A metallocene catalyst and a method for preparing the same

Abstract

The present application relates to a kind of metallocene catalyst and its preparation method, the carrier of catalyst is metal organic framework material, the metal organic framework material is one or several in zinc, iron or zirconium organic framework, the organic ligand of the metal organic framework material contains amino aromatic carboxylic acid.In the introduction of nitrogen atom in the carrier of metallocene catalyst, can be coordinated with metallocene catalyst, change the electronic effect around the active center of metallocene catalyst, improve the activity of catalyst.On the other hand, the nanopore of carrier is composed of multiple cubic structures, ensure the independence of nanopore during polymerization, even if some parts are broken during polymerization, other parts that keep cubic structure can continue to provide nanospace for reaction, i.e.the active center has independent space, avoid double-molecule deactivation, improve the activity of catalyst.

Description

Technical Field

[0001] This invention belongs to the field of catalysts, specifically relating to a metallocene catalyst and its preparation method. Background Technology

[0002] Metallocene compounds offer numerous advantages as catalysts for olefin polymerization, such as uniform distribution of comonomers, low soluble content, and good transparency. However, direct application of these metallocene compounds in olefin polymerization requires a homogeneous reaction system, resulting in poor polymer morphology, severe reactant adhesion to the reactor, and difficult product handling. These issues limit the industrial application of metallocene catalysts. A solution is to support the metallocene catalyst on inert porous particulate supports, such as silica gel, magnesium chloride, and clay.

[0003] Currently, the most reported studies on supported metallocene catalysts utilize SiO2 as the support. For example, CN1095474C, CN1049439C, CN1157419C, US4808561, and US5026797 all disclose supported metallocene catalysts using SiO2 as the support. However, the active sites on this type of catalyst support lack independent space, making them prone to bimolecular deactivation, which leads to a decrease in catalyst activity.

[0004] Metallocene catalysts have also been prepared using molecular sieves as supports. CN1718596A discloses a supported metallocene catalyst obtained by supporting Cp₂ZrCl₂ on MAO-treated SBA-15. However, the catalytic efficiency of the supported metallocene catalyst disclosed in CN1718596A needs further improvement. CN1923862A discloses an olefin polymerization catalyst supported on mesoporous molecular sieves, obtained by supporting a semi-sandwich metallocene compound on MAO-treated SBA-15. However, the highest catalytic efficiency of the catalyst disclosed in CN1923862A is only 10⁶ gPE / (molZr·h). Furthermore, the synthesis conditions for ordered mesoporous molecular sieves are relatively strict, which is not conducive to reducing the cost of supported metallocene catalysts obtained using ordered mesoporous molecular sieves as supports.

[0005] Therefore, how to prepare supported metallocene catalysts with high catalytic efficiency remains a technical problem that urgently needs to be solved.

[0006] Metal-organic frameworks (MOFs) are organic-inorganic hybrid materials with intramolecular pores, formed by the self-assembly of organic ligands and inorganic metal ions or clusters through coordination bonds. They can be applied in fields such as gas storage and separation, chiral resolution, selective catalysis, and drug delivery. In addition to coordinating with ligands, the metal centers in MOFs also coordinate with solvent molecules present during synthesis (such as DMF and H₂O). These solvent molecules can be removed through various methods such as heating and vacuum activation, resulting in unsaturated metal centers that can be used for reactions such as oxidation, ring opening, epoxidation, hydrogenation of carbon-carbon bonds, and isomerization. Chinese patent CN105289732B discloses MOFs as a support for loading the metal peroxide species MO(O₂)₂ as a catalyst in oxidative desulfurization reactions, maintaining high activity and stability. Chinese patent CN106064087B discloses a method for preparing a VOCs catalytic combustion catalyst. It utilizes the three-dimensional porous structure of a metal-organic framework (MOF) for secondary loading of metal oxides, thereby increasing the loading of catalytic components and promoting the formation of small-sized, uniformly distributed catalytic components. Chinese patent CN101920213B invents a low-temperature SCR denitration catalyst using a MOF as a support. This involves impregnating an MOF catalyst support with oxides of one or more metal elements (Mn, Fe, Cu, V, Ce) as the active component, followed by drying, calcination, and sieving to obtain the catalyst. US patent US8372779B2 discloses a porous MOF containing a bidentate organic compound coordinated with a metal ion, wherein the metal ion is Al, and the bidentate organic compound is terephthalic acid. This catalyst is applied in the field of electrochemistry. Chinese patent CN108025286A discloses a composition and method comprising a metal-organic framework for selective olefin oligomerization. The MOF catalyst comprises multiple metal ions, each metal ion coordinated to at least one ligand, and the at least one metal ion is Ni. 2+ The at least one ligand comprises at least two N-heterocyclic aromatic groups arranged around the organic core, wherein the N-heterocyclic aromatic groups are selected from imidazole, triazole, and tetraazole. Chinese Patent CN107602737A discloses the application of a chromium-based metal-organic framework material in olefin polymerization, wherein the chromium-based metal-organic framework material is Cr-MIL-100 or Cr-MIL-101. Chinese Patent CN104803818A discloses a method for liquid-phase ethylene oligomerization and polymerization in the presence of a metal-organic framework material, wherein the catalyst system used contains a metal-organic framework material composed of a transition metal ion and at least a bidentate coordinated organic ligand, wherein the transition metal ion is selected from metal ions V. III Cr III Fe II Co II NiII One or more of the following can be selected: at least bidentate organic ligands, wherein the organic ligands are selected from one or more of terephthalic acid, 1,3,5-benzenetricarboxylic acid, 2,5-dihydroxyterephthalic acid, 2-amino-1,4-benzoic acid, triphenyl dicarboxylic acid, pyrene-2,7-dicarboxylic acid, biphenyl dicarboxylic acid, and naphthalenedicarboxylic acid. The product obtained by this technical solution is a C4-C10 low-carbon olefin. The transition metal framework node is used as the active center, and the degree of freedom to adjust the catalytic performance of the active center is small.

[0007] Currently, there are no metallocene catalysts using metal framework materials as supports in existing technologies. However, it is possible to use metal-organic framework materials as supports for metallocene catalysts, thereby providing a new type of metallocene catalyst that can alter the electronic effects around the active centers of polyolefin catalysts and improve catalyst performance.

[0008] The structural characteristics of metallocene catalyst ligands make it difficult to prepare MOF materials, meaning that MOF materials cannot be directly used to prepare metallocene catalysts. However, MOF materials can be used as supports for metallocene catalysts, and active components can be loaded onto the MOF materials. The functional groups on the MOF materials can be used to modify the active sites of the catalyst, changing the electronic and steric effects of the active sites and improving the catalyst performance. Summary of the Invention

[0009] The purpose of this invention is to provide a metallocene catalyst to solve the problem of low catalytic efficiency of existing supported metallocene catalysts.

[0010] Another object of the present invention is to provide a method for preparing a metallocene catalyst.

[0011] To achieve the above objectives, the present invention provides a metallocene catalyst, wherein the catalyst support is a metal-organic framework material, wherein the metal-organic framework material is one or more of zinc, iron or zirconium organic frameworks, and the organic ligand of the metal-organic framework material contains an amino aromatic carboxylic acid.

[0012] The metallocene catalyst of the present invention has an organic ligand that is one or more of 2-aminoterephthalic acid, 2,5-diaminoterephthalic acid and 2-amino-4,4-biphenylcarboxylic acid.

[0013] To achieve the above objectives, the present invention also provides a method for preparing a metallocene catalyst, comprising the following steps:

[0014] (1) At room temperature, a metal salt and an amino aromatic carboxylic acid ligand with a molar ratio of 1:1 to 5:1 are added to a first organic solvent and mixed evenly. The metal salt is one or more of zinc salt, iron salt and zirconium salt. After standing, a template agent is added. The molar ratio of the template agent to the amino aromatic carboxylic acid ligand is 3:1 to 6:1. After reacting at 50 to 150°C for 6 to 24 hours, a silanol with the same molar amount as the template agent is added. The reaction time is 1 to 6 hours. After washing with a second organic solvent and drying, the metal-organic framework material, i.e., the catalyst support, is obtained.

[0015] (2) The metallocene compound and the co-catalyst are added to a hydrocarbon solvent to react and the catalyst mother liquor is obtained.

[0016] (3) The catalyst support is added to the catalyst mother liquor and the reaction is carried out to obtain the catalyst.

[0017] In the specific application of the catalyst, the slurry catalyst obtained after the reaction can be used directly in the polymerization reaction, or the slurry catalyst can be filtered, washed, and dried under reduced pressure to obtain a solid supported catalyst, which can then be used in the polymerization reaction.

[0018] The molar ratio of the metal salt to the amino-aromatic carboxylic acid ligand is 1:1 to 5:1. A lower ratio results in smaller pore sizes. Since the coordination number of the metal directly affects the pore configuration and size, a smaller ratio increases the effective coordination number of the metal, leading to lower porosity and smaller pore sizes. Conversely, if the coordination number of the metal is too low, the resulting pores may be too large, or even contain inorganic salts, making it impossible to construct the pore structure, which is detrimental to obtaining the target product. Adding a template agent during the preparation of the metal-organic framework can increase the specific surface area of ​​the framework material, while adding silanol can uniformly anchor the metallocene active centers onto the metal-organic framework material.

[0019] The reaction time after adding silanol is 1 to 6 hours, with the optimal reaction time being 2 to 4 hours. The longer the reaction time, the larger the crystal size and the smaller the specific surface area. Conversely, if the reaction time is too short, the metal and ligands cannot coordinate, which is not conducive to obtaining the target product.

[0020] In the preparation method of the metallocene catalyst of the present invention, the standing time in step (1) is 1 to 5 hours.

[0021] The method for preparing the metallocene catalyst of the present invention, wherein the silanol has the general formula R 1 R 2 R 3 Si-OH, where R 1 R 2 R 3The functional groups can be the same or different. Specific examples include, but are not limited to, trimethylsilanol, tert-butyldiphenylsilanol, tert-butyldimethylsilanol, and triisopropylsilanol.

[0022] The method for preparing the metallocene catalyst of the present invention, wherein the catalyst support prepared in step (1) has a pore size of 0.5–15 nm and a specific surface area of ​​400–3000 m² 2 / g; preferably, the pore size is 1-8 nm and the specific surface area is 600-2000 m². 2 / g.

[0023] The method for preparing the metallocene catalyst of the present invention, wherein the metallocene compound conforms to the general formula: (Y)Cp*mMXn;

[0024] In the formula, Cp* is a substituted or unsubstituted cyclopentadiene, indene, or fluorenyl group, and the substituent is a C1 to C20 alkyl, alkoxy, silyl, arylalkoxy, hydroxyl, or halogen group. Indene and fluorenyl groups can also exist in the form of hydrogenation. m takes an integer from 1 to 4. When m ≥ 2, multiple Cp* groups may be the same or different.

[0025] Y represents a bridging group. If the general formula is a non-bridging metallocene complex, then Y does not represent any element. If the general formula is a bridging metallocene complex, then Y is selected from SiR2, CR2, SiR2SiR2, CR2CR2, CR=CR, CR2SiCR2, GeR2, BR, or BR2, where R is a hydrogen atom or a C1-C20 alkyl, aryl, silyl, haloalkyl, haloaryl, arylalkyl, alkylaryl, haloarylalkyl, or haloalkylaryl.

[0026] M is a transition metal from Group 4 or Group 5 of the periodic table, preferably titanium, zirconium, or hafnium.

[0027] X is selected from one of hydrogen, halogen, hydrocarbon group, substituted hydrocarbon group, hydrocarbon oxygen group, aromatic hydrocarbon oxygen group, acid radical, and amino group.

[0028] n is an integer from 1 to 3 that satisfies the M valence state. When n is 2 or greater, multiple X bases may be the same or different.

[0029] Suitable metallocene compounds include, but are not limited to, di(cyclopentadienyl)zirconia dichloride, di(cyclopentadienyl)hafnium dichloride, di(cyclopentadienyl)titanium dichloride, di(cyclopentadienyl)dimethylzirconia, di(cyclopentadienyl)dimethylhafnium, di(n-butylcyclopentadienyl)zirconia dichloride, di(pentamethylcyclopentadienyl)zirconia dichloride, di(tert-butylcyclopentadienyl)zirconia dichloride, dimethylbis(cyclopentadienyl)silylzirconia dichloride, di(indenyl)ethylene-bridged dizirconia dichloride, or di(4,5,6,7-tetrahydro-1-indenyl)zirconia dichloride, dimethylsilyldi(2-methyl-4-naphthylindenyl)zirconia dichloride, and dimethylsilyldi(2-methyl-4-phenylindenyl)zirconia dichloride.

[0030] The method for preparing the metallocene catalyst of the present invention uses an alkylaluminoxane compound or an organoboron compound as a cocatalyst. Alkylaluminoxane compounds include, but are not limited to, methylaluminoxane, ethylaluminoxane, butylaluminoxane, pentylaluminoxane, decylaluminoxane, modified methylaluminoxane, or mixtures thereof, preferably methylaluminoxane. Organoboron compounds include neutral boron compounds, borates, and combinations thereof, such as fluoroorganoboron compounds and fluoroorganoboronate compounds. Fluoroboronate compounds include, but are not limited to, tetra(2,3,5,6-tetrafluorophenyl)borate, tetra(pentafluorophenyl)borate, N,N-dimethylaniline[3,5-bis(trifluoromethyl)phenyl]borate, or mixtures thereof; fluoroorganoboron compounds include, but are not limited to, tris(pentafluorophenyl)borane, tris[3,5-bis(trifluoromethyl)phenyl]boron, or mixtures thereof.

[0031] The preparation method of the metallocene catalyst of the present invention uses one or more of octadecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide and tetradecyltrimethylammonium chloride as the template agent.

[0032] In the preparation method of the metallocene catalyst of the present invention, in step (1), the first organic solvent is one or more of N,N-diethylformamide, dimethyl sulfoxide and dimethylamide, and the second organic solvent is one or more of tetrahydrofuran, diethyl ether, methanol and ethanol.

[0033] The preparation method of the metallocene catalyst of the present invention includes the following steps: in step (2), the weight ratio of the co-catalyst to the metallocene compound is (5-30):1, and the reaction is carried out at -20℃ to 80℃ for 2-10 hours to obtain the catalyst mother liquor; in step (3), the weight ratio of the catalyst support to the co-catalyst in the catalyst mother liquor is (5-20):1, and the reaction is carried out at 0℃ to 80℃ for 2-8 hours to obtain the catalyst.

[0034] The beneficial effects of this invention are:

[0035] Introducing nitrogen atoms into the metallocene catalyst support allows for coordination with the catalyst, altering the electronic effects around the active sites and enhancing catalyst activity. Furthermore, the nanopores of the support, composed of multiple cubic-like structures, ensure the independence of these nanopores during polymerization. Even if some parts break down during polymerization, the remaining cubic structures can continuously provide nanospace for the reaction. This means the active sites have independent spaces, preventing bimolecular deactivation and further improving catalyst activity.

[0036] The catalyst is suitable for the homopolymerization or copolymerization of olefins, especially the homopolymerization of ethylene and propylene, or all polymerization processes of ethylene and propylene with other α-olefins, including gas-phase, slurry, and solution polymerization processes. α-olefins include, but are not limited to, ethylene, propylene, butene, pentene, hexene, and octene. Detailed Implementation

[0037] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description.

[0038] Evaluation and analysis methods:

[0039] Test method:

[0040] Specific surface area: BET method (rapid specific surface area and pore size analyzer).

[0041] Kong Rong: BJH method.

[0042] Pore ​​size: BET method (rapid specific surface area and pore size analyzer).

[0043] Example 1

[0044] At room temperature, 0.2 mol of Zn(NO3)2·4H2O and 0.1 mol of 2-aminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.3 mol of hexadecyltrimethylammonium bromide (CTAB) was added. After reacting at 120 °C for 20 hours, 0.3 mol of trimethylsilanol was added. After reacting for 2 hours, the mixture was washed with tetrahydrofuran and dried to obtain product a.

[0045] 20g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.15g of di(pentamethylcyclopentadienyl)zirconia dichloride and stirred at 50°C for 2 hours to obtain the catalyst mother liquor.

[0046] Then, 20g of product a was added to the mother liquor, and the reaction was continued at 30°C for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0047] Example 2

[0048] At room temperature, 0.4 mol of FeCl3·6H2O and 0.1 mol of 2,5-diaminoterephthalic acid were added to 500 mL of N,N-diethylformamide and mixed thoroughly. After standing for 3 hours, 0.5 mol of octadecyltrimethylammonium bromide was added, and the mixture was reacted at 120 °C for 12 hours. Then, 0.5 mol of trimethylsilanol was added. After reacting for 3 hours, the mixture was washed with tetrahydrofuran and dried to obtain product b.

[0049] 25g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.2g of di(n-butylcyclopentadienyl)zirconia dichloride and stirred at 50°C for 2 hours to obtain the catalyst mother liquor.

[0050] Then, 37.5g of product b was added to the mother liquor, and the reaction was continued at 50°C for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0051] Example 3

[0052] At room temperature, 0.2 mol of Zn(NO3)2·4H2O and 0.1 mol of 2,5-diaminoterephthalic acid were added to 500 mL of dimethyl sulfoxide and mixed thoroughly. After standing for 5 hours, 0.6 mol of tetradecyltrimethylammonium bromide was added, and the mixture was reacted at 110 °C for 18 hours. Then, 0.6 mol of triisopropylsilanol was added. After reacting for 2 hours, the mixture was washed with tetrahydrofuran and dried to obtain product c.

[0053] 25g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.2g of di(n-butylcyclopentadienyl)zirconia dichloride and stirred at 50°C for 2 hours to obtain the catalyst mother liquor.

[0054] Then, 30g of product c was added to the mother liquor, and the reaction was continued at 20℃ for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0055] Example 4

[0056] At room temperature, 0.3 mol of Zn(NO3)2·4H2O and 0.1 mol of 2-aminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.6 mol of octadecyltrimethylammonium chloride was added, and after reacting at 110 °C for 16 hours, 0.6 mol of triisopropylsilanol was added. After reacting for 4 hours, the product was washed with tetrahydrofuran and dried to obtain product d.

[0057] 20g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.3g of dimethylsilylbis(2-methyl-4-phenylindenyl)zirconia dichloride and stirred at 50°C for 2 hours to obtain the catalyst mother liquor.

[0058] Then, 10g of product d was added to the mother liquor, and the reaction was continued at 40℃ for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0059] Example 5

[0060] At room temperature, 0.4 mol of ZrCl4 and 0.1 mol of 2,5-diaminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.5 mol of hexadecyltrimethylammonium chloride was added, and the mixture was reacted at 110 °C for 6 hours. Then, 0.5 mol of triisopropylsilanol was added. After reacting for 4 hours, the mixture was washed with tetrahydrofuran and dried to obtain product e.

[0061] 20g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.3g of dimethylsilylbis(2-methyl-4-naphthylindenyl)zirconia dichloride and stirred at 50°C for 2 hours to obtain the catalyst mother liquor.

[0062] Then, 15g of product e was added to the mother liquor, and the reaction was continued at 10℃ for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0063] Example 6

[0064] At room temperature, 0.1 mol of FeCl3·6H2O and 0.1 mol of 2,5-diaminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.3 mol of tetradecyltrimethylammonium chloride was added, and after reacting at 110 °C for 20 hours, 0.3 mol of triisopropylsilanol was added. After reacting for 4 hours, the product was washed with tetrahydrofuran and dried to obtain product f.

[0065] 20g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.3g of dimethylsilylbis(2-methyl-4-naphthylindenyl)zirconia dichloride and stirred at 80°C for 2 hours to obtain the catalyst mother liquor.

[0066] Then, 12g of product f was added to the mother liquor, and the reaction was continued at 10℃ for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0067] Example 7

[0068] At room temperature, 0.3 mol of Zn(NO3)2·4H2O and 0.1 mol of 2-amino-4,4-biphenyl dicarboxylic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.6 mol of hexadecyltrimethylammonium bromide (CTAB) was added. After reacting at 50 °C for 24 hours, 0.6 mol of trimethylsilanol was added. After reacting for 6 hours, the product was washed with tetrahydrofuran and dried to obtain g of product.

[0069] 20g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.15g of di(n-butylcyclopentadienyl)zirconia dichloride and stirred at 50°C for 10 hours to obtain the catalyst mother liquor.

[0070] Then, 40g of product g was added to the mother liquor, and the reaction was continued at 10℃ for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0071] Example 8

[0072] At room temperature, 0.4 mol of ZrCl4 and 0.1 mol of 2-aminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.5 mol of hexadecyltrimethylammonium bromide (CTAB) was added, and the mixture was reacted at 110 °C for 12 hours. After a period of time, 0.5 mol of triisopropylsilanol was added. After reacting for 4 hours, the product was washed with tetrahydrofuran and dried to obtain product h.

[0073] 20g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.15g of ethylidene-bridged di(1-indenyl)zirconia dichloride and stirred at 10°C for 6 hours to obtain the catalyst mother liquor.

[0074] Then, 20g of product h was added to the mother liquor, and the reaction was continued at 10℃ for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0075] Example 9

[0076] At room temperature, 0.2 mol of ZrCl4 and 0.1 mol of 2,5-diaminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.6 mol of hexadecyltrimethylammonium bromide (CTAB) was added, and after reacting at 110 °C for 12 hours, 0.6 mol of tert-butyldiphenylsilanol was added. After reacting for 4 hours, the product was washed with tetrahydrofuran and dried to obtain product i.

[0077] 20g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.15g of dimethylsilylbis(2-methyl-4-naphthylindenyl)zirconia dichloride and stirred at 50°C for 2 hours to obtain the catalyst mother liquor.

[0078] Then, 20g of product i was added to the mother liquor, and the reaction was continued at 20°C for 8 hours. After removing the solvent, a solid powder catalyst was obtained.

[0079] Example 10

[0080] At room temperature, 0.5 mol of FeCl3·6H2O and 0.1 mol of 2-aminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.6 mol of hexadecyltrimethylammonium bromide (CTAB) was added. After reacting at 110 °C for 12 hours, 0.6 mol of triisopropylsilanol was added. After reacting for 4 hours, the product was washed with tetrahydrofuran and dried to obtain product j.

[0081] 20g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.15g of dimethylsilylbis(2-methyl-4-naphthylindenyl)zirconia dichloride and stirred at 50°C for 2 hours to obtain the catalyst mother liquor.

[0082] Then, 30g of product j was added to the mother liquor, and the reaction was continued at 10℃ for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0083] Example 11

[0084] At room temperature, 0.45 mol of ZrCl4 and 0.2 mol of 2,5-diaminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.6 mol of hexadecyltrimethylammonium bromide (CTAB) was added, and after reacting at 120 °C for 14 hours, 0.6 mol of tert-butyldiphenylsilanol was added. After reacting for 4 hours, the product was washed with tetrahydrofuran and dried to obtain product k.

[0085] 20g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.15g of bis(tetramethylcyclopentadienyl)zirconia dichloride and stirred at 50°C for 2 hours to obtain the catalyst mother liquor.

[0086] Then, 35g of product k was added to the mother liquor, and the reaction was continued at 30°C for 5 hours. After removing the solvent, a solid powder catalyst was obtained.

[0087] Example 12

[0088] At room temperature, 0.45 mol of ZrCl4 and 0.15 mol of 2,5-diaminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.45 mol of hexadecyltrimethylammonium bromide (CTAB) was added, and the mixture was reacted at 150 °C for 18 hours. Then, 0.45 mol of trimethylsilanol was added. After reacting for 4 hours, the mixture was washed with tetrahydrofuran and dried to obtain product l.

[0089] 20g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.15g of dimethylsilylbis(2-methyl-4-naphthylindenyl)zirconia dichloride and stirred at 50°C for 2 hours to obtain the catalyst mother liquor.

[0090] Then, 30g of product l was added to the mother liquor, and the reaction was continued at 10℃ for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0091] Example 13

[0092] At room temperature, 0.3 mol of Zn(NO3)2·4H2O and 0.1 mol of 2,5-diaminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.3 mol of hexadecyltrimethylammonium bromide (CTAB) was added. After reacting at 100 °C for 14 hours, 0.3 mol of triisopropylsilanol was added. After reacting for 4 hours, the product was washed with tetrahydrofuran and dried to obtain product m.

[0093] 20g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.15g of di(n-butylcyclopentadienyl)zirconia dichloride and stirred at -20°C for 2 hours to obtain the catalyst mother liquor.

[0094] Then, 26g of product m was added to the mother liquor, and the reaction was continued at 0℃ for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0095] Example 14

[0096] At room temperature, 0.45 mol of FeCl3·6H2O and 0.2 mol of 2,5-diaminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 1.2 mol of hexadecyltrimethylammonium bromide (CTAB) was added. After reacting at 110 °C for 20 hours, 1.2 mol of tert-butyldimethylsilanol was added. After reacting for 4 hours, the product was washed with tetrahydrofuran and dried to obtain product n.

[0097] A catalyst mother liquor was obtained by stirring 7.5 g of a 10% (w / w) methylaluminoxane toluene solution with 0.15 g of dimethylsilylbis(1-indenyl)zirconia at 50 °C for 2 hours.

[0098] Then 7.5g of product n was added to the mother liquor, and the reaction was continued at 80℃ for 2 hours. After removing the solvent, a solid powder catalyst was obtained.

[0099] Example 15

[0100] At room temperature, 0.5 mol of ZrCl4 and 0.1 mol of 2,5-diaminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.3 mol of hexadecyltrimethylammonium bromide (CTAB) was added, and after reacting at 120 °C for 15 hours, 0.3 mol of tert-butyldiphenylsilanol was added. After reacting for 4 hours, the product was obtained by washing with tetrahydrofuran and drying.

[0101] 45g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.15g of di(tert-butylcyclopentadienyl)zirconia dichloride and stirred at 50°C for 2 hours to obtain the catalyst mother liquor.

[0102] Then, 68g of product o was added to the mother liquor, and the reaction was continued at 0℃ for 8 hours. After removing the solvent, a solid powder catalyst was obtained.

[0103] Example 16

[0104] At room temperature, 0.3 mol of ZrCl4, 0.2 mol of Zn(NO3)2·4H2O, and 0.1 mol of 2,5-diaminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.3 mol of hexadecyltrimethylammonium bromide (CTAB) was added, and the mixture was reacted at 120 °C for 15 hours. Then, 0.3 mol of tert-butyldiphenylsilanol was added. After reacting for 4 hours, the mixture was washed with tetrahydrofuran and dried to obtain product p.

[0105] 45g of a 10% (w / w) methylaluminoxane toluene solution was mixed with 0.15g of di(tert-butylcyclopentadienyl)zirconia dichloride and stirred at 50°C for 2 hours to obtain the catalyst mother liquor.

[0106] Then, 45g of product p was added to the mother liquor, and the reaction was continued at 0℃ for 8 hours. After removing the solvent, a solid powder catalyst was obtained.

[0107] Comparative Example 1

[0108] 20 g of a 10% (w / w) methylaluminoxane toluene solution and 0.15 g of di(pentamethylcyclopentadienyl)zirconia dichloride were added to a reactor and stirred at 50 °C for 2 hours. Then, 20 g of Grace Davison 955 silica support (activated at 600 °C) was added to the reactor and the reaction was continued at 30 °C for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0109] Comparative Example 2

[0110] 25 g of a 10% (w / w) methylaluminoxane toluene solution and 0.2 g of di(n-butylcyclopentadienyl)zirconia dichloride were added to a reactor and stirred at 50 °C for 2 hours. Then, 37.5 g of Grace Davison 955 silica support (activated at 600 °C) was added to the reactor and the reaction was continued at 50 °C for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0111] Comparative Example 3

[0112] 25 g of a 10% (w / w) methylaluminoxane toluene solution and 0.2 g of di(n-butylcyclopentadienyl)zirconia dichloride were added to a reactor and stirred at 50 °C for 2 hours. Then, 30 g of Grace Davison 955 silica support (activated at 600 °C) was added to the reactor and the reaction was continued at 20 °C for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0113] Comparative Example 4

[0114] 20 g of a 10% (w / w) methylaluminoxane toluene solution and 0.3 g of dimethylsilylbis(2-methyl-4-phenylindenyl)zirconia dichloride were added to a reactor and stirred at 50 °C for 2 hours. Then, 10 g of Grace Davison 955 silica support (activated at 600 °C) was added to the reactor and the reaction was continued at 40 °C for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0115] Comparative Example 5

[0116] 20 g of a 10% (w / w) methylaluminoxane toluene solution and 0.3 g of dimethylsilylbis(2-methyl-4-naphthylindenyl)zirconia dichloride were added to a reactor and stirred at 50 °C for 2 hours. Then, 15 g of Grace Davison 955 silica support (activated at 600 °C) was added to the reactor and the reaction was continued at 10 °C for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0117] Comparative Example 6

[0118] At room temperature, 0.2 mol of Mg(NO3)2·6H2O and 0.1 mol of 2-aminoterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.3 mol of hexadecyltrimethylammonium bromide (CTAB) was added. After reacting at 120 °C for 20 hours, 0.3 mol of trimethylsilanol was added. After reacting for 2 hours, the mixture was washed with tetrahydrofuran and dried to obtain product q.

[0119] A 10% (w / w) solution of methylaluminoxane toluene was mixed with 0.15 g of di(pentamethylcyclopentadienyl)zirconia dichloride and stirred at 50 °C for 2 hours to obtain a catalyst mother liquor.

[0120] Then, 20g of product q was added to the mother liquor, and the reaction was continued at 30℃ for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0121] 20 g of a 10% (w / w) methylaluminoxane toluene solution and 0.3 g of dimethylsilylbis(2-methyl-4-naphthylindenyl)zirconia dichloride were added to a reactor and stirred at 80 °C for 2 hours to obtain a catalyst mother liquor. Then, 12 g of Grace Davison 955 silica support (activated at 600 °C) was added to the reactor, and the reaction was continued at 10 °C for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0122] Comparative Example 7

[0123] At room temperature, 0.2 mol of Zn(NO3)2·4H2O and 0.1 mol of 2,5-dihydroxyterephthalic acid were added to 500 mL of dimethylformamide and mixed thoroughly. After standing for 1 hour, 0.3 mol of hexadecyltrimethylammonium bromide (CTAB) was added. After reacting at 120 °C for 20 hours, 0.3 mol of trimethylsilanol was added. After reacting for 2 hours, the mixture was washed with tetrahydrofuran and dried to obtain product r.

[0124] A 10% (w / w) solution of methylaluminoxane toluene was mixed with 0.15 g of di(pentamethylcyclopentadienyl)zirconia dichloride and stirred at 50 °C for 2 hours to obtain a catalyst mother liquor.

[0125] Then, 20g of product r was added to the mother liquor, and the reaction was continued at 30℃ for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0126] 20 g of a 10% (w / w) methylaluminoxane toluene solution and 0.15 g of di(n-butylcyclopentadienyl)zirconia dichloride were added to a reactor and stirred at 50 °C for 10 hours to obtain a catalyst mother liquor. Then, 40 g of Grace Davison 955 silica support (activated at 600 °C) was added to the reactor, and the reaction was continued at 10 °C for 4 hours. After removing the solvent, a solid powder catalyst was obtained.

[0127] Catalysts used in ethylene polymerization:

[0128] In a 10L reactor, the catalysts of Examples 1, 2, 3, 7, 8, 11, 13, 14, 15, 16, Comparative Examples 1, 2, 3, 6, and 7 were used for the homopolymerization of ethylene. 2Kg of hexane was added to the reactor, followed by 0.5g of catalyst. Ethylene was purged at 1MPa and polymerized at 80°C for 1 hour, at which point the reaction was terminated. The reactor was then cooled to room temperature, and the activity of the catalyst was tested. The activity of the obtained catalysts is shown in Table 2.

[0129] Catalysts used in propylene polymerization:

[0130] In a 10L reactor, catalysts from Examples 4, 5, 6, 9, 10, 12, Comparative Example 4, and Comparative Example 5 were used for homopolymerization of propylene. 3 kg of propylene was added to the reactor, followed by 0.5 g of catalyst. The reaction was terminated after polymerization at 70°C for 1 hour. The reactor was then cooled to room temperature, and the activity of the catalyst was tested. The activity of the obtained catalyst is shown in Table 3.

[0131] Table 1. Pore size characterization of intermediate products

[0132]

[0133] Table 2 Catalysts for Ethylene Polymerization

[0134]

[0135]

[0136] Table 3 Catalysts for propylene polymerization

[0137]

[0138] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A metallocene catalyst, wherein the catalyst support is a metal-organic framework material, characterized in that, The metal-organic framework material is one or more of zinc, iron or zirconium organic frameworks, and the organic ligand of the metal-organic framework material is one or more of 2-aminoterephthalic acid, 2,5-diaminoterephthalic acid and 2-amino-4,4-biphenyl dicarboxylic acid. The preparation method of the support is as follows: At room temperature, a metal salt and an organic ligand with a molar ratio of 1:1 to 5:1 are added to a first organic solvent and mixed evenly. The metal salt is one or more of zinc salt, iron salt, and zirconium salt. After standing, a template agent is added, with a molar ratio of template agent to organic ligand of 3:1 to 6:

1. After reacting at 50 to 150°C for 6 to 24 hours, a silanol with the same molar amount as the template agent is added, and the reaction time is 1 to 6 hours. After washing with a second organic solvent and drying, the metal-organic framework material, i.e., the catalyst support, is obtained. The template agent is one or more of octadecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and tetradecyltrimethylammonium chloride; The silanol is one or more of trimethylsilanol, tert-butyldiphenylsilanol, tert-butyldimethylsilanol, and triisopropylsilanol.

2. The method for preparing the metallocene catalyst according to claim 1, characterized in that, Includes the following steps: (1) At room temperature, a metal salt and an organic ligand with a molar ratio of 1:1 to 5:1 are added to a first organic solvent and mixed evenly. The metal salt is one or more of zinc salt, iron salt and zirconium salt. After standing, a template agent is added. The molar ratio of the template agent to the organic ligand is 3:1 to 6:

1. After reacting at 50 to 150°C for 6 to 24 hours, a silanol with the same molar amount as the template agent is added. The reaction time is 1 to 6 hours. After washing with a second organic solvent and drying, the metal-organic framework material, i.e., the catalyst support, is obtained. (2) The metallocene compound and the co-catalyst are added to a hydrocarbon solvent to react and the catalyst mother liquor is obtained; (3) The catalyst support is added to the catalyst mother liquor and the reaction is carried out to obtain the catalyst.

3. The method for preparing the metallocene catalyst according to claim 2, characterized in that, The settling time in step (1) is 1 to 5 hours.

4. The method for preparing the metallocene catalyst according to claim 2, characterized in that, The catalyst support prepared in step (1) has a pore size of 0.5–15 nm and a specific surface area of ​​400–3000 m². 2 / g.

5. The method for preparing the metallocene catalyst according to claim 2, characterized in that, The catalyst support prepared in step (1) has a pore size of 1–8 nm and a specific surface area of ​​600–2000 m². 2 / g.

6. The method for preparing the metallocene catalyst according to claim 2, characterized in that, The metallocene compound conforms to the general formula: (Y)Cp*mMXn; In the formula, Cp* is a substituted or unsubstituted cyclopentadiene, indene, or fluorenyl group, and the substituent is a C1 to C20 alkyl, alkoxy, silyl, arylalkoxy, hydroxyl, or halogen group; m is an integer from 1 to 4, and when m≥2, multiple Cp* groups may be the same or different. Y represents a bridging group. If the general formula is a non-bridging metallocene complex, then Y does not represent any element. If the general formula is a bridging metallocene complex, then Y is selected from Si(R)2, C(R)2, Si(R)2Si(R)2, C(R)2C(R)2, CR=CR, Ge(R)2 or BR, where R is a hydrogen atom or a C1-C20 alkyl, aryl, silyl, haloalkyl, haloaryl, arylalkyl, alkylaryl, haloarylalkyl or haloalkylaryl. M is a transition metal in Group 4 or Group 5 of the periodic table; X is selected from one of hydrogen, halogen, hydrocarbon group, substituted hydrocarbon group, hydrocarbon oxygen group, aromatic hydrocarbon oxygen group, acid radical, and amino group; n is an integer from 1 to 3 that satisfies the M valence state. When n is 2 or greater, multiple X bases may be the same or different.

7. The method for preparing the metallocene catalyst according to claim 6, characterized in that, Indene and fluorenyl exist in hydrogenated forms.

8. The method for preparing the metallocene catalyst according to claim 6, characterized in that, M represents titanium, zirconium, or hafnium.

9. The method for preparing the metallocene catalyst according to claim 2, characterized in that, The cocatalyst is an alkylaluminoxane compound or an organoboron compound.

10. The method for preparing the metallocene catalyst according to claim 2, characterized in that, In step (1), the first organic solvent is one or more of N,N-diethylformamide, dimethyl sulfoxide and dimethylamide, and the second organic solvent is one or more of tetrahydrofuran, diethyl ether, methanol and ethanol.

11. The method for preparing the metallocene catalyst according to claim 2, characterized in that, In step (2), the weight ratio of the co-catalyst to the metallocene compound is (5-30):1, and the reaction is carried out at -20℃ to 80℃ for 2-10 hours to obtain the catalyst mother liquor; in step (3), the weight ratio of the catalyst support to the co-catalyst in the catalyst mother liquor is (5-20):1, and the reaction is carried out at 0℃ to 80℃ for 2-8 hours to obtain the catalyst.

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