A method for removing metallocene catalysts

Abstract

The present invention discloses a method for removing a metallocene catalyst. The method includes: using a metal-organic framework coordination polymer to remove the metallocene catalyst. By using this method, the metallocene catalyst after α-olefin polymerization can be effectively removed, and the removal effect is good.

Description

Technical Field

[0001] The present invention relates to a method for removing metallocene catalysts. Background Art

[0002] Metallocene poly-α-olefins prepared by catalyzing α-olefins with metallocene compounds are a kind of fully synthetic hydrocarbon lubricant base oil, which has the advantages of high viscosity index, excellent low-temperature performance, good thermal oxidation stability, low volatility, good shear stability, etc. These characteristics determine that metallocene poly-α-olefins can be used in high-severity environments, including power transmission systems and gear oils, compressor lubricants, transmission fluids and industrial lubricants. With the increasing requirements of society for energy utilization efficiency and ecological environmental protection, the demand for high-performance metallocene poly-α-olefin lubricant base oils is increasing. During the preparation of metallocene poly-α-olefins, the polymerized catalyst needs to be removed. At present, there are mainly methods such as pickling and adsorption by solids such as diatomaceous earth. For example, CN101490105B discloses a method for preparing polyolefins using metallocene catalysts. Specifically, it removes the residual catalyst by using a solid sorbent. The solid sorbent is selected from silica, alumina, aluminosilicate, amorphous silicate, amorphous aluminate, titanium dioxide, zirconium oxide, magnesium oxide, calcium oxide, natural modified clay, synthetic modified clay, zeolite, diatomaceous earth, natural cellulose materials and synthetic cellulose materials. However, the existing methods for adsorbing and removing metallocene catalysts have problems such as a large amount of adsorbent added and the need to improve the removal effect. Summary of the Invention

[0003] In view of the above problems existing in the prior art, the present invention provides a new method for removing metallocene catalysts. By using this method, the metallocene catalyst after α-olefin polymerization can be effectively removed, and the removal effect is good.

[0004] In a first aspect of the present invention, a method for removing metallocene catalysts is provided, including: using a metal-organic framework coordination polymer to remove metallocene catalysts.

[0005] In some embodiments of the removal method according to the present invention, preferably, the metal-organic framework coordination polymer is selected from at least one of UiO-66, UiO-66-NH2, UiO-66-MM, UiO-66-Br, UiO-66-Br2, UiO-66-CO2H, UiO-67, MIL-100(Al), MIL-100(Fe), MIL-53(Al), MIL-53(Cr), MIL-127, MIL-101-NH2(Cr), MIL-125-NH2(Ti), Zn-MOF-508, Zn-DMOF-A, Zn-DMOF-TM, CAU-10-H, CAU-10-CH3, CAU-10-NO2, CAU-10-NH2, CAU-10-OH, CAU-10-OCH3, MOF-801-P, MOF-801-SC, MOF-802, MOF-804, MOF-841, DUT-51(Zr), DUT-51(Hf), and DUT-67(Zr). In the present invention, the metal-organic framework coordination polymer can be obtained by commercial purchase or by synthesis.

[0006] In some embodiments of the removal method according to the present invention, preferably, the metal-organic framework coordination polymer is subjected to washing, soaking, and drying treatments.

[0007] In some embodiments of the removal method according to the present invention, the solution for washing can be at least one of N,N-dimethylformamide, methanol, ethanol, and chloroform. The number of washing times can be 2 - 4 times.

[0008] In some embodiments of the removal method according to the present invention, the solution for soaking can be at least one of methanol, ethanol, tetrahydrofuran, and chloroform. The conditions for soaking include: the temperature is 0 - 100 °C, and the time is 1 hour - 3 days.

[0009] In some embodiments of the removal method according to the present invention, the drying can be vacuum drying. The conditions for drying can include: the temperature is 0 - 200 °C, preferably 50 - 200 °C, and the time is 1 - 24 hours, preferably 8 - 24 hours.

[0010] In some embodiments of the removal method according to the present invention, the method for preferably subjecting the metal-organic framework coordination polymer to washing, soaking, and drying treatments can include: rinsing 2 - 4 times with N,N-dimethylformamide, then soaking in methanol for 1 hour - 3 days, during which fresh methanol needs to be replaced for soaking, then vacuum drying, and then drying and activating in vacuo at 0 - 200 °C for 1 - 24 hours to obtain a solid sample.

[0011] In some embodiments of the removal method according to the present invention, preferably, the weight ratio of the metal-organic framework coordination polymer to the product mixture containing the metallocene catalyst is 1:100000 - 1:10. In the present invention, in the product mixture containing the metallocene catalyst, the content of the metallocene catalyst can have a relatively wide selection range. For example, calculated as metal, the content of the metallocene catalyst can be, but is not limited to, 1 - 10000 ppm.

[0012] In some embodiments of the removal method according to the present invention, the α-olefin polymerization can be a conventional α-olefin polymerization method in the art. For example, in the presence of a metallocene catalyst, an activator, and a solvent, the α-olefin monomer is polymerized.

[0013] In some embodiments of the removal method according to the present invention, the activator can be an alkylaluminum and / or a borate.

[0014] In some embodiments of the removal method according to the present invention, the chemical general formula of the alkylaluminum can be AlR3, where R is an alkyl group of C1 - C 10 alkyl group, preferably, the alkylaluminum is selected from at least one of trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, triisohexylaluminum, tri-n-hexylaluminum, triisoheptylaluminum, tri-n-heptylaluminum, triisooctylaluminum, tri-n-octylaluminum, triisononylaluminum, tri-n-nonylaluminum, triisodecylaluminum, and tri-n-decylaluminum.

[0015] In some embodiments of the removal method according to the present invention, the borate can be selected from at least one of dimethylanilinium tetrakis(pentafluorophenyl)borate, diethylanilinium tetrakis(pentafluorophenyl)borate, dibutylanilinium tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(pentafluorophenyl)borate, diethylammonium tetrakis(pentafluorophenyl)borate, and tributylammonium tetrakis(pentafluorophenyl)borate.

[0016] In some embodiments of the removal method according to the present invention, the solvent can be an alkane solvent and / or an aromatic solvent, more preferably at least one of hexane, heptane, octane, nonane, decane, cyclohexane, benzene, toluene, and xylene.

[0017] In some embodiments of the removal method according to the present invention, the conditions of the polymerization reaction can include: temperature is 20 - 200 °C, pressure is 0.1 - 2 MPa, and time is 0.5 - 5 h.

[0018] In some embodiments of the removal method according to the present invention, preferably, the conditions of the removal include: temperature is 0 - 150 °C, and time is 10 - 180 min.

[0019] In some embodiments of the removal method according to the present invention, preferably, the metallocene catalyst is a metallocene catalyst after α-olefin polymerization. In the present invention, the α-olefin polymerization reaction can be a conventional α-olefin polymerization reaction in the art. There are no particular limitations on the conditions for the α-olefin polymerization reaction, and the purpose is to enable the α-olefin polymerization reaction.

[0020] In some embodiments of the removal method according to the present invention, preferably, the α-olefin is selected from one or more of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene.

[0021] In some embodiments of the removal method according to the present invention, preferably, the metallocene catalyst is a metallocene compound containing zirconium element and / or a metallocene compound containing hafnium element.

[0022] In some embodiments of the removal method according to the present invention, preferably, the metallocene catalyst is selected from dimethylsilylbis(n-propylcyclopentadienyl)zirconium dichloride, dimethylsilylbis(indenyl)zirconium dichloride, diethylsilylbis(indenyl)zirconium dichloride, diphenylsilylbis(4,7-dimethylindenyl)zirconium dichloride, dimethylsilylbis(4,7-dimethylindenyl)zirconium dichloride, dimethylsilylbis(indenyl)zirconium dichloride, diphenylsilylbis(2-methylcyclopentadienyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(2-methylindenyl)zirconium dichloride, dimethylsilylbis(2-methyl-3-butylcyclopentadienyl)zirconium dichloride, dimethylsilylbis(cyclopentadienyl)zirconium dichloride, diethylmethylenecyclopentadienyl(3,5-dimethylphenylindenyl)zirconium dichloride, diethylmethylenecyclopentadienyl(4,7-dimethylindenyl)zirconium dichloride, dimethylmethylenecyclopentadienyl(4,7-dimethylindenyl)zirconium dichloride, dimethylsilylcyclopentadienyl(4,7-dimethylindenyl)zirconium dichloride, dimethylsilylcyclopentadienyl(3,5-dimethylphenylindenyl)zirconium dichloride, dimethylsilylbis(2-methylcyclopentadienyl)zirconium dichloride, dimethylsilylbis(2-methylindenyl)zirconium dichloride, dimethylsilylcyclopentadienyl(2-methylindenyl)zirconium dichloride, dimethylsilylbis(n-propylcyclopentadienyl)hafnium dichloride, dimethylsilylbis(indenyl)hafnium dichloride, diethylsilylbis(indenyl)hafnium dichloride, diphenylsilylbis(4,7-dimethylindenyl)hafnium dichloride, dimethylsilylbis(4,7-dimethylindenyl)hafnium dichloride, dimethylsilylbis(indenyl)hafnium dichloride, diphenylsilylbis(2-methylcyclopentadienyl)hafnium dichloride, ethylenebis(indenyl)hafnium dichloride, ethylenebis(2-methylindenyl)hafnium dichloride, dimethylsilylbis(2-methyl-3-butylcyclopentadienyl)hafnium dichloride, dimethylsilylbis(cyclopentadienyl)hafnium dichloride, diethylmethylenecyclopentadienyl(3,5-dimethylphenylindenyl)hafnium dichloride, diethylmethylenecyclopentadienyl(4,7-dimethylindenyl)hafnium dichloride, dimethylmethylenecyclopentadienyl(4,7-dimethylindenyl)hafnium dichloride, dimethylsilylcyclopentadienyl(4,7-dimethylindenyl)hafnium dichloride, dimethylsilylcyclopentadienyl(3,5-dimethylphenylindenyl)hafnium dichloride, dimethylsilylbis(2-methylcyclopentadienyl)hafnium dichloride, dimethylsilylbis(2-methylindenyl)hafnium dichloride, and dimethylsilylcyclopentadienyl(2-methylindenyl)hafnium dichloride, at least one of them.

[0023] Advantages of the present invention:

[0024] By using the method of the present invention, the metallocene catalyst after α-olefin polymerization can be effectively removed, and the removal effect is good. Specific embodiments

[0025] To make the present invention easier to understand, the present invention will be described in detail below in conjunction with embodiments. These embodiments are only illustrative and are not limited to the application scope of the present invention.

[0026]

Preparation Example 1

[0027] Prepare metal-organic framework coordination polymer UiO-66:

[0028] Add 5 mmol of zirconium chloride, 5 mmol of terephthalic acid, 1 mL of 37 wt% concentrated hydrochloric acid, and 50 mL of N,N-dimethylformamide into a 100 mL autoclave, ultrasonicate for 15 minutes, seal, heat at 120 °C for 2 days, cool naturally, and filter. Then, rinse with N,N-dimethylformamide 3 times, then soak in methanol for 2 days, during which fresh methanol needs to be replaced for soaking, then vacuum dry, and then dry and activate in vacuum at 150 °C for 12 hours to obtain a solid sample.

[0029]

Preparation Example 2

[0030] Prepare metal-organic framework coordination polymer UiO-66-Br:

[0031] Prepare UiO-66-Br according to the method of Preparation Example 1, except that terephthalic acid is replaced with 2-bromoterephthalic acid.

[0032]

Preparation Example 3

[0033] Prepare metal-organic framework coordination polymer MIL-100(Al):

[0034] Add 7.5 mmol of aluminum nitrate, 5 mmol of benzene-1,3,5-tricarboxylic acid, and 50 mL of ethanol into a 100 mL autoclave, ultrasonicate for 15 minutes, seal, heat at 120 °C for 2 days, cool naturally, and filter. Then, rinse with ethanol 3 times, then soak in ethanol for 2 days, during which fresh ethanol needs to be replaced for soaking, then vacuum dry, and then dry and activate in vacuum at 150 °C for 12 hours to obtain a solid sample.

[0035]

Preparation Example 4

[0036] Prepare metal-organic framework coordination polymer Zn-MOF-508:

[0037] 5 mmol of zinc nitrate, 5 mmol of terephthalic acid, 2.5 mmol of 4,4'-bipyridine, 25 mL of ethanol and 25 mL of N,N-dimethylformamide were added to a 100 mL autoclave, sonicated for 15 minutes, sealed, heated at 120 °C for 2 days, cooled naturally, and filtered. Then, it was rinsed 3 times with N,N-dimethylformamide, and then soaked in methanol for 2 days. During this period, fresh methanol needed to be replaced for soaking. Then it was dried in vacuum, and then dried and activated at 150 °C in vacuum for 12 hours to obtain a solid sample.

[0038]

Preparation Example 5

[0039] Prepare metal-organic framework coordination polymer CAU-10-H:

[0040] 5 mmol of aluminum sulfate, 5.2 mmol of isophthalic acid, 40 mL of water and 10 mL of N,N-dimethylformamide were added to a 100 mL autoclave, sonicated for 15 minutes, sealed, heated at 120 °C for 2 days, cooled naturally, and filtered. Then, it was rinsed 3 times with N,N-dimethylformamide, and then soaked in methanol for 2 days. During this period, fresh methanol needed to be replaced for soaking. Then it was dried in vacuum, and then dried and activated at 150 °C in vacuum for 12 hours to obtain a solid sample.

[0041]

Preparation Example 6

[0042] Prepare metal-organic framework coordination polymer MOF-801-P:

[0043] 5 mmol of zirconium oxychloride, 5 mmol of fumaric acid, 10 mL of formic acid and 40 mL of N,N-dimethylformamide were added to a 100 mL autoclave, sonicated for 15 minutes, sealed, heated at 120 °C for 2 days, cooled naturally, and filtered. Then, it was rinsed 3 times with N,N-dimethylformamide, and then soaked in methanol for 2 days. During this period, fresh methanol needed to be replaced for soaking. Then it was dried in vacuum, and then dried and activated at 150 °C in vacuum for 12 hours to obtain a solid sample.

[0044]

Preparation Example 7

[0045] Prepare metal-organic framework coordination polymer DUT-51(Zr):

[0046] 5 mmol of zirconium chloride, 3.35 mmol of dithieno[3,2-b:2',3'-d]thiophene-2,6-dicarboxylic acid, 10 g of benzoic acid and 50 ml of N,N-dimethylformamide were added to a 100 mL autoclave, sonicated for 15 minutes, sealed, heated at 120 °C for 2 days, cooled naturally, and filtered. Then, it was rinsed 3 times with N,N-dimethylformamide, and then soaked in methanol for 2 days. Fresh methanol needed to be replaced during the soaking process. Then, it was dried under vacuum and then dried and activated at 150 °C in vacuum for 12 hours to obtain a solid sample.

[0047]

Example 1

[0048] 20 g of 1-decene and 40 mL of toluene were added to a 100 mL flask filled with nitrogen, heated at a constant temperature of 100 °C for 30 minutes, and 10 mL of a toluene solution of a metallocene catalyst (10 mg of dimethylsilylbis(indenyl)zirconium dichloride, 15 mg of dimethylphenylammonium tetrakis(pentafluorophenyl)borate, 10 mg of triethylaluminum) was added. After reacting for 1 hour, a product mixture containing the metallocene catalyst was obtained. The filtrate was taken to test the metal content (the content before addition), and the results are shown in Table 1.

[0049] 10 wt% of UiO-66 in the product mixture containing the metallocene catalyst was added at 100 °C, stirred for 30 minutes, filtered, and the filtrate was taken to test the metal content. The results are shown in Table 1 below.

[0050]

Examples 2-7

[0051] According to the method of Example 1, except that UiO-66 was replaced with the metal-organic framework coordination polymers obtained in Preparation Examples 2-7. The results are shown in Table 1 below.

[0052]

Example 8

[0053] According to the method of Example 1, except that the addition amount of UiO-66 was 0.1 wt% of the product mixture containing the metallocene catalyst (replacing 10 wt% of UiO-66 with 0.1 wt% of UiO-66). The results are shown in Table 1 below.

[0054]

Example 9

[0055] According to the method of Example 1, except that the addition amount of UiO-66 was 0.001 wt% of the product mixture containing the metallocene catalyst (replacing 10 wt% of UiO-66 with 0.001 wt% of UiO-66). The results are shown in Table 1 below.

[0056]

Example 10

[0057] According to the method of Example 1, except that the addition temperature of 100 °C was replaced with 120 °C. The results are shown in Table 1 below.

[0058]

Example 11

[0059] According to the method of Example 1, the difference is that the addition temperature of 100 °C is replaced by 150 °C. The results are shown in Table 1 below.

[0060]

Example 12

[0061] According to the method of Example 1, the difference is that the addition temperature of 100 °C is replaced by 30 °C. The results are shown in Table 1 below.

[0062]

Example 13

[0063] According to the method of Example 1, the difference is that the stirring time of 30 minutes is replaced by 60 minutes. The results are shown in Table 1 below.

[0064]

Example 14

[0065] According to the method of Example 1, the difference is that the stirring time of 30 minutes is replaced by 90 minutes. The results are shown in Table 1 below.

[0066]

Comparative Example 1

[0067] According to the method of Example 1, the difference is that UiO-66 (metal-organic framework coordination polymer) is replaced by alumina. The results are shown in Table 1 below.

[0068]

Comparative Example 2

[0069] According to the method of Example 1, the difference is that UiO-66 (metal-organic framework coordination polymer) is replaced by diatomite. The results are shown in Table 1 below.

[0070] Table 1. Removal effect

[0071]

[0072] It can be seen from Examples 1-14 and Comparative Examples 1-2 that under the same addition amount, stirring time and temperature, the effect is that the adsorption amount of the metal-organic framework coordination polymer is more, indicating that the method of the present invention can effectively remove the metallocene catalyst after α-olefin polymerization, and the removal effect is good.

[0073] The above are only the preferred examples of the present invention. It should be pointed out that for those of ordinary skill in the art, under the technical inspiration provided by the present invention, as common general knowledge in the art, other equivalent variations and improvements can also be made, which should also be regarded as the protection scope of the present invention.

Claims

1. A method for removing a metallocene catalyst, comprising: Removing metallocene catalysts using metal-organic framework coordination polymers; The metal-organic framework coordination polymers are selected from at least one of UIO-66, UIO-66-NH2, UIO-66-MM, UIO-66-Br, UIO-66-Br2, UIO-66-CO2H, UIO-67, MIL-100(Al), MIL-100(Fe), MIL-53(Al), MIL-53(Cr), MIL-127, MIL-101-NH2(Cr), MIL-125-NH2(Ti), Zn-MOF-508, Zn-DMOF-A, Zn-DMOF-TM, CAU-10-H, CAU-10-CH3, CAU-10-NO2, CAU-10-NH2, CAU-10-OH, CAU-10-OCH3, MOF-801-P, MOF-801-SC, MOF-802, MOF-804, MOF-841, DUT-51(Zr), DUT-51(Hf), and DUT-67(Zr); The metallocene catalyst is a metallocene catalyst after α-olefin polymerization.

2. The removal method according to claim 1, wherein The metal-organic framework coordination polymer is subjected to soaking, washing, and drying treatments.

3. The removal method according to claim 2, wherein The drying conditions include: a temperature of 0-200 °C and a time of 1-24 hours.

4. The removal method according to any one of claims 1-3, wherein The weight ratio of the metal-organic framework coordination polymer to the product mixture containing the metallocene catalyst is 1:100000 - 1:

10.

5. The removal method according to any one of claims 1-3, wherein The removal conditions include: a temperature of 0-150 °C and a time of 10-180 min.

6. The removal method according to any one of claims 1-3, wherein The α-olefin is selected from one or more of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene.

7. The removal method according to any one of claims 1-3, wherein The metallocene catalyst is a metallocene compound containing zirconium element and / or a metallocene compound containing hafnium element.

8. The removal method according to any one of claims 1-3, wherein The metallocene catalyst is selected from at least one of dimethylsilylbis(n-propylcyclopentadienyl)zirconium dichloride, dimethylsilylbis(indenyl)zirconium dichloride, diethylsilylbis(indenyl)zirconium dichloride, diphenylsilylbis(4,7-dimethylindenyl)zirconium dichloride, dimethylsilylbis(4,7-dimethylindenyl)zirconium dichloride, dimethylsilylbis(indenyl)zirconium dichloride, diphenylsilylbis(2-methylcyclopentadienyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(2-methylindenyl)zirconium dichloride, dimethylsilylbis(2-methyl-3-butylcyclopentadienyl)zirconium dichloride, dimethylsilylbis(cyclopentadienyl)zirconium dichloride, diethylmethylenecyclopentadienyl(3,5-dimethylphenylindenyl)zirconium dichloride, diethylmethylenecyclopentadienyl(4,7-dimethylindenyl)zirconium dichloride, dimethylmethylenecyclopentadienyl(4,7-dimethylindenyl)zirconium dichloride, dimethylsilylcyclopentadienyl(4,7-dimethylindenyl)zirconium dichloride, dimethylsilylcyclopentadienyl(3,5-dimethylphenylindenyl)zirconium dichloride, dimethylsilylbis(2-methylcyclopentadienyl)zirconium dichloride, dimethylsilylbis(2-methylindenyl)zirconium dichloride, dimethylsilylcyclopentadienyl(2-methylindenyl)zirconium dichloride, dimethylsilylbis(n-propylcyclopentadienyl)hafnium dichloride, dimethylsilylbis(indenyl)hafnium dichloride, diethylsilylbis(indenyl)hafnium dichloride, diphenylsilylbis(4,7-dimethylindenyl)hafnium dichloride, dimethylsilylbis(4,7-dimethylindenyl)hafnium dichloride, dimethylsilylbis(indenyl)hafnium dichloride, diphenylsilylbis(2-methylcyclopentadienyl)hafnium dichloride, ethylenebis(indenyl)hafnium dichloride, ethylenebis(2-methylindenyl)hafnium dichloride, dimethylsilylbis(2-methyl-3-butylcyclopentadienyl)hafnium dichloride, dimethylsilylbis(cyclopentadienyl)hafnium dichloride, diethylmethylenecyclopentadienyl(3,5-dimethylphenylindenyl)hafnium dichloride, diethylmethylenecyclopentadienyl(4,7-dimethylindenyl)hafnium dichloride, dimethylmethylenecyclopentadienyl(4,7-dimethylindenyl)hafnium dichloride, dimethylsilylcyclopentadienyl(4,7-dimethylindenyl)hafnium dichloride, dimethylsilylcyclopentadienyl(3,5-dimethylphenylindenyl)hafnium dichloride, dimethylsilylbis(2-methylcyclopentadienyl)hafnium dichloride, dimethylsilylbis(2-methylindenyl)hafnium dichloride, and dimethylsilylcyclopentadienyl(2-methylindenyl)hafnium dichloride.

Images