Process for the preparation of supported metal titanium catalysts and their use in the polymerization of olefins

Abstract

This invention discloses a method for preparing supported titanium metal catalysts and their application in olefin polymerization, belonging to the field of catalyst technology. This invention abandons traditional design concepts and proposes a core technological innovation scheme of "introducing oxygen-containing ionic groups into the catalyst ligand." Specifically, these oxygen-containing ionic groups can, on the one hand, generate strong interactions with the support surface, effectively increasing the loading rate of the metal catalyst; on the other hand, their unique site structure can guide the metal active centers to be loaded on the support surface in a specific "face-up" configuration, thereby significantly improving the polymerization performance of the catalyst. Furthermore, this invention can precisely regulate and enhance the olefin polymerization activity of the catalyst based on the electronic effects exhibited by different supports and metal ions, while simultaneously achieving effective control of the polymer molecular weight, demonstrating significant technical advantages.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, specifically to a method for preparing supported titanium metal catalysts and their application in olefin polymerization. Background Technology

[0002] The annual production of synthetic plastics exceeds 380 million tons, with polyolefins accounting for more than half. Over the past few decades, the design and development of high-performance catalysts have received significant attention from both academia and industry. Academic research on polyolefins has primarily focused on homogeneous systems due to their inherent advantages, such as well-defined molecular structures and the ability to be rationally modified, making them suitable for mechanistic studies. In contrast, the polyolefin industry mainly utilizes heterogeneous systems because they allow for control over product morphology, enabling continuous polymerization processes and preventing reactor fouling. This difference poses a significant challenge to the practical application of high-performance polyolefin catalysts in industrialization research. One possible solution is the heterogeneous formation of homogeneous metal complexes on a solid support through surface organometallic (coordination) chemistry. This method has been extensively studied in the field of organic conversion, giving rise to numerous high-performance catalytic systems. This concept is of great significance for the scientific research and industrial development of polyolefins: it not only combines the core advantages of both types of catalysts but also provides entirely new solutions to existing technological bottlenecks. In fact, a large number of heterogeneous polymerization systems based on pre-transition metal catalysts have already been successfully applied in industrial production.

[0003] The conventional methods for supporting olefin polymerization catalysts on solid supports fall into two main categories: one is to pretreat the support using a co-catalyst before introducing the catalyst into the treated solid support; the other is to design reactive groups in the catalyst structure, which then react with the co-catalyst supported on the solid support to prepare a supported catalyst. However, these commonly used preparation routes generally have several drawbacks: on the one hand, the weak interaction between the active metal species and the solid support easily leads to catalyst leaching problems; on the other hand, the characteristics of this interaction often result in the metal center being loaded on the support surface in a "face-down" structure, which significantly limits the polymerization activity of the active sites on the monomer.

[0004] This study addresses the significant application value of supported transition metal catalysts in the heterogeneous polymerization of olefins, as well as the many key challenges that remain unresolved in this field. Summary of the Invention

[0005] The purpose of this invention is to provide a catalyst that exhibits high thermal stability, catalytic activity, and polymer molecular weight in the homopolymerization of olefins, and is used to prepare ultra-high molecular weight polyethylene.

[0006] To solve the above-mentioned technical problems, the technical solution of this application is as follows: This application provides a method having Figure 1 Supported catalysts in the form of, structural formula as Figure 1 As shown: Further, R1 and R2 are selected from hydrogen, C1-C20 hydrocarbon groups, substituted silyl groups, C1-C20 substituted hydrocarbon groups, phenyl or substituted phenyl groups; R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17 and R18 are independently selected from hydrogen, C1-C20 hydrocarbon groups, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silyl groups, C1-C20 substituted hydrocarbon groups, phenyl or substituted phenyl groups.

[0007] Furthermore, X and Y are independently derived from fluorine, chlorine, bromine, iodine, C1-C20 hydrocarbon groups, aryl groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, boron-containing groups, aluminum-containing groups, phosphorus-containing groups, silicon-containing groups, or tin-containing groups, and M can be a metal such as lithium, sodium, or potassium.

[0008] Furthermore, the specific preparation steps of the supported catalyst are as follows: Under an argon or nitrogen atmosphere, a ligand with structure (II) and a metal source M are added to a solvent and reacted at room temperature for 1-12 hours. Then, a titanium source solution is added. After reacting at room temperature for 1-12 hours, the mixture is filtered to remove the solvent, yielding a complex with structure (IM). A certain amount of the complex (IM) is added to an organic solvent containing a carrier, stirred for 1-120 minutes, and then filtered and washed to obtain the complex as shown in the image. Figure 1 The supported catalyst shown.

[0009] Furthermore, the mass ratio of the complex (IM) to the support in the supported catalyst is between 1:20 and 50,000.

[0010] Furthermore, the structural formula of reaction (A) is as follows: Further, R1 is selected from hydrogen, C1-C12 hydrocarbon group, substituted silyl group, C1-C12 substituted hydrocarbon group, phenyl or substituted phenyl group; R2, R3, R4, R5, R6, R7, R8 and R9 are independently selected from hydrogen, C1-C12 hydrocarbon group, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silyl group, C1-C12 substituted hydrocarbon group, phenyl or substituted phenyl group.

[0011] Furthermore, the carrier is selected from one or more solid inorganic or organic materials such as silicon dioxide, magnesium oxide, titanium dioxide, zinc oxide, aluminum oxide, magnesium chloride, glass fiber, graphene, expanded graphite, ammonium polyphosphate, and carbon black.

[0012] Furthermore, ligands having the structure of formula (II) are composed of (a) and (b) Prepared by reaction in an organic solvent.

[0013] Furthermore, an application of catalytic olefin polymerization includes the following steps: Olefins are polymerized in organic solvents under conditions of 0-200°C and 0.1-50 MPa.

[0014] Furthermore, olefins include one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecene, and 1-octadecene.

[0015] Furthermore, the polymerization process employs slurry polymerization, loop polymerization, gas-phase polymerization, or other forms of polymerization technology.

[0016] Furthermore, the organic solvent is a hydrocarbon with 12 carbon atoms, including but not limited to hexane, toluene, chlorobenzene, and mixtures thereof.

[0017] The beneficial effects of this invention are: This application provides a method having Figure 1 A novel supported iron catalyst is developed, incorporating an OM structure at the para-position of the coordinated nitrogen atom. By introducing metal ions such as lithium, sodium, and potassium, the electron cloud density of the metal center is modulated through electronic effects, thereby enhancing the catalyst's catalytic activity and thermal stability in olefin polymerization, and improving the polymer molecular weight. Simultaneously, the ionized structure alters the catalyst's solubility in the polymerization solvent, leading to the preparation of polymers with controllable morphology. Furthermore, based on the acidity / basicity of the support and steric effects, bimodal polyethylene can be prepared.

[0018] This invention abandons traditional design concepts and proposes a technological innovation centered on "introducing oxygen-containing ionic groups into the catalyst ligand." Specifically, these oxygen-containing ionic groups can, on the one hand, generate strong interactions with the support surface, effectively increasing the loading rate of the metal catalyst; on the other hand, their unique site structure can guide the metal active centers to be loaded onto the support surface in a specific "face-up" configuration, thereby significantly improving the polymerization performance of the catalyst. Furthermore, this invention can precisely regulate and enhance the olefin polymerization activity of the catalyst based on the electronic effects exhibited by different supports and metal ions, while simultaneously achieving effective control over the polymer molecular weight, demonstrating significant technical advantages. Attached Figure Description Figure 1 This is a structural diagram of a supported catalyst.

[0019] Figure 2 The structure diagram of the supported catalyst is shown in formula (I1), (I2), (I3) or (I4).

[0020] Figure 3 This is the specific reaction formula for the supported catalyst.

[0021] Figure 4 It is a ligand with the structure of formula (II). Detailed Implementation

[0022] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0023] According to embodiments of this application, a catalyst is provided, the catalyst having Figure 1 Supported catalysts in the form of: R1 and R2 are selected from hydrogen, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, and R18, which are independently derived from hydrogen, C1-C20 hydrocarbon groups, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silyl groups, C1-C20 substituted hydrocarbon groups, phenyl, or substituted phenyl groups; X and Y are independently derived from chlorine, bromine, C1-C20 hydrocarbon groups, aryl, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, boron-containing groups, aluminum-containing groups, phosphorus-containing groups, silicon-containing groups, or tin-containing groups, wherein the X and Y moieties can bond to each other to form a ring; M can be a metal such as lithium, sodium, or potassium.

[0024] The carrier is selected from one or more solid inorganic or organic materials such as silicon dioxide, magnesium oxide, titanium dioxide, zinc oxide, aluminum oxide, magnesium chloride, glass fiber, graphene, expanded graphite, ammonium polyphosphate, and carbon black.

[0025] Specifically, having Figure 1 The supported catalysts have structures of formula (I1), formula (I2), formula (I3) or formula (I4); Under an argon or nitrogen atmosphere, a ligand having the structure of formula (II) and a metal source M are added to a solvent and reacted at room temperature for 1-12 hours. Then, a solution of a titanium or nickel metal source is added. After reacting at room temperature for 1-12 hours, the mixture is filtered to remove the solvent, yielding a complex with the structure of formula (IM). A certain amount of the complex (IM) is added to an organic solvent containing a carrier, stirred for 1-120 minutes, and then filtered and washed to obtain the complex as shown in the figure. Figure 1 The supported catalysts shown have a mass ratio of complex (IM) to support ranging from 1:20 to 50000. Reaction (A) A ligand having the structure of formula (II) is characterized in that R1 is selected from hydrogen, C1-C12 hydrocarbon group, substituted silyl group, C1-C12 substituted hydrocarbon group, phenyl or substituted phenyl group; and R2, R3, R4, R5, R6, R7, R8 and R9 are independently selected from hydrogen, C1-C12 hydrocarbon group, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silyl group, C1-C12 substituted hydrocarbon group, phenyl or substituted phenyl group. Specifically, R1 is selected from hydrogen, C1-C6 hydrocarbon group, C1-C6 substituted hydrocarbon group, phenyl or substituted phenyl; R2, R3, R4, R5, R6, R7, R8 and R9 are independently selected from hydrogen, C1-C6 hydrocarbon group, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silicon group, C1-C6 substituted hydrocarbon group, phenyl or substituted phenyl; More specifically, ligands having the structure of formula (II) are composed of (a) and (b) Prepared by reaction in an organic solvent.

[0026] Specifically, ligands having the structure of formula (II) have the structures of formula (II 1), formula (II 2), formula (II 3), or formula (II 4); According to embodiments of this application, an application for catalytic olefin polymerization is also provided, comprising: have Figure 1 Supported catalysts in this form are used to catalyze the polymerization of olefins. The olefins include one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecene, and 1-octadecene.

[0027] The polymerization process employs slurry polymerization, loop polymerization, gas-phase polymerization, or other polymerization techniques.

[0028] Polymerization typically takes place in organic solvents, such as hydrocarbons, cyclic hydrocarbons, or aromatic hydrocarbons. To facilitate reactor operation and polymerization products, organic solvents can be hydrocarbons with fewer than 12 carbon atoms, such as, but not limited to, hexane, toluene, chlorobenzene, and mixtures thereof.

[0029] The polymerization temperature is maintained between 0℃ and 200℃.

[0030] The polymerization pressure can vary from 0.1 to 50 MPa.

[0031] To further understand the present invention, the catalyst provided by the present invention will be described in detail below with reference to the embodiments. The scope of protection of the present invention is not limited by the following embodiments.

[0032] The following examples illustrate the specific content of the present invention. The data provided include ligand synthesis, catalyst synthesis, and ethylene polymerization or copolymerization methods. Catalyst synthesis and polymerization processes are carried out under anhydrous and oxygen-free conditions. All sensitive substances are stored in a glove box, all solvents are rigorously dried and dehydrated, and ethylene gas is purified using a dehydration and deoxygenation column. All supports are dried. Unless otherwise specified, all raw materials are commercially available.

[0033] Silica gel columns were made of 200-300 mesh silica gel, and NMR was performed using a Bruker 400MHz NMR instrument. Elemental analysis was conducted by the Physics and Chemistry Center of the University of Science and Technology of China. Molecular weight and molecular weight distribution were determined by GPC (polystyrene columns, HR2 and HR4, oven temperature 45℃, using Water 1515 and Water 2414 pumps; mobile phase was tetrahydrofuran, flow rate 1.0 mL / min, using polydisperse polystyrene as the standard). Mass spectrometry was performed using a Thermo LTQ Orbitrap XL (ESI+) or P-SIMS-Glyof Bruker Daltonics Inc (EI+). Single-crystal X-ray diffraction analysis was performed using an Oxford Diffraction GeminiS Ultra CCD single-crystal diffractometer, Cu Kα (λ=1.54184 Å) at room temperature.

[0034] Example 1: Preparation of 2-tert-butyl-6-((p-tolyl)imino)methyl)1,4-benzenediol (II1) A mixture of 1.5 g (7.7 mmol) of 3-tert-butyl-2,5-dihydroxybenzaldehyde, 0.91 g (8.4 mmol) of p-aminophenol, and 1 mL of formic acid was dissolved in 50 mL of methanol and refluxed overnight at 80 °C. The reaction mixture was concentrated and recrystallized from hexane to give a yellow solid compound, 2-tert-butyl-6-((p-tolylimino)methyl)1,4-benzenediol (1.85 g, 85% yield). 1 H NMR (400 MHz, CHLOROFORM- D ) δ 8.54 (s, 1H, -N=CH ), 7.21 (s, 4H), 6.96 (s, 1H), 6.74 (s, 1H), 2.38 (s, 3H, -Me ), 1.45(s, 9H, -tBu ). 13 C NMR (101 MHz, CHLOROFORM- D) δ 161.98, 154.91, 147.05, 145.93,139.31, 136.86, 130.07, 121.09, 119.01, 118.91, 115.01, 77.43, 77.11, 76.79,35.07, 29.33, 21.13. Example 2: Preparation of 2-tert-butyl-6-(((pentafluorophenyl)imino))methyl)1,4-benzenediol The difference between this embodiment and Example 1 is that (II2) the raw materials were replaced with 3-tert-butyl-2,5-dihydroxybenzaldehyde (1.4 g, 7.2 mmol) and 2,3,4,5,6-pentafluoroaniline (1.32 g, 7.2 mmol). The final product was a yellow powder, compound L2, with a mass of 2.1 g and a yield of 82%. 1 H NMR (400 MHz, CHLOROFORM- D ) δ 8.73 (s, 1H , -N=CH ),7.04 (s, 1H), 6.70 (s, 1H), 1.45 (s, 9H, -tBu ). 19 F NMR (376 MHz, CHLOROFORM- D )δ -151.80, -151.82, -151.86, -151.88, -158.14, -158.19, -158.25, -162.16, -162.17, -162.21, -162.23, -162.27, -162.29. 13 C NMR (101 MHz, CHLOROFORM- D ) δ170.74, 155.61, 147.35, 140.08, 121.39, 118.24, 115.55, 77.41, 77.30, 77.10,76.78, 35.16, 29.25. Example 3: Preparation of 2-tert-butyl-6-(((trifluoromethylphenyl)imino))methyl)1,4-benzenediol The difference between this example and Example 1 is that the raw materials were replaced with 3-(tert-butyl)-2,5-dihydroxybenzaldehyde (0.87 g, 4.5 mmol) and 4-(trifluoromethyl)aniline (0.73 g, 4.5 mmol). The final product was a yellow powder, L3 (1.31 g, 86% yield). 1 H NMR (400 MHz, CHLOROFORM- D) δ 8.53 (s, 1H, -CH=N ), 7.68 (d, J = 8.2 Hz, 2H), 7.35 (d, J = 8.1 Hz, 2H), 7.00 (d, J = 3.0 Hz, 1H), 6.74 (d, J =3.0 Hz, 1H), 1.46 (s, 9H, -tBu ). 19 F NMR (376 MHz, CHLOROFORM- D ) δ -62.07. 13 CNMR (101 MHz, CHLOROFORM- D ) δ 164.66, 155.15, 151.64, 147.25, 139.67, 126.73,126.69, 121.55, 120.14, 118.52, 115.31, 77.42, 77.10, 76.79, 35.12, 29.29. Example 4: Preparation of 2-tert-butyl-6-(((4-tert-butylphenyl)imino))methyl)1,4-benzenediol The difference between this example and Example 1 is that the raw materials were replaced with 3-(tert-butyl)-2,5-dihydroxybenzaldehyde (0.8 g, 4.1 mmol) and 4-(tert-butyl)aniline (0.61 g, 4.1 mmol). The final product was a yellow powder, L4 (1.12 g, 90% yield). 1 H NMR (400 MHz, CHLOROFORM- D ) δ 8.54 (s, 1H, -CH=N ), 7.44 (d, J = 8.3Hz, 2H), 7.26 – 7.19 (m, 2H), 6.95 (d, J = 3.0 Hz, 1H), 6.72 (d, J = 2.7 Hz, 1H), 1.46 (s, 9H, -tBu ), 1.35 (s, 9H, -tBu ). 13 C NMR (101 MHz, CHLOROFORM- D) δ 162.16,154.99, 150.17, 146.99, 145.84, 139.35, 126.37, 120.86, 119.08, 118.95,115.11, 77.44, 77.13, 76.81, 35.08, 34.69, 31.69, 31.47, 29.35, 22.76, 14.23. Example 5: Preparation of catalyst (I1) Under nitrogen protection, ligand (II1) (1 mmol) and 2 eq. NaH were dissolved in 20 mL of toluene and stirred for 1 h. Then, 0.5 eq of titanium tetrachloride (TiCl4) was added, and the reaction was continued for another 1 h. Under nitrogen protection, the solution was filtered through filter paper and washed three times with toluene (20 mL). The filtrate was collected and concentrated, then recrystallized from n-hexane to obtain a red solid catalyst (370 mg, 91% yield). 1 H NMR (600 MHz, DMSO-D6) δ 8.83 (s, 2H, -CH=N ), 7.33 (d, J =8.3 Hz, 4H), 7.26 (s, 4H), 6.88 (d, J = 3.1 Hz, 2H), 6.85 (d, J = 2.2 Hz, 2H), 2.33 (s, 6H, -Me ), 1.38 (s, 18H, -tBu ). 13 C NMR (101 MHz, DMSO) δ 164.11,145.65, 137.81, 137.74, 130.40, 129.37, 128.67, 125.78, 121.70, 115.71,67.48, 34.90, 29.62, 25.59, 21.52, 21.09. Example 6: Preparation of catalyst (I2) Under nitrogen protection, ligand (II2) (1 mmol) and 2 eq. NaH were dissolved in 20 mL of toluene and stirred for 1 h. Then, 0.5 eq. TiCl4 was added, and the reaction was continued for 1 h. Under nitrogen protection, the solution was filtered through filter paper and washed three times with toluene (20 mL). The filtrate was collected and concentrated, and recrystallized from n-hexane to give a red solid catalyst (370 g, 91% yield). 1 H NMR (600 MHz, DMSO-) D 6) δ 8.99 (s, 2H, -CH=N ), 7.02 (d, J= 2.9 Hz, 2H), 6.90 (d, J =1.6 Hz, 2H), 1.38 (s, 18H, -tBu ). 13 C NMR (101 MHz, DMSO) δ 173.82, 153.35,149.95, 138.55, 137.81, 129.36, 128.66, 125.77, 121.73, 118.81, 116.08,67.48, 55.42, 35.45, 35.00, 30.78, 29.58, 29.51, 25.59, 21.50. Example 7: Preparation of catalyst (I3) Under nitrogen protection, ligand (II3) (1 mmol) and 2 eq. NaH were dissolved in 20 mL of toluene and stirred for 1 h. Then, 0.5 eq. TiCl4 was added, and the reaction was continued for 1 h. Under nitrogen protection, the mixture was filtered through filter paper and washed three times with toluene (20 mL). The filtrate was collected and concentrated, and recrystallized from n-hexane to give a red solid catalyst (370 g, 91% yield). 1 H NMR(600 MHz, DMSO-D6) δ 8.80 (s, 2H, -CH=N), 7.29 (d, J = 8.3 Hz, 2H), 7.24 (d,J = 7.6 Hz, 2H), 7.20 – 7.12 (m, 4H), 6.84 (d, J = 3.2 Hz, 2H), 6.64 (d, J =8.3 Hz, 2H), 1.32 (s, 18H, -tBu).13C NMR (101 MHz, DMSO) δ 129.37, 128.68,126.64, 125.79, 67.48, 29.61, 25.59, 21.52. Example 8: Preparation of catalyst (I4) Under nitrogen protection, ligand (II4) (1 mmol) and 2 eq. NaH were dissolved in 20 mL of toluene and stirred for 1 h. Then, 0.5 eq. TiCl4 was added, and the reaction was continued for 1 h. Under nitrogen protection, the mixture was filtered through filter paper and washed three times with toluene (20 mL). The filtrate was collected and concentrated, and recrystallized from n-hexane to give a red solid catalyst (370 g, 91% yield).

[0035] Application Example 1: Ethylene polymerization was carried out using the catalysts prepared in Examples 5-8, respectively. The specific polymerization methods are as follows: Inside a glove box, 28 mL of dry heptane and a magnetic stir bar were added to a 250 mL autoclave (equipped with a magnetic stirrer, oil bath heating device, and thermometer). Then, 5 μmol of the supported catalyst prepared in Examples 5-8 was injected into the pressure flask; subsequently, 500 equivalents of Et₂AlCl were added to the same flask. The flask was connected to the ethylene gas line, and the temperature was adjusted to the target value and held at equilibrium for 15 minutes. The reaction was vigorously stirred for 0.5 hours at an ethylene pressure of 8 atm to carry out the polymerization reaction. After reaching the set reaction time, 5% acidic methanol was added to terminate the polymerization reaction. The polymer was separated by filtration and then dried under low pressure.

[0036] The results of ethylene polymerization catalyzed by the catalysts prepared in Examples 5-8 are shown in Table 1: Wherein, a) polymerization conditions: catalyst 1 μmol, n-heptane = 30 mL, ethylene = 8 atm, time = 10 min; yield and activity data are the average of at least two experiments; b) activity unit is 10⁶ g·mol⁻¹. -1 ·h -1 c. Viscosity-average molecular weight = 104 gmol -1 The molecular weight was determined in decahydronaphthalene at 150°C using an IVS800 fully automated viscosity measurement system; the melting point was determined using differential scanning calorimetry (DSC, during the second heating process).

[0037] As shown in Table 1, the catalyst in this application can catalyze ethylene polyolefins under certain conditions, with the highest activity reaching 3.92 × 10⁶ g·mol⁻¹. -1 •h -1 It has a melting point of up to 136.7℃ and a viscosity-average molecular weight of up to 446.0×104 g / mol, making it suitable for preparing ultra-high molecular weight polyethylene.

[0038] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention.

Claims

1. A method for preparing a supported titanium metal catalyst, characterized in that, The structural formula is shown in Figure 1.

2. The method for preparing the supported titanium metal catalyst according to claim 1, characterized in that, R1 and R2 are selected from hydrogen, C1-C20 hydrocarbon groups, substituted silyl groups, C1-C20 substituted hydrocarbon groups, phenyl or substituted phenyl groups; R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17 and R18 are independently selected from hydrogen, C1-C20 hydrocarbon groups, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silyl groups, C1-C20 substituted hydrocarbon groups, phenyl or substituted phenyl groups.

3. The method for preparing the supported titanium metal catalyst according to claim 1, characterized in that, X and Y are independently derived from fluorine, chlorine, bromine, iodine, C1-C20 hydrocarbon groups, aryl groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, boron-containing groups, aluminum-containing groups, phosphorus-containing groups, silicon-containing groups, or tin-containing groups, and M can be a metal such as lithium, sodium, or potassium.

4. The method for preparing the supported titanium metal catalyst according to claim 1, characterized in that, As shown in reaction (A), the specific preparation steps of the supported catalyst are as follows: Under an argon or nitrogen atmosphere, ligands with the structure of formula (II) and metal source M are added to a solvent and reacted at room temperature for 1-12 hours. Then, a titanium source solution is added. After reacting at room temperature for 1-12 hours, the mixture is filtered to remove the solvent, yielding a complex with the structure of formula (IM). A certain amount of the complex (IM) is added to an organic solvent with a supported substrate, stirred for 1-120 minutes, and filtered and washed to obtain the supported catalyst shown in Figure 1. The mass ratio of the complex (IM) to the support in the supported catalyst is 1:20-50000.

5. The method for preparing the supported titanium metal catalyst according to claim 1, characterized in that, The structural formula of reaction (A) is as follows: 。 6. The method for preparing the supported titanium metal catalyst according to claim 1, characterized in that, R1 is selected from hydrogen, C1-C12 hydrocarbon group, substituted silicon group, C1-C12 substituted hydrocarbon group, phenyl or substituted phenyl group; R2, R3, R4, R5, R6, R7, R8 and R9 are independently selected from hydrogen, C1-C12 hydrocarbon group, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silicon group, C1-C12 substituted hydrocarbon group, phenyl or substituted phenyl group.

7. The method for preparing the supported titanium metal catalyst according to claim 4, characterized in that, The carrier is selected from one or more solid inorganic or organic materials such as silicon dioxide, magnesium oxide, titanium dioxide, zinc oxide, aluminum oxide, magnesium chloride, glass fiber, graphene, expanded graphite, ammonium polyphosphate, and carbon black.

8. The method for preparing the supported titanium metal catalyst according to claim 4, characterized in that, The ligand having the structure of formula (II) is composed of (a) and (b) Prepared by reaction in an organic solvent.

9. The application of the supported titanium metal catalyst according to claim 1 in olefin polymerization.

10. An application of catalytic olefin polymerization, characterized in that, Includes the following steps: Olefins are polymerized in organic solvents under conditions of 0-200℃ and 0.1-50MPa pressure. The olefins include one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecene, and 1-octadecene. The polymerization process employs slurry polymerization, loop polymerization, gas-phase polymerization, or other forms of polymerization technology. The organic solvent is a hydrocarbon with 12 carbon atoms, including but not limited to hexane, toluene, chlorobenzene and mixtures thereof.

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