Fluorine aryl boron salt compound dispersion system as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of olefin polymerization, and discloses a fluorine aryl boron salt compound dispersion system and a preparation method and application thereof, the preparation method comprises the following steps: 1) dissolving a fluorine aryl boron salt compound in a good solvent to prepare a saturated solution; (2) adding the saturated solution into a poor solvent under the action of stirring and ultrasonic treatment, and stirring and carrying out ultrasonic treatment for 3-10 minutes after the saturated solution is added; 3) filtering the suspension obtained in the step 2) to obtain a solid; under a stirring condition, purging and drying the solid with hot nitrogen, and then treating the solid at high temperature under reduced pressure; and 4) dispersing the solid obtained in the step 3) in an alkane solvent to obtain the fluorine aryl boron salt compound dispersion system. The preparation method is low in process cost, the particle size of the fluorine aryl boron salt compound in the prepared dispersion system is adjustable, and the purity is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of olefin polymerization, and in particular relates to a fluoroaryl boron salt compound dispersion system and a preparation method and application thereof. Background Art

[0002] Aromatic boron compounds are important fine chemicals used in catalysts such as metallocene polyolefin catalysts and hydrogen storage materials. In particular, they are important core co-catalysts in metallocene catalyst systems and have very important uses. They can ionize metallocene compounds and exhibit excellent catalytic performance in olefin polymerization.

[0003] Tetrakis(pentafluoroaryl)borate can show the performance of highly efficient catalysis of olefin polymerization by ionizing metallocene compounds. It is a new generation of co-catalyst for metallocene catalysts and one of the best substitutes for the conventional co-catalyst methylaluminoxane MAO.

[0004] Long-chain ammonium tetrakis(pentafluoroaryl)borate is a type of tetrakis(pentafluoroaryl)borate, which has a better catalytic effect as a co-catalyst. However, this type of compound contains long-chain organic ammonium ions, has a large molecular weight, and is generally a highly viscous liquid. Therefore, the organic cations for tetrakis(pentafluoroaryl)borate are currently mainly short-chain proton ammonium cations or triarylmethyl cations.

[0005] Patent document US6162950A discloses a method for obtaining triphenylmethyl tetrakis(pentafluorophenyl)borate by an ion exchange reaction between potassium tetrakis(pentafluoroaryl)borate and N,N-dimethylphenylammonium chloride in water to obtain N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and a method for obtaining triphenylmethyl tetrakis(pentafluorophenyl)borate by an ion exchange reaction between potassium tetrakis(pentafluoroaryl)borate and triphenylmethane chloride in a normal hexane solvent.

[0006] Patent document US6169208A discloses a method for obtaining N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate by an ion exchange reaction between magnesium tetrakis(pentafluoroaryl)borate and N,N-dimethylphenylammonium chloride in water.

[0007] Patent document US5473036 discloses a method for preparing pentafluorophenylmagnesium bromide from diethyl ether, pentafluorobromobenzene and magnesium, adding butyl ether and boron trifluoride etherate, heating and distilling to remove the diethyl ether, stirring at room temperature and then heating to react to obtain a tetrakis(pentafluorophenyl)borate magnesium bromide solution, and adding the solution to an N,N-dimethylanilinium hydrochloride aqueous solution to react to prepare N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate white crystals.

[0008] The commonly used solvents for olefin solution polymerization are non-polar solvents such as hexane, heptane, and cyclohexane. In these solvent systems, fluorinated aryl borate ammonium salts, trityl carbocation fluorinated aryl borate, and fluorinated aryl boranes that exhibit strong ionic bonds are difficult to dissolve or disperse into a relatively stable suspension. The difficulty in solubility or poor dispersibility leads to the risk of these compounds settling and causing pipeline blockage during the material transmission process of the solution polymerization process.

[0009] There is no simple and low-cost dissolution / dispersion technology in non-polar organic solvents such as hexane in the current public reports. Summary of the invention

[0010] In view of the above problems existing in the prior art, the object of the present invention is to provide a fluoroaryl borate compound dispersion system and a preparation method and application thereof, which can produce a dispersion system with good fluidity in a pipeline.

[0011] The first aspect of the present invention provides a method for preparing a fluoroaryl boron salt compound dispersion system, the preparation method comprising the following steps:

[0012] 1) dissolving a fluoroaryl borate compound in a good solvent to prepare a saturated solution;

[0013] 2) adding the saturated solution to the poor solvent under stirring and ultrasound, and after the addition is completed, stirring and ultrasound are continued for another 3 to 10 minutes;

[0014] 3) filtering the suspension obtained in step 2) to obtain a solid; blowing the solid dry with hot nitrogen under stirring, and then treating the solid at high temperature and reduced pressure;

[0015] 4) dispersing the solid obtained in step 3) in an alkane solvent to obtain the fluoroaryl boron salt compound dispersion system.

[0016] The second aspect of the present invention provides a fluoroaryl borate compound dispersion system obtained by the above-mentioned preparation method.

[0017] The third aspect of the present invention provides the use of the above-mentioned fluoroaryl boron 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 prepare a stable fluoroaryl borate compound dispersion system, solve the problem of transporting the fluoroaryl borate compound during use, and the particle size of the fluoroaryl borate compound in the prepared dispersion system is adjustable, and the purity is further improved.

[0020] This dispersion process can adjust the particle size of the compound, avoiding the dust hazards existing in the mechanical grinding process and the potential risk of carbonization and deactivation of the compound or even dust explosion caused by 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. DETAILED DESCRIPTION

[0022] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

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

[0024] 1) dissolving a fluoroaryl borate compound in a good solvent to prepare a saturated solution;

[0025] 2) adding the saturated solution to the poor solvent under stirring and ultrasound, and after the addition is completed, stirring and ultrasound are continued for another 3 to 10 minutes;

[0026] 3) filtering the suspension obtained in step 2) to obtain a solid; blowing the solid dry with hot nitrogen under stirring, and then treating the solid at high temperature and reduced pressure;

[0027] 4) dispersing the solid obtained in step 3) in an alkane solvent to obtain the fluoroaryl boron salt compound dispersion system.

[0028] In the present invention, the good solvent is a conventionally pure polar organic good solvent, and the good solvent can be selected from at least one of ethyl acetate, chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, ethyl ether, dibutyl ether, methyl tert-butyl ether, propylene oxide, methyl butyl 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 dissolving conditions in step 1) include: a temperature of 25 to 140° C. and a pressure of 1 to 3 atm under stirring.

[0030] The dissolution of the compound in the present invention can also be carried out by stirring ultrasonic waves to dissolve the compound to be treated quickly and prepare a saturated solution. The good solvent used is of ordinary reagent purity and does not require ultra-drying and deoxygenation.

[0031] In the present invention, the poor solvent in step 2) is an organic non-polar solvent, and the poor solvent can be selected from at least one of heptane, cyclohexane, n-hexane, petroleum ether, pentane and octane. The poor solvent is preferably n-hexane, cyclohexane, petroleum ether or pentane.

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

[0033] In step 2) of the present invention, the stirring speed is 200 to 600 rpm, the ultrasonic power is 3 to 8 Kw, and the saturated solution is added for 20 to 40 minutes.

[0034] In the present invention, a saturated solution is added to a poor solvent, and the crystal nuclei are crushed under the action of mechanical stirring and ultrasonic ultrasound, thereby causing the compound to form a fine powder, and the purity is further improved. Specifically, the saturated solution is quickly added to a large amount of poor solvent at a certain temperature (the same as the temperature of the saturated solution) through a high-pressure spray device, and the crystal nucleus growth process is in an unstable state under the mechanical action of rapid stirring and ultrasonic waves emitted by an ultrasonic device (the ultrasonic transmitting device is composed of a rod-shaped ultrasonic transmitting unit embedded in the kettle jacket, which is evenly distributed in the side wall jacket and the bottom jacket of the kettle), splitting the crystal nucleus to produce more crystal nuclei, and realizing the effect of compound particle refinement. This step not only plays a role in particle size adjustment, but also plays a role in recrystallization purification. The compound particle size can be adjusted to less than 100μm (Dv90), and the controllable range of different objects under different process conditions is distributed in 15-100μm, and the purity can be further improved.

[0035] According to the present invention, the filtration in step 3) uses a G4 or G5 sand core or an ultra-high molecular weight polyethylene filter element pressure filtration device. The selected filter element with a pore size can filter out the mother liquid and filter out the prepared powder well, and the selected type of filter element has an excellent self-lubricating effect, which makes the subsequent cleaning process easier.

[0036] In the present invention, the temperature of the hot nitrogen in step 3) is 80-150°C and the purge time is 0.5-2h. The hot nitrogen is passed through the solid powder to preliminarily remove low-boiling impurities and the solvent on the surface of the product. To avoid product clusters, mechanical stirring is continued during the drying process.

[0037] According to the present invention, the temperature of the high temperature and reduced pressure treatment is 90 to 150° C. and the treatment time is 20 to 50 hours. Under the action of high temperature and reduced pressure, the residual solvent and other low boiling point impurities on the surface of the solid powder are deeply removed. Mechanical stirring is continued during the process to avoid uneven heating between the powders or particle agglomeration.

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

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

[0040] According to the present invention, the structure of the fluoroaryl boron 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 C6-C30 aromatic group substituted with fluorine; R 1 , R 2 , R 3 Each is independently selected from C1-C30 alkyl, C1-C30 alkoxy, halogenated 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, halogenated 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, pyrenyl, 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, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6 ... 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 anthracenylmethyl, etc.

[0044] According to a second aspect of the present invention, the present invention provides a fluoroaryl borate compound dispersion system obtained by the above-mentioned preparation method. The particle size of the fluoroaryl borate compound in the dispersion system is within 100 μm (Dv90) and the purity is improved. The dispersion system has good fluidity in a pipeline.

[0045] According to a third aspect of the present invention, the present invention provides a use of the above-mentioned fluoroaryl boron salt compound dispersion system in olefin polymerization.

[0046] The dispersion system prepared by the low-cost dispersion process of the present invention can improve the sedimentation and transportation performance of the fluoroaryl borate compound, and can be transported by a pump in olefin polymerization, thereby solving the problems existing in the specific use of the fluoroaryl borate compound.

[0047] The substances and parameters not limited in the present invention can be selected according to the prior art and belong to the conventional technical means in the field. Unless otherwise specified, the operations and processing methods involved in the present invention belong to the 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 the following examples, but is not limited to these examples.

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

[0050] 1. Particle size of fluoroaryl borate compounds: Malvern laser particle size analyzer, equipment model: Mastersizer3000

[0051] 2. Purity of fluoroaryl borate compounds: High performance liquid chromatography (HPLC), equipment model: Agilent1260

[0052] Example 1

[0053] 2.0Kg of boric acid ammonium salt raw material (N,N-dibutylanilinium tetrakis(pentafluorophenyl)borate, purity 95%) was loaded into a 15L kettle (1#) and replaced with nitrogen. 10L of dichloromethane was added to the kettle. The kettle (1#) was heated to 65°C and stirred to dissolve. After complete dissolution, the dichloromethane solution was slowly introduced into the kettle (2#) containing 50L of 65°C n-hexane. During the introduction, the kettle (2#) was continuously stirred rapidly at a speed of 500 rpm, and the built-in ultrasonic device (w=5Kw) of the kettle (2#) was turned on for 30 minutes. The introduction time lasted for 30 minutes. After the introduction of the dichloromethane solution was completed, the stirring and ultrasonication were maintained for another 5 minutes. The suspension in the kettle (2#) was introduced into the kettle (3#), and the mother liquor was filtered out in situ. The filtration was carried out using an ultra-high molecular weight polyethylene filter element pressure filtration device, purged with hot nitrogen at 100°C, and mechanical stirring was continued for 60 minutes. Stop the hot nitrogen purge. Remove low-boiling impurities and residual solvents in situ at 100°C in vacuum, continue mechanical stirring, and maintain for 24 hours to obtain a sample with a purity of 98%. Introduce 10L of normal-temperature n-hexane into the kettle (3#), stir until the suspension is evenly dispersed, and then introduce the suspension from the kettle (3#) into the transport tank through a retractable bottom tube to achieve further purification and then prepare a target product dispersion system with good fluidity (suspended matter particle size Dv(90)<100μm).

[0054] The ammonium borate salt sample powder after particle size adjustment was sampled and prepared into a suspension with a volume mass fraction of 200 g / L using n-hexane. Sedimentation: The time required for the above suspension with a height of 10 cm to completely settle was 125 s. Pump delivery: The liquid delivery 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 volume mass fraction of 200 g / L in 612 s.

[0055] Example 2

[0056] 2.0Kg of trityl carbocation borate raw material (trityl tetrakis(pentafluorophenyl) borate ammonium salt, purity 96%) was loaded into a 15L kettle (1#) and replaced with nitrogen. 10L of ethyl acetate was added to the kettle. The kettle (1#) was heated to 80°C and stirred to dissolve. After complete dissolution, the ethyl acetate solution was slowly introduced into a kettle (2#) containing 50L of 80°C n-hexane. During the introduction, the kettle (2#) was continuously and rapidly stirred at a speed of 500 rpm, and the ultrasonic device (w=5Kw) built into the kettle (2#) was turned on for 30 minutes. The introduction time lasted for 30 minutes. After the introduction of the ethyl acetate solution was completed, stirring and ultrasonication were maintained for another 5 minutes. The suspension in the kettle (2#) was introduced into the kettle (3#), the mother liquor was filtered out in situ, and the filtration was carried out using an ultra-high molecular weight polyethylene filter element pressure filtration device, purged with hot nitrogen at 100°C, and mechanical stirring was continued for 60 minutes. The hot nitrogen purging was stopped. The low-boiling impurities and residual solvents were removed by vacuum at 120°C in situ, and mechanical stirring was continued for 36 hours to obtain a sample with a purity of 98%. 10L of normal-temperature n-hexane was introduced into the kettle (3#), and after stirring until a uniformly dispersed suspension was obtained, the suspension was introduced from the kettle (3#) into a transport tank through a retractable bottom tube to achieve further purification and then formulated into a target product dispersion system with good fluidity (suspended matter particle size Dv(90)<100μm).

[0057] The trityl carbocation borate sample powder after particle size adjustment was sampled and prepared into a suspension with a volume mass fraction of 200 g / L using n-hexane. Sedimentation: The time required for the above suspension with a height of 10 cm to completely settle was 126 s. Pump delivery: The liquid delivery 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 volume mass fraction of 200 g / L in 610 s.

[0058] Example 3

[0059] 2.0Kg of boric acid ammonium salt raw material (N,N-dibutylanilinium tetrakis(pentafluorophenyl)borate, purity 96%) was loaded into a 15L kettle (1#) and replaced with nitrogen. 10L of chloroform was added to the kettle. The kettle (1#) was heated to 80°C and stirred to dissolve. After complete dissolution, the chloroform solution was slowly introduced into the kettle (2#) containing 50L of 80°C petroleum ether. During the introduction, the kettle (2#) was continuously stirred rapidly at a stirring speed of 500 rpm, and the built-in ultrasonic device (w=5Kw) of the kettle (2#) was turned on for 30 minutes. The introduction time lasted for 30 minutes. After the chloroform solution was introduced, stirring and ultrasonication were maintained for another 5 minutes. The suspension in the kettle (2#) was introduced into the kettle (3#), the mother liquor was filtered out in situ, and the filtration was carried out using an ultra-high molecular weight polyethylene filter element pressure filtration device, 100°C hot nitrogen purge, continuous mechanical stirring, and maintained for 60 minutes. Stop the hot nitrogen purge. The low-boiling impurities and residual solvents were removed by vacuum at 120°C in situ, and mechanical stirring was continued for 24 hours to obtain a sample with a purity of 99%. 10L of petroleum ether at room temperature was introduced into the kettle (3#), and after stirring until a uniformly dispersed suspension was obtained, the suspension was introduced from the kettle (3#) into a transport tank through a retractable bottom tube to achieve further purification and then formulated into a target product dispersion system with good fluidity (suspended matter particle size Dv(90)<100μm).

[0060] The ammonium borate salt sample powder after particle size adjustment was sampled and prepared into a suspension with a volume mass fraction of 200 g / L with petroleum ether. Sedimentation: The time required for the above suspension with a height of 10 cm to completely settle was 123 s. Pump delivery: The liquid delivery 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 volume mass fraction of 200 g / L in 610 s.

[0061] Example 4

[0062] 2.0Kg of trityl carbocation borate raw material (trityl tetrakis(pentafluorophenyl) borate ammonium salt, purity 95%) was loaded into a 15L kettle (1#) and replaced with nitrogen. 10L of chloroform was added to the kettle. The kettle (1#) was heated to 80°C and stirred to dissolve. After complete dissolution, the chloroform solution was slowly introduced into the kettle (2#) containing 50L of 80°C petroleum ether. During the introduction, the kettle (2#) was continuously and rapidly stirred at a speed of 500 rpm, and the ultrasonic device (w=5Kw) built into the kettle (2#) was turned on for 30 minutes. The introduction time lasted for 30 minutes. After the introduction of the chloroform solution was completed, stirring and ultrasonication were maintained for another 5 minutes. The suspension in the kettle (2#) was introduced into the kettle (3#), the mother liquor was filtered out in situ, and the filtration was carried out using an ultra-high molecular weight polyethylene filter element pressure filtration device, purged with hot nitrogen at 100°C, and mechanical stirring was continued for 60 minutes. The hot nitrogen purge was stopped. The low-boiling impurities and residual solvents were removed by vacuum at 120°C in situ, and mechanical stirring was continued for 24 hours to obtain a sample with a purity of 99%. 10L of petroleum ether at room temperature was introduced into the kettle (3#), and after stirring until a uniformly dispersed suspension was obtained, the suspension was introduced from the kettle (3#) into a transport tank through a retractable bottom tube to achieve further purification and then formulated into a target product dispersion system with good fluidity (suspended matter particle size Dv(90)<100μm).

[0063] The trityl carbocation borate sample powder after particle size adjustment was sampled and prepared into a suspension with a volume mass fraction of 200 g / L with petroleum ether. Sedimentation: The time required for the above suspension with a height of 10 cm to completely settle was 126 s. Pump delivery: The liquid delivery 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 volume mass fraction of 200 g / L in 613 s.

[0064] Example 5

[0065] 2.0Kg of ammonium borate raw material (N,N-dimethylanilinium tetra(pentafluorophenyl)borate, purity 96%) was loaded into a 15L kettle (1#) and replaced with nitrogen. 10L of carbon tetrachloride was added to the kettle. The kettle (1#) was heated to 80°C and stirred to dissolve. After complete dissolution, the carbon tetrachloride solution was slowly introduced into a kettle (2#) containing 50L of 80°C petroleum ether. During the introduction, the kettle (2#) was continuously stirred rapidly at a speed of 500 rpm, and the ultrasonic device (w=5Kw) built into the kettle (2#) was turned on for 30 minutes. The introduction time lasted for 30 minutes. After the introduction of the carbon tetrachloride solution was completed, stirring and ultrasonication were maintained for another 5 minutes. The suspension in the kettle (2#) was introduced into the kettle (3#), the mother liquor was filtered out in situ, the filtration was carried out using a G4 sand core, hot nitrogen purge at 100°C, continuous mechanical stirring, and maintained for 60 minutes. The hot nitrogen purge was stopped. The low-boiling impurities and residual solvents were removed in situ at 100°C in vacuum, and mechanical stirring was continued for 24 hours to obtain a sample with a purity of 98%. 10L of petroleum ether at room temperature was introduced into the kettle (3#), and after stirring to a uniformly dispersed suspension, the suspension was introduced from the kettle (3#) into a transport tank through a retractable bottom tube to achieve further purification and then formulated into a target product dispersion system with good fluidity (suspended matter particle size Dv(90)<100μm).

[0066] The ammonium borate salt sample powder after particle size adjustment was sampled and prepared into a suspension with a volume mass fraction of 200 g / L with petroleum ether. Sedimentation: The time required for the above suspension with a height of 10 cm to completely settle was 124 s. Pump delivery: The liquid delivery 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 volume mass fraction of 200 g / L in 611 s.

[0067] Example 6

[0068] 2.0Kg of ammonium borate raw material (N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, purity 96%) was loaded into a 15L kettle (1#) and replaced with nitrogen. 10L 1,2-dichloroethane was added to the kettle. Heat the kettle (1#) to 90°C and stir to dissolve. After complete dissolution, the 1,2-dichloroethane solution was slowly introduced into the kettle (2#) containing 50L 90°C octane. During the introduction, the kettle (2#) was continuously stirred rapidly at a speed of 500 rpm, and the built-in ultrasonic device (w=5Kw) of the kettle (2#) was turned on for 30 minutes. The introduction time lasted for 30 minutes. After the introduction of the 1,2-dichloroethane solution was completed, stirring and ultrasonication were maintained for 5 minutes. The suspension in the kettle (2#) was introduced into the kettle (3#), and the mother liquor was filtered out in situ. The filtration was carried out using a G4 sand core, and hot nitrogen was purged at 120°C, and mechanical stirring was continued for 60 minutes. The hot nitrogen purging was stopped. Low-boiling impurities and residual solvents were removed in situ at 120°C in a vacuum, and mechanical stirring was continued for 36 hours to obtain a sample with a purity of 98%. 10L of normal-temperature n-octane was introduced into the kettle (3#), and after stirring until the suspension was evenly dispersed, the suspension was introduced from the kettle (3#) into a transport tank through a retractable bottom tube to achieve further purification and then formulated into a target product dispersion system with good fluidity (suspended matter particle size Dv(90)<100μm).

[0069] The ammonium borate salt sample powder after particle size adjustment was sampled and prepared into a suspension with a volume mass fraction of 200 g / L using n-octane. Sedimentation: The time required for the above suspension with a height of 10 cm to completely settle was 126 s. Pump delivery: The liquid delivery 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 volume mass fraction of 200 g / L in 613 s.

[0070] Example 7

[0071] 2.0Kg of boric acid ammonium salt raw material (N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, purity 96%) was loaded into a 15L kettle (1#) and replaced with nitrogen. 10L of acetonitrile was added to the kettle. The kettle (1#) was heated to 80°C and stirred to dissolve. After complete dissolution, the acetonitrile solution was slowly introduced into the kettle (2#) containing 50L of cyclohexane at 80°C. During the introduction, the kettle (2#) was continuously stirred rapidly at a stirring speed of 500 rpm, and the built-in ultrasonic device (w=5Kw) of the kettle (2#) was turned on for 30 minutes. The introduction time lasted for 30 minutes. After the acetonitrile solution was introduced, stirring and ultrasonication were maintained for another 5 minutes. The suspension in the kettle (2#) was introduced into the kettle (3#), the mother liquor was filtered out in situ, and the filtration was carried out using a G4 sand core, purged with hot nitrogen at 140°C, and mechanical stirring was continued for 80 minutes. The hot nitrogen purge was stopped. The low-boiling impurities and residual solvents were removed in situ at 140°C in vacuum, and mechanical stirring was continued for 48 hours to obtain a sample with a purity of 97%. 10L of room-temperature cyclohexane was introduced into the kettle (3#), and after stirring until a uniformly dispersed suspension was obtained, the suspension was introduced from the kettle (3#) into a transport tank through a retractable bottom tube to achieve further purification and then formulated into a target product dispersion system with good fluidity (suspended matter particle size Dv(90)<100μm).

[0072] The ammonium borate salt sample powder after particle size adjustment was sampled and prepared into a suspension with a volume mass fraction of 200 g / L using cyclohexane. Sedimentation: The time required for the above suspension with a height of 10 cm to completely settle was 126 s. Pump delivery: The liquid delivery 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 volume mass fraction of 200 g / L in 616 s.

[0073] Example 8

[0074] 2.0Kg of boric acid ammonium salt raw material (N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, purity 96%) was loaded into a 15L kettle (1#) and replaced with nitrogen. 10L of methyl tert-butyl ether was added to the kettle. The kettle (1#) was heated to 80°C and stirred to dissolve. After complete dissolution, the methyl tert-butyl ether solution was slowly introduced into the kettle (2#) containing 50L of 80°C petroleum ether. During the introduction, the kettle (2#) was continuously stirred rapidly at a stirring speed of 500 rpm, and the built-in ultrasonic device (w=5Kw) of the kettle (2#) was turned on for 30 minutes. The introduction time lasted for 30 minutes. After the chloroform solution was introduced, stirring and ultrasonication were maintained for another 5 minutes. The suspension in the kettle (2#) was introduced into the kettle (3#), and the mother liquor was filtered out in situ. The filtration used a G4 sand core, purged with hot nitrogen at 100°C, and mechanical stirring was maintained for 60 minutes. Stop the hot nitrogen purge. The low-boiling impurities and residual solvents were removed by vacuum at 120°C in situ, and mechanical stirring was continued for 24 hours to obtain a sample with a purity of 99%. 10L of petroleum ether at room temperature was introduced into the kettle (3#), and after stirring until a uniformly dispersed suspension was obtained, the suspension was introduced from the kettle (3#) into a transport tank through a retractable bottom tube to achieve further purification and then formulated into a target product dispersion system with good fluidity (suspended matter particle size Dv(90)<100μm).

[0075] The ammonium borate salt sample powder after particle size adjustment was sampled and prepared into a suspension with a volume mass fraction of 200 g / L with petroleum ether. Sedimentation: The time required for the above suspension with a height of 10 cm to completely settle was 127 s. Pump delivery: The liquid delivery 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 volume mass fraction of 200 g / L in 619 s.

[0076] Example 1

[0077] An ammonium borate salt (N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, purity 96%) sample powder without particle size adjustment was weighed and prepared into a suspension with a volume mass fraction of 200 g / L using cyclohexane.

[0078] Sedimentation: The time required for complete sedimentation of the ammonium borate salt / cyclohexane suspension (suspended matter particle size Dv(90)≈500 μm) obtained above by shaking and dispersing at a height of 10 cm: 32 s.

[0079] Pump delivery conditions: The liquid delivery pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100 mL / min) delivers (liquid level difference: 40 cm) 1 L of the above-obtained ammonium borate salt / cyclohexane suspension that was dispersed and mixed by continuous magnetic stirring, and takes 686 seconds.

[0080] Comparative Example 2

[0081] A sample powder of trityl carbenium borate (trityl tetrakis(pentafluorophenyl)borate ammonium salt, purity 96%) without particle size adjustment was weighed and prepared into a suspension with a volume mass fraction of 200 g / L using n-hexane.

[0082] Sedimentation: The time required for complete sedimentation of the trityl carbenium borate / n-hexane suspension (particle size of the suspension Dv(90)≈500 μm) obtained above by shaking and dispersing at a height of 10 cm was 32 s.

[0083] Pump delivery conditions: The liquid delivery pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100 mL / min) delivers (liquid level difference: 40 cm) 1 L of the above-obtained trityl carbenium ion borate / n-hexane suspension that is dispersed and mixed by continuous magnetic stirring, and takes 686 seconds.

[0084] Example 3

[0085] The ammonium borate salt (N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, purity 96%) sample powder without particle size adjustment was weighed and prepared into a suspension with a volume mass fraction of 200 g / L with petroleum ether.

[0086] Sedimentation: The time required for complete sedimentation of the ammonium borate salt / petroleum ether suspension (particle size of the suspended matter Dv(90)≈500 μm) obtained by shaking and dispersing at a height of 10 cm: 30 s.

[0087] Pump delivery conditions: The liquid delivery pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100 mL / min) delivers (liquid level difference: 40 cm) 1 L of the above-obtained ammonium borate salt / petroleum ether suspension that is dispersed and mixed by continuous magnetic stirring, and takes 689 seconds.

[0088] Example 4

[0089] An ammonium borate salt (N,N-dibutylanilinium tetrakis(pentafluorophenyl)borate, purity 96%) sample powder without particle size adjustment was weighed and prepared into a suspension with a volume mass fraction of 200 g / L using petroleum ether.

[0090] Sedimentation: The time required for complete sedimentation of the ammonium borate salt / petroleum ether suspension (particle size of the suspended matter Dv(90)≈500 μm) obtained by shaking and dispersing at a height of 10 cm was 33 s.

[0091] Pump delivery conditions: The liquid delivery pump (type: peristaltic pump; brand: LONGER; model: BT100-2J; set flow rate: 100 mL / min) delivers (liquid level difference: 40 cm) 1 L of the above-obtained ammonium borate salt / petroleum ether suspension that is dispersed and mixed by continuous magnetic stirring, and takes 690 s.

[0092] Compared with the comparative example, the fluoroaryl borate compound dispersion system prepared by the method of the present invention is less likely to settle, is more smoothly transported, requires less time, and the fluoroaryl borate compound in the system has a higher purity.

[0093] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes 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 fluoroaryl borate compound dispersion system, characterized in that: The preparation method comprises the following steps: 1) dissolving a fluoroaryl borate compound in a good solvent to prepare a saturated solution; 2) adding the saturated solution to the poor solvent under stirring and ultrasound, and after the addition is completed, stirring and ultrasound are continued for another 3 to 10 minutes; 3) filtering the suspension obtained in step 2) to obtain a solid; blowing the solid dry with hot nitrogen under stirring, and then treating the solid at high temperature and reduced pressure; 4) dispersing the solid obtained in step 3) in an alkane solvent to obtain the fluoroaryl boron salt compound dispersion system.

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

3. The method for preparing a fluoroaryl borate compound dispersion according to claim 1, wherein: The dissolving conditions in step 1) include: a temperature of 25 to 140° C. and a pressure of 1 to 3 atm under stirring.

4. The method for preparing a fluoroaryl borate compound dispersion system according to claim 1, wherein: The poor 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 a fluoroaryl borate compound dispersion system according to claim 1, wherein: The volume ratio of the poor solvent used in step 2) to the good solvent used in step 1) is 3:1 to 8:

1.

6. The method for preparing a fluoroaryl borate compound dispersion system according to claim 1, wherein: In step 2), the stirring speed is 200 to 600 rpm, the ultrasonic power is 3 to 8 Kw, and the saturated solution is added for 20 to 40 minutes.

7. The method for preparing a fluoroaryl borate compound dispersion system according to claim 1, wherein: The filtration in step 3) uses a G4 or G5 sand core or an ultra-high molecular weight polyethylene filter element pressure filtration device.

8. The method for preparing a fluoroaryl borate compound dispersion system according to claim 1, wherein: In step 3), the temperature of the hot nitrogen is 80-150° C. and the purging time is 0.5-2 h; the temperature of the high-temperature reduced-pressure treatment is 90-150° C. and the treatment time is 20-50 h.

9. A fluoroaryl borate compound dispersion system obtained by the preparation method described in any one of claims 1 to 8.

10. Use of the fluoroaryl boron salt compound dispersion system according to claim 9 in olefin polymerization.

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