaryl)borate is a type of tetra(pentafluoroaryl)borate, which exhibits better catalytic performance as a co-catalyst. However, due to the presence of long-chain organic ammonium ions, these compounds have large molecular weights and are generally highly viscous liquids. Therefore, the main organic cations for tetra(pentafluoroaryl)borate are currently short-chain protonated ammonium cations or triarylmethyl cations.

[0005] Patent document US6162950A discloses a method for obtaining N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate by ion exchange reaction of potassium tetra(pentafluoroaryl)borate with N,N-dimethylphenylammonium chloride in water, and a method for obtaining triphenylmethyltetra(pentafluorophenyl)borate by ion exchange reaction of potassium tetra(pentafluoroaryl)borate with triphenylchloromethane in n-hexane solvent.

[0006] Patent document US6169208A discloses a method for obtaining N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate by ion exchange reaction of magnesium tetra(pentafluoroaryl)borate with N,N-dimethylphenylammonium chloride in water.

[0007] Patent document US5473036 discloses a method for preparing magnesium pentafluorophenyl bromide by preparing diethyl ether, pentafluorobromobenzene and magnesium, then adding butyl ether and boron trifluoride diethyl ether, removing the diethyl ether by heating and distillation, stirring at room temperature and heating to react, obtaining a magnesium tetra(pentafluorophenyl)borate solution, and adding it to an aqueous solution of N,N-dimethylphenylammonium hydrochloride to react and prepare white crystals of N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate.

[0008] Common solvents used in olefin solution polymerization include nonpolar solvents such as hexane, heptane, and cyclohexane. In these solvent systems, fluorinated arylborates, triphenylmethyl carbocation fluorinated arylborates, and fluorinated arylboranes, exhibiting strong ionic bonds, are difficult to dissolve or disperse into relatively stable suspensions. This poor solubility or dispersion leads to a risk of sedimentation and pipeline blockage during material transport in solution polymerization processes.

[0009] Currently, there are no publicly available reports on simple and low-cost dissolution / dispersion techniques for non-polar organic solvents such as hexane. Summary of the Invention

[0010] In view of the above-mentioned problems in the prior art, the purpose of this invention is to provide a fluoroarylboron salt compound dispersion system, its preparation method and application, which can produce a dispersion system with good flowability in pipelines.

[0011] The first aspect of the present invention provides a method for preparing a dispersion system of fluoroarylboron salt compounds, the method comprising the following steps:

[0012] 1) Dissolve the fluoroarylboron salt compound in a good solvent to prepare a saturated solution;

[0013] 2) Under the action of stirring and sonication, the saturated solution is added to the unsuitable solvent. After the addition is complete, stirring and sonication are continued for another 3 to 10 minutes.

[0014] 3) Filter the suspension obtained in step 2) to obtain a solid; under stirring conditions, dry the solid by blowing it with hot nitrogen gas, and then treat the solid with high temperature and reduced pressure.

[0015] 4) Disperse the solid obtained in step 3) in an alkane solvent to obtain the dispersion system of the fluoroarylboron salt compound.

[0016] A second aspect of the present invention provides a dispersion system of fluoroarylboron salt compounds prepared by the above-described preparation method.

[0017] A third aspect of the present invention provides the application of the above-described fluoroarylboron salt compound dispersion system in olefin polymerization.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] The preparation method of the present invention can obtain a stable dispersion system of fluoroarylboron salt compounds, solving the problem of transporting fluoroarylboron salt compounds during use. Moreover, the particle size of the fluoroarylboron salt compounds in the obtained dispersion system is adjustable, and the purity is further improved.

[0020] This dispersion process allows for particle size adjustment of the compound, avoiding the dust hazards present in mechanical grinding and the potential risks of compound carbonization and deactivation, or even dust explosion, caused by the instantaneous high temperature during mechanical grinding.

[0021] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0022] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0023] According to a first aspect of the present invention, the present invention provides a method for preparing a dispersion system of fluoroarylboron salt compounds, the method comprising the following steps:

[0024] 1) Dissolve the fluoroarylboron salt compound in a good solvent to prepare a saturated solution;

[0025] 2) Under the action of stirring and sonication, the saturated solution is added to the unsuitable solvent. After the addition is complete, stirring and sonication are continued for another 3 to 10 minutes.

[0026] 3) Filter the suspension obtained in step 2) to obtain a solid; under stirring conditions, dry the solid by blowing it with hot nitrogen gas, and then treat the solid with high temperature and reduced pressure.

[0027] 4) Disperse the solid obtained in step 3) in an alkane solvent to obtain the dispersion system of the fluoroarylboron salt compound.

[0028] In this invention, the good solvent is a conventionally pure polar organic good solvent, which can be selected from at least one of ethyl acetate, chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, diethyl ether, dibutyl ether, methyl tert-butyl ether, propylene oxide, methyl methyl ketone, tetrahydrofuran, dioxane, ethanol, methanol, acetone, acetonitrile, benzene, and toluene. The good solvent is preferably dichloromethane, 1,2-dichloroethane, or acetonitrile.

[0029] According to the present invention, the conditions for dissolution in step 1) include: a temperature of 25 to 140°C and a pressure of 1 to 3 atm under stirring.

[0030] In this invention, the compounds can also be dissolved using stirring and ultrasonication to rapidly dissolve the compounds and prepare a saturated solution. The solvent used is of ordinary reagent grade, and ultra-dry deoxygenation is not required.

[0031] In this invention, the undesirable solvent in step 2) is an organic nonpolar solvent, which may be selected from at least one of heptane, cyclohexane, n-hexane, petroleum ether, pentane, and octane. Preferably, the undesirable solvent is n-hexane, cyclohexane, petroleum ether, or pentane.

[0032] According to the present invention, the volume ratio of the amount of poor solvent used in step 2) to the amount of good solvent used in step 1) is 3:1 to 8:1.

[0033] In step 2) of this invention, the stirring speed is 200-600 rpm, the ultrasonic power is 3-8 kW, and the addition time of the saturated solution is 20-40 min.

[0034] In this invention, a saturated solution is added to a poor solvent, and the crystal nuclei are broken up under the action of mechanical stirring and ultrasonic waves, thereby causing the compound to form a fine powder and further improving its purity. Specifically, the saturated solution is rapidly added to a large amount of poor solvent at a certain temperature (the same temperature as the saturated solution) through a high-pressure spray device. Under the mechanical action of rapid stirring and ultrasonic waves emitted by the ultrasonic device, the crystal nucleus growth process is made unstable (the ultrasonic emitting device consists of rod-shaped ultrasonic emitting units embedded in the jacket of the reactor, which are uniformly distributed in the side wall jacket and bottom jacket of the reactor), splitting the crystal nuclei to generate more crystal nuclei and achieving the effect of refining the compound particles. This step not only plays a role in particle size adjustment but also in recrystallization and purification. The compound particle size can be adjusted to below 100 μm (Dv90), and the controllable range of different guest particles under different process conditions is 15-100 μm, and the purity can be further improved.

[0035] According to the present invention, the filtration in step 3) employs a pressure filtration device using G4 or G5 sand cores or ultra-high molecular weight polyethylene filter elements. The selected filter element with the appropriate pore size can effectively filter out the mother liquor and extract the prepared powder. Furthermore, the selected type of filter element has excellent self-lubricating properties, which simplifies the subsequent cleaning process.

[0036] In this invention, the temperature of the hot nitrogen gas in step 3) is 80–150°C, and the purging time is 0.5–2 hours. Hot nitrogen gas is circulated through the solid powder to initially remove low-boiling-point impurities and solvents from the product surface. To avoid product agglomeration, continuous mechanical stirring is performed during the drying process.

[0037] According to the present invention, the high-temperature and low-pressure treatment is carried out at a temperature of 90–150°C for a duration of 20–50 hours. Under high temperature and low pressure, residual solvents and other low-boiling-point impurities on the surface of the solid powder are thoroughly removed. Continuous mechanical stirring is performed during the process to prevent uneven heating or particle agglomeration.

[0038] In this invention, the alkane solvent in step 4) can be selected from at least one of heptane, cyclohexane, n-hexane, petroleum ether, pentane, and octane. Hexane and petroleum ether, commonly used in olefin solution polymerization systems, are preferred. The fluoroarylboron salt compound is dispersed to a certain mass fraction as needed to achieve pipeline transport of the target compound.

[0039] Unless otherwise specified, the solvents mentioned in this invention are of ordinary industrial grade purity and have not undergone deoxygenation and dehydration treatment.

[0040] According to the present invention, the structure of the fluoroarylboron salt compound is shown in formula (1):

[0041]

[0042] In formula (1), A is NH or a carbon atom; B is a boron atom; Ar is a fluorinated C6-C30 aryl group; R 1 R 2 R 3 Each of the substituents is independently selected from C1-C30 alkyl, C1-C30 alkoxy, halo-C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aryloxy; the substituent is selected from one or more of C1-C30 alkyl, halo-C1-C30 alkyl and (C6-C30)aryl(C1-C30)alkyl.

[0043] Specifically, the (C6-C30)aryl (C1-C30)alkyl group can be 1-naphthyl, 2-naphthyl, o-tolyl, pyrene, biphenyl, benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (4,6-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,4,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (2,3,4,5 ...4,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (2,3,4,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, ( (Phenyl)methyl, (2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl, (tert-butylphenyl)methyl, (n-pentylphenyl)methyl, (neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl, (n-decylphenyl)methyl, (n-decylphenyl)methyl, (n-tetradecylphenyl)methyl, naphthylmethyl or anthracene methyl, etc.

[0044] According to a second aspect of the present invention, a fluoroarylboron salt compound dispersion system prepared by the above-described preparation method is provided. In this dispersion system, the particle size of the fluoroarylboron salt compound is within 100 μm (Dv90), and the purity is improved. The dispersion system exhibits good flowability in pipelines.

[0045] According to a third aspect of the present invention, the present invention provides an application of the above-described fluoroarylboron salt compound dispersion system in olefin polymerization.

[0046] The dispersion system obtained by the present invention through a low-cost dispersion process can improve the sedimentation and transport performance of fluoroarylboron salt compounds. It can be transported by pump in olefin polymerization, thus solving the problems existing in the specific use of fluoroarylboron salt compounds.

[0047] The substances and parameters not specified in this invention can be selected according to existing technology and are conventional techniques in the field. Unless otherwise specified, the operations and processing methods involved in this invention are conventional methods in the field, the instruments used are conventional instruments in the field, and the raw materials used are commercially available.

[0048] The present invention will be further described below with reference to embodiments. However, the invention is not limited to these embodiments.

[0049] In the following examples and comparative examples, the methods for measuring the relevant data are as follows:

[0050] 1. Particle size of fluoroarylboron salt compounds: Malvern laser particle size analyzer, model: Mastersizer3000

[0051] 2. Purity of fluoroarylboron salt compounds: High performance liquid chromatography (HPLC), equipment model: Agilent 1260

[0052] Example 1

[0053] 2.0 kg of ammonium borate raw material (N,N-dibutylphenylammonium tetra(pentafluorophenyl)borate, purity 95%) was loaded into a 15 L reactor (1#) and purged with nitrogen. 10 L of dichloromethane was added to the reactor. The reactor (1#) was heated to 65 °C and stirred to dissolve. After complete dissolution, the dichloromethane solution was slowly transferred to a reactor (2#) containing 50 L of n-hexane at 65 °C. During the transfer, the reactor (2#) was continuously and rapidly stirred at 500 rpm, and the built-in ultrasonic device (w = 5 kW) was activated for 30 min. The transfer process continued for 30 min. After the dichloromethane solution was completely transferred, stirring and ultrasonication were maintained for another 5 min. The suspension in reactor (2#) was transferred to reactor (3#), and the mother liquor was filtered out in situ using an ultra-high molecular weight polyethylene filter cartridge pressure filter, purged with 100 °C hot nitrogen, and continuously mechanically stirred for 60 min. Stop hot nitrogen purging. Remove low-boiling-point impurities and residual solvents in situ at 100℃ under vacuum, and continue mechanical stirring for 24 hours to obtain a sample with a purity of 98%. Add 10L of room-temperature n-hexane to the reactor (3#), stir until a uniformly dispersed suspension is formed, and then transfer the suspension from the reactor (3#) to a transport tank through a retractable bottom tube to achieve further purification before preparing a target product dispersion system with good flowability (suspended particle size Dv(90) < 100μm).

[0054] The above-mentioned ammonium borate salt sample powder, after particle size adjustment, was prepared into a suspension with a volume mass fraction of 200 g / L using n-hexane. Sedimentation: The time required for the above suspension to completely settle to a height of 10 cm was 125 s. Pump delivery: The time taken to deliver 1 L of the above-prepared suspension with a volume mass fraction of 200 g / L using a liquid transfer pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100 mL / min) was 612 s.

[0055] Example 2

[0056] 2.0 kg of triphenylmethyl carborate raw material (triphenylmethyl tetra(pentafluorophenyl)borate ammonium salt, purity 96%) was loaded into a 15L reactor (1#) and purged with nitrogen. 10L of ethyl acetate was added to the reactor. The reactor (1#) was heated to 80°C and stirred to dissolve. After complete dissolution, the ethyl acetate solution was slowly transferred to a reactor (2#) containing 50L of n-hexane at 80°C. During the transfer, the reactor (2#) was continuously and rapidly stirred at 500 rpm, and the built-in ultrasonic device (w=5Kw) was turned on for 30 minutes. The transfer time was maintained for 30 minutes. After the ethyl acetate solution was completely transferred, stirring and ultrasonication were continued for another 5 minutes. The suspension in reactor (2#) was transferred to reactor (3#), and the mother liquor was filtered out in situ using an ultra-high molecular weight polyethylene filter cartridge pressure filter, purged with hot nitrogen at 100°C, and continuously mechanically stirred for 60 minutes. The hot nitrogen purging was then stopped. In situ, the boiling point impurities and residual solvents were removed under vacuum at 120℃. The mixture was continuously mechanically stirred for 36 hours to obtain a sample with a purity of 98%. 10L of room temperature n-hexane was introduced into the reactor (3#) and stirred until a uniformly dispersed suspension was formed. The suspension was then transferred from the reactor (3#) to a transport tank through a retractable bottom tube to achieve further purification before being formulated into a target product dispersion system with good flowability (suspended particle size Dv(90) < 100μm).

[0057] The above-mentioned triphenylmethyl carborate sample powder, after particle size adjustment, was prepared into a suspension with a volume mass fraction of 200 g / L using n-hexane. Sedimentation: The time required for the above suspension to completely settle to a height of 10 cm was 126 s. Pump delivery: The time taken to deliver 1 L of the above-prepared suspension with a volume mass fraction of 200 g / L using a liquid transfer pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100 mL / min) was 610 s.

[0058] Example 3

[0059] 2.0 kg of ammonium borate raw material (N,N-dibutylphenylammonium tetra(pentafluorophenyl)borate, purity 96%) was loaded into a 15L reactor (1#) and purged with nitrogen. 10L of chloroform was added to the reactor. The reactor (1#) was heated to 80°C and stirred to dissolve. After complete dissolution, the chloroform solution was slowly introduced into a reactor (2#) containing 50L of petroleum ether at 80°C. During the introduction, the reactor (2#) was continuously and rapidly stirred at 500 rpm, and the built-in ultrasonic device (w=5Kw) was turned on for 30 minutes. The introduction time was maintained for 30 minutes. After the chloroform solution was completely introduced, stirring and ultrasonication were maintained for another 5 minutes. The suspension in reactor (2#) was introduced into reactor (3#), and the mother liquor was filtered out in situ using an ultra-high molecular weight polyethylene filter cartridge pressure filter, purged with hot nitrogen at 100°C, and continuously mechanically stirred for 60 minutes. The hot nitrogen purging was then stopped. In situ, the boiling point impurities and residual solvents were removed under vacuum at 120℃. The mixture was continuously mechanically stirred for 24 hours to obtain a sample with a purity of 99%. 10L of room temperature petroleum ether was introduced into the reactor (3#) and stirred until a uniformly dispersed suspension was formed. The suspension was then transferred from the reactor (3#) to a transport tank through a retractable bottom tube to achieve further purification before being formulated into a target product dispersion system with good flowability (suspended particle size Dv(90) < 100μm).

[0060] The above-mentioned ammonium borate salt sample powder, after particle size adjustment, was prepared into a suspension with a volumetric mass fraction of 200 g / L using petroleum ether. Sedimentation: The time required for the above suspension to completely settle to a height of 10 cm was 123 s. Pump delivery: The time taken to deliver 1 L of the above-prepared suspension with a volumetric mass fraction of 200 g / L using a liquid transfer pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100 mL / min) was 610 s.

[0061] Example 4

[0062] 2.0 kg of triphenylmethyl carborate raw material (triphenylmethyl tetra(pentafluorophenyl)borate ammonium salt, purity 95%) was loaded into a 15L reactor (1#) and purged with nitrogen. 10L of chloroform was added to the reactor. The reactor (1#) was heated to 80°C and stirred to dissolve. After complete dissolution, the chloroform solution was slowly introduced into a reactor (2#) containing 50L of petroleum ether at 80°C. During the introduction, the reactor (2#) was continuously and rapidly stirred at a speed of 500 rpm, and the built-in ultrasonic device (w=5Kw) was turned on for 30 minutes. The introduction time was maintained for 30 minutes. After the chloroform solution was completely introduced, stirring and ultrasonication were maintained for another 5 minutes. The suspension in reactor (2#) was introduced into reactor (3#), and the mother liquor was filtered out in situ using an ultra-high molecular weight polyethylene filter cartridge pressure filter, purged with hot nitrogen at 100°C, and continuously mechanically stirred for 60 minutes. The hot nitrogen purging was then stopped. In situ, the boiling point impurities and residual solvents were removed under vacuum at 120℃. The mixture was continuously mechanically stirred for 24 hours to obtain a sample with a purity of 99%. 10L of room temperature petroleum ether was introduced into the reactor (3#) and stirred until a uniformly dispersed suspension was formed. The suspension was then transferred from the reactor (3#) to a transport tank through a retractable bottom tube to achieve further purification before being formulated into a target product dispersion system with good flowability (suspended particle size Dv(90) < 100μm).

[0063] The above-mentioned triphenylmethyl carborate sample powder, after particle size adjustment, was prepared into a suspension with a volumetric mass fraction of 200 g / L using petroleum ether. Sedimentation: The time required for the above suspension to completely settle to a height of 10 cm was 126 s. Pump delivery: A liquid transfer pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100 mL / min) took 613 s to deliver 1 L of the above-prepared suspension with a volumetric mass fraction of 200 g / L.

[0064] Example 5

[0065] 2.0 kg of ammonium borate raw material (N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, purity 96%) was loaded into a 15L reactor (1#) and purged with nitrogen. 10L of carbon tetrachloride was added to the reactor. The reactor (1#) was heated to 80°C and stirred to dissolve. After complete dissolution, the carbon tetrachloride solution was slowly introduced into a reactor (2#) containing 50L of petroleum ether at 80°C. During the introduction, the reactor (2#) was continuously and rapidly stirred at 500 rpm, and the built-in ultrasonic device (w=5kW) was turned on for 30 minutes. The introduction time was maintained for 30 minutes. After the carbon tetrachloride solution was completely introduced, stirring and ultrasonication were maintained for another 5 minutes. The suspension in reactor (2#) was introduced into reactor (3#), and the mother liquor was filtered out in situ using a G4 sintered glass filter. The filter was purged with hot nitrogen at 100°C and continuously mechanically stirred for 60 minutes. The hot nitrogen purging was then stopped. In situ, the boiling point impurities and residual solvents were removed under vacuum at 100℃. The mixture was continuously mechanically stirred for 24 hours to obtain a sample with a purity of 98%. 10L of room temperature petroleum ether was introduced into the reactor (3#) and stirred until a uniformly dispersed suspension was formed. The suspension was then transferred from the reactor (3#) to a transport tank through a retractable bottom tube to achieve further purification before being formulated into a target product dispersion system with good flowability (suspended particle size Dv(90) < 100μm).

[0066] The above-mentioned ammonium borate salt sample powder, after particle size adjustment, was prepared into a suspension with a volumetric mass fraction of 200 g / L using petroleum ether. Sedimentation: The time required for the above suspension to completely settle to a height of 10 cm was 124 s. Pump delivery: A liquid transfer pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100 mL / min) delivered 1 L of the above-prepared suspension with a volumetric mass fraction of 200 g / L in 611 s.

[0067] Example 6

[0068] 2.0 kg of ammonium borate raw material (N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, purity 96%) was loaded into a 15 L reactor (1#) and purged with nitrogen. 10 L of 1,2-dichloroethane was added to the reactor. The reactor (1#) was heated to 90 °C and stirred to dissolve. After complete dissolution, the 1,2-dichloroethane solution was slowly poured into a reactor (2#) containing 50 L of 90 °C octane. During the pouring, the reactor (2#) was continuously and rapidly stirred at a speed of 500 rpm, and the built-in ultrasonic device (w = 5 kW) was turned on for 30 min. The pouring process continued for 30 min. After the 1,2-dichloroethane solution was completely poured in, stirring and ultrasonication were maintained for another 5 min. The suspension in vessel (2#) was transferred to vessel (3#), and the mother liquor was filtered out in situ using G4 sintered glass. The filter was purged with hot nitrogen at 120°C and continuously stirred mechanically for 60 minutes. The hot nitrogen purging was then stopped. Low-boiling-point impurities and residual solvents were removed in situ under vacuum at 120°C and continuously stirred mechanically for 36 hours, resulting in a sample purity of 98%. 10 L of room-temperature n-octane was introduced into vessel (3#), and the suspension was stirred until it was uniformly dispersed. The suspension was then transferred from vessel (3#) to a transport tank through a retractable bottom tube for further purification before being formulated into a target product dispersion system with good flowability (suspended particle size Dv(90) < 100 μm).

[0069] The above-mentioned ammonium borate salt sample powder, after particle size adjustment, was prepared into a suspension with a volumetric mass fraction of 200 g / L using n-octane. Sedimentation: The time required for the above suspension to completely settle to a height of 10 cm was 126 s. Pump delivery: The time taken to deliver 1 L of the above-prepared suspension with a volumetric mass fraction of 200 g / L using a liquid transfer pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100 mL / min) was 613 s.

[0070] Example 7

[0071] 2.0 kg of ammonium borate raw material (N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, purity 96%) was loaded into a 15L reactor (1#) and purged with nitrogen. 10L of acetonitrile was added to the reactor. The reactor (1#) was heated to 80°C and stirred to dissolve. After complete dissolution, the acetonitrile solution was slowly transferred to a reactor (2#) containing 50L of cyclohexane at 80°C. During the transfer, the reactor (2#) was continuously and rapidly stirred at 500 rpm, and the built-in ultrasonic device (w=5kW) was turned on for 30 minutes. The transfer time was maintained for 30 minutes. After the acetonitrile solution was completely transferred, stirring and ultrasonication were maintained for another 5 minutes. The suspension in reactor (2#) was transferred to reactor (3#), and the mother liquor was filtered out in situ using a G4 sintered glass filter. The filter was purged with hot nitrogen at 140°C and continuously mechanically stirred for 80 minutes. The hot nitrogen purging was then stopped. In situ, the boiling point impurities and residual solvents were removed under vacuum at 140℃. The mixture was continuously stirred mechanically for 48 hours to obtain a sample with a purity of 97%. 10L of room temperature cyclohexane was introduced into the reactor (3#) and stirred until a uniformly dispersed suspension was formed. The suspension was then transferred from the reactor (3#) to a transport tank through a retractable bottom tube to achieve further purification before being formulated into a target product dispersion system with good flowability (suspended particle size Dv(90) < 100μm).

[0072] The above-mentioned ammonium borate salt sample powder, after particle size adjustment, was prepared into a suspension with a volumetric mass fraction of 200 g / L using cyclohexane. Sedimentation: The time required for the above suspension to completely settle to a height of 10 cm was 126 s. Pump delivery: The time taken to deliver 1 L of the above-prepared suspension with a volumetric mass fraction of 200 g / L using a liquid transfer pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100 mL / min) was 616 s.

[0073] Example 8

[0074] 2.0 kg of ammonium borate raw material (N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, purity 96%) was loaded into a 15 L reactor (1#) and purged with nitrogen. 10 L of methyl tert-butyl ether was added to the reactor. The reactor (1#) was heated to 80 °C and stirred to dissolve. After complete dissolution, the methyl tert-butyl ether solution was slowly transferred to a reactor (2#) containing 50 L of 80 °C petroleum ether. During the transfer, the reactor (2#) was continuously and rapidly stirred at 500 rpm, and the built-in ultrasonic device (w = 5 kW) was turned on for 30 min. The transfer was continued for 30 min. After the chloroform solution was transferred, stirring and ultrasonication were maintained for another 5 min. The suspension in reactor (2#) was transferred to reactor (3#), and the mother liquor was filtered out in situ using a G4 sintered glass filter. The filter was purged with hot nitrogen at 100 °C and continuously mechanically stirred for 60 min. The hot nitrogen purging was then stopped. In situ, the boiling point impurities and residual solvents were removed under vacuum at 120℃. The mixture was continuously mechanically stirred for 24 hours to obtain a sample with a purity of 99%. 10L of room temperature petroleum ether was introduced into the reactor (3#) and stirred until a uniformly dispersed suspension was formed. The suspension was then transferred from the reactor (3#) to a transport tank through a retractable bottom tube to achieve further purification before being formulated into a target product dispersion system with good flowability (suspended particle size Dv(90) < 100μm).

[0075] The above-mentioned ammonium borate salt sample powder, after particle size adjustment, was prepared into a suspension with a volumetric mass fraction of 200 g / L using petroleum ether. Sedimentation: The time required for the above suspension to completely settle to a height of 10 cm was 127 s. Pump delivery: A liquid transfer pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100 mL / min) took 619 s to deliver 1 L of the above-prepared suspension with a volumetric mass fraction of 200 g / L.

[0076] Example 1

[0077] Weigh out unadjusted ammonium borate (N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, purity 96%) sample powder and prepare a suspension with a volume mass fraction of 200 g / L using cyclohexane.

[0078] Sedimentation: The time required for the above-obtained ammonium borate / cyclohexane suspension (particle size Dv(90)≈500μm) to completely settle after shaking and dispersing at a height of 10cm was 32s.

[0079] Pump delivery status: Liquid transfer pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100mL / min) delivered (liquid level difference: 40cm) 1L of the above-obtained ammonium borate / cyclohexane suspension, which was continuously magnetically stirred and dispersed, in 686s.

[0080] Comparative Example 2

[0081] Weigh out the unadjusted triphenylmethyl carborate (triphenylmethyl tetra(pentafluorophenyl)borate ammonium salt, purity 96%) sample powder and prepare a suspension with a volume mass fraction of 200 g / L using n-hexane.

[0082] Sedimentation: The time required for the above-obtained triphenylmethyl carborate / n-hexane suspension (particle size Dv(90)≈500μm) to completely settle after being shaken and dispersed at a height of 10cm was 32s.

[0083] Pump delivery status: Liquid transfer pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100mL / min) delivered (liquid level difference: 40cm) 1L of the above-obtained triphenylmethyl carborate / n-hexane suspension, which was continuously magnetically stirred and dispersed, in 686s.

[0084] Example 3

[0085] Weigh out unadjusted ammonium borate (N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, purity 96%) sample powder and prepare a suspension with a volume mass fraction of 200 g / L using petroleum ether.

[0086] Sedimentation: The time required for the above-obtained ammonium borate / petroleum ether suspension (particle size Dv(90)≈500μm) to completely settle after shaking and dispersing at a height of 10cm was 30s.

[0087] Pump delivery status: Liquid transfer pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100mL / min) delivered (liquid level difference: 40cm) 1L of the above-obtained ammonium borate / petroleum ether suspension, which was continuously magnetically stirred and dispersed, in 689s.

[0088] Example 4

[0089] Weigh out unadjusted ammonium borate (N,N-dibutylphenylammonium tetra(pentafluorophenyl)borate, purity 96%) sample powder and prepare a suspension with a volume mass fraction of 200 g / L using petroleum ether.

[0090] Sedimentation: The time required for the above-obtained ammonium borate / petroleum ether suspension (particle size Dv(90)≈500μm) to completely settle after shaking and dispersing at a height of 10cm was 33s.

[0091] Pump delivery status: Liquid transfer pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100mL / min) delivered (liquid level difference: 40cm) 1L of the above-obtained ammonium borate / petroleum ether suspension, which was continuously magnetically stirred and dispersed, in 690s.

[0092] Compared with the comparative example, the fluoroarylboron salt compound dispersion system prepared by the method of the present invention is less prone to sedimentation, transports more smoothly, requires less time, and has higher purity.

[0093] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A method for preparing a dispersion system of fluoroarylboron salt compounds, characterized in that, The preparation method includes the following steps: 1) dissolving the fluoroarylboron salt compound in a good solvent to prepare a saturated solution; 2) adding the saturated solution to a poor solvent under stirring and sonication, and continuing stirring and sonication for 3-10 minutes after the addition is complete; 3) filtering the suspension obtained in step 2) to obtain a solid; drying the solid by blowing it with hot nitrogen under stirring conditions, and then treating the solid under high temperature and reduced pressure; 4) dispersing the solid obtained in step 3) in an alkane solvent to obtain the fluoroarylboron salt compound dispersion system; the structure of the fluoroarylboron salt compound is shown in formula (1): In formula (1), A is NH or a carbon atom; B is a boron atom; Ar is a fluorinated C6-C30 aryl group; R 1 R 2 R 3 Each is independently selected from C1-C30 alkyl, C1-C30 alkoxy, halo-C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aryloxy; the substituent is selected from C1-C30 alkyl, halo-C1-C30 alkyl, 1-naphthyl, 2-naphthyl, o-tolyl, pyrene, biphenyl, benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl, (2, One of (3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl, (tert-butylphenyl)methyl, (n-pentylphenyl)methyl, (neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl, (n-decylphenyl)methyl, (n-tetradecylphenyl)methyl, naphthylmethyl, and anthracenemethyl.

2. The method for preparing the fluoroarylboron salt compound dispersion system according to claim 1, wherein, The good solvent is selected from at least one of ethyl acetate, chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, diethyl ether, dibutyl ether, methyl tert-butyl ether, propylene oxide, methyl methyl ketone, tetrahydrofuran, dioxane, ethanol, methanol, acetone, acetonitrile, benzene, and toluene.

3. The method for preparing the fluoroarylboron salt compound dispersion system according to claim 1, wherein, The conditions for dissolution in step 1) include: a temperature of 25~140℃ and a pressure of 1~3 atm under stirring.

4. The method for preparing the fluoroarylboron salt compound dispersion system according to claim 1, wherein, The unsuitable solvent in step 2) and the alkane solvent in step 4) are each selected from at least one of heptane, cyclohexane, n-hexane, petroleum ether, pentane and octane.

5. The method for preparing the fluoroarylboron salt compound dispersion system according to claim 1, wherein, The volume ratio of the amount of poor solvent used in step 2) to the amount of good solvent used in step 1) is 3:1 to 8:

1.

6. The method for preparing the fluoroarylboron salt compound dispersion system according to claim 1, wherein, In step 2), the stirring speed is 200-600 rpm, the ultrasonic power is 3-8 kW, and the saturated solution is added over a period of 20-40 minutes.

7. The method for preparing the fluoroarylboron salt compound dispersion system according to claim 1, wherein, The filtration in step 3) uses a pressure filtration device with G4 or G5 sand cores or ultra-high molecular weight polyethylene filter elements.

8. The method for preparing the fluoroarylboron salt compound dispersion system according to claim 1, wherein, In step 3), the temperature of the hot nitrogen gas is 80~150℃ and the purging time is 0.5~2h; the temperature of the high-temperature depressurization treatment is 90~150℃ and the treatment time is 20~50h.

9. A fluoroarylboron salt compound dispersion system prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the fluoroarylboron salt compound dispersion system according to claim 9 in olefin polymerization.

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