Synthesis of hybrid coordination titanium zirconium hafnium metal catalyst and application of hybrid coordination titanium zirconium hafnium metal catalyst in olefin polymerization

Abstract

The invention discloses synthesis of a pyridylamine and thioether amine hybrid coordination titanium-zirconium-hafnium metal catalyst and application of the pyridylamine and thioether amine hybrid coordination titanium-zirconium-hafnium metal catalyst in the field of polyolefin. The three-dimensional effect and the electronic effect of the model metal catalyst can be conveniently regulated and controlled by changing substituent groups, so that different catalytic properties are realized, and polyolefin high polymer materials with various structures and various properties are prepared. The novel pyridylamine and thioether amine hybridized and coordinated titanium-zirconium-hafnium metal catalyst has the characteristics of simple synthesis, high product yield, rich and diversified structures and high activity; in the presence of a promoter (such as [Ph3C] [B (C6F5) 4] and the like), the compound shows extremely high activity, and the highest activity is 28200kg (PE). Mol <-1 > (Hf). H <-1 >. In addition, the pyridylamine and thioether amine hybrid coordination titanium-zirconium-hafnium metal catalyst reported by the invention has good high temperature resistance and copolymerization performance, and is suitable for olefin high-temperature solution polymerization to prepare a high-performance polyolefin elastomer (POE). Therefore, the report of the invention has original innovation, and can enhance the competitive capacity of the polyolefin high polymer material technology market in China.

Description

Technical Field

[0001] This invention relates to the preparation of coordination polymerization metal catalysts and their application in the field of polyolefins. Background Technology

[0002] Polyolefins are polymer materials polymerized from olefin monomers and are essential materials for national economic development and daily life. Polyolefins are an important class of polymer materials, mainly including LDPE, LLDPE, HDPE, PP, EPR and POE. These materials have low density, excellent wear resistance and chemical stability, and good processing performance. Their raw materials are widely available and low cost, and they are widely used in packaging, construction, automobile manufacturing, electronics and electrical appliances and agriculture. With the development of technology, their performance is constantly optimized and their application prospects are becoming increasingly broad. With the development of molecular catalysts, the precise control of the molecular structure of polyolefins has been achieved through active olefin polymerization. Non-metallocene catalysts provide a wide range of space for catalyst design and synthesis due to their structural diversity and unique catalytic performance. In 2005, Lancaster et al. reported a titanium metal catalyst hybridized with salicylaldehyde imine and pyrrolidine amine (J.Am.Chem.Soc.,2004,126(35):10798-10799). This synthetic method retains the stereochemical rigidity of the octahedral geometry while producing novel catalysts that combine the advantageous properties of two parent ligands. In 2014, Yuguo Ma et al. reported a class of hybrid titanium metal catalysts with two different salicylaldehyde imine ligands (Macromolecules, 2014, 47(23): 8164-8170), further expanding the research scope of hybrid catalysts.

[0003] This invention reports the synthesis of a pyridine amine and thioether amine hybrid coordination titanium-zirconium-hafnium metal catalyst and its application in olefin polymerization. By changing the substituents, the steric and electronic effects of this type of metal catalyst can be easily tuned, thereby achieving different catalytic properties and preparing polyolefin polymers with various structures and properties. The novel pyridine amine and thioether amine hybrid coordination titanium-zirconium-hafnium metal catalyst reported in this invention features simple synthesis, high product yield, diverse structures, and high activity; it exhibits extremely high activity, reaching up to 28200 kg (PE)·mol in the presence of co-catalysts (such as [Ph3C][B(C6F5)4]). -1 (Hf)·h -1 Furthermore, the pyridine amine and thioether amine hybridized coordination titanium-zirconium-hafnium metal compounds reported in this invention possess excellent high-temperature resistance and copolymerization properties, making them suitable for high-temperature solution polymerization of olefins to prepare high-performance polyolefin elastomers (POEs). Therefore, this invention is original and innovative, and can enhance the competitiveness of my country's polyolefin polymer materials technology market. Summary of the Invention

[0004] The purpose of this invention is to provide a synthesis of a pyridine amine and thioether amine hybrid coordination titanium zirconium hafnium metal catalyst and its application in the preparation of polyolefin elastomers.

[0005] This invention provides a titanium-zirconium-hafnium metal catalyst with hybrid coordination of pyridine amine and thioether amine as shown in formula (I):

[0006]

[0007] Where M is selected from titanium, zirconium, and hafnium; R 1 Selected from C1-C8 alkyl, isopropyl, fluorine, chlorine, and bromine; R 2 Selected from C1-C8 alkyl, phenyl, and substituted phenyl groups.

[0008] Preferably, the metal compound of the present invention is selected from any one of the following complexes:

[0009] C1:L1L3HfMe2,L1=pyridine-CH=N-2,6-diisopropylphenyl,L3=C6H5-NH-C6H5-S-Me;

[0010] C2:L2L3HfMe2,L2=pyridine-CH=N-2,6-dimethylphenyl,L3=C6H5-NH-C6H5-S-Me;

[0011] C3:L2L4HfMe2,L2=pyridine-CH=N-2,6-dimethylphenyl,L4=C6H5-NH-C6H5-S-C6H5;

[0012] This invention provides a method for preparing the above-mentioned pyridine amine and thioether amine hybrid coordinated titanium zirconium hafnium metal catalyst, comprising the following steps:

[0013] A metal chloride was dissolved in 30-100 mL of anhydrous solvent, and 4.0-5.0 molar equivalents of methyl magnesium bromide were added. The mixture was stirred at low temperature for 2 hours under nitrogen protection, and then 1 molar equivalent of pyridineimine ligand was added. The mixture was stirred for another 5 hours. The solvent was removed under reduced pressure, and the mixture was extracted with a good solvent to obtain a pyridineamine-coordinated titanium-zirconium-hafnium metal catalyst. Under a nitrogen atmosphere, the pyridineamine-coordinated titanium-zirconium-hafnium metal catalyst was dissolved in 20-80 mL of anhydrous solvent, and 1 molar equivalent of thioetheramine ligand was added. The mixture was reacted for 1-6 hours, and the solvent was removed under reduced pressure. The mixture was extracted with a good solvent to obtain the pyridineamine and thioetheramine hybridized coordinated titanium-zirconium-hafnium metal catalyst described in claim 1.

[0014] In the above preparation method, the metal salt MCl4 is selected from one of TiCl4, ZrCl4, and HfCl4.

[0015] In the above preparation method, the anhydrous solvent is selected from benzene, toluene, xylene, and n-hexane; the good solvent is selected from n-hexane, n-pentane, n-heptane, cyclohexane, and toluene.

[0016] This invention also provides the application of the above-mentioned pyridine amine and thioether amine hybrid coordination titanium zirconium hafnium metal catalyst for catalytic olefin polymerization.

[0017] In the above applications, the olefin is one or more of ethylene, propylene, styrene, 1-butene, 1-hexene, 1-octene, and norbornene.

[0018] The catalyst described above also contains a co-catalyst, which is one or more of tripentafluorophenylboron, triphenylcarbazide tetra(pentafluorophenyl)borate, aluminoxane, alkylaluminum, and alkylaluminum chloride. The aluminoxane is methylaluminoxane, ethylaluminoxane, or isobutylaluminoxane; the alkylaluminum is trimethylaluminum, triethylaluminum, triisobutylaluminum, or tri-n-hexylaluminum; and the alkylaluminum chloride is diethylaluminum chloride, sesqui-diethylaluminum chloride, or ethylaluminum dichloride.

[0019] In the above polymerization reaction, the polymerization temperature is 0-200℃, the polymerization pressure is 0.1-5MPa, and the polymerization solvent is one or more of toluene, hexane, and heptane.

[0020] This invention provides the preparation of a pyridine amine and thioether amine hybrid coordination titanium-zirconium-hafnium metal catalyst, and its application in catalyzing olefin polymerization. The pyridine amine and thioether amine hybrid coordination titanium-zirconium-hafnium metal catalyst reported in this invention is characterized by simple preparation, high activity, high temperature resistance, good copolymerization performance, and diverse structures, making it suitable for high-temperature solution polymerization of olefins to prepare polyolefin elastomers (POEs). Attached Figure Description

[0021] Figure 1 This is the 1H NMR spectrum of catalyst C1.

[0022] Figure 2 This is the 1H NMR spectrum of catalyst C2.

[0023] Figure 3 This is the 1H NMR spectrum of catalyst C3.

[0024] Figure 4 This is the crystal structure diagram of catalyst C1.

[0025] Figure 5 This is the crystal structure diagram of catalyst C3.

[0026] Figure 6 The GPC spectrum of the polymer prepared in Example 4 is shown.

[0027] The present invention is further illustrated by examples, but is not limited thereto. These examples will enable those skilled in the art to gain a more comprehensive understanding of the invention.

[0028] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0029] In this invention, pyridinium ligands L1 and L2 were synthesized according to the method described in the literature (Eur.J.Inorg.Chem.,2023,26(8),e202200725), and thioetheramine ligands L3 and L4 were synthesized according to the method described in the literature (Inorg.Chem.,2024,63(42),19676-19686).

[0030] The present invention is described below with reference to specific embodiments.

[0031] Example 1: Preparation of Catalyst C1

[0032]

[0033] Hafnium tetrachloride (6.00 g, 18.8 mmol) was weighed and added to 60 mL of anhydrous toluene. Under conditions of -40 °C (acetonitrile-liquid nitrogen bath), 30.0 mL / 90.1 mmol methyl magnesium bromide solution (3 M) was slowly added, and the mixture was stirred for 2 hours. Then, ligand L1 (5 g / 18.8 mmol) was added, and the mixture was reacted at -40 °C in the dark for 2 hours, then allowed to return to room temperature for another 12 hours. After the reaction was complete, the solvent was removed, and the product was extracted with toluene and filtered to obtain the target product 1. Under a nitrogen atmosphere, product 1 (1.52 g, 3 mmol) was weighed and added to 15 mL of anhydrous toluene. Simultaneously, ligand L3 (0.65 g, 3 mmol) was weighed in another Shrek flask and added to 15 mL of anhydrous toluene. The L3 solution was slowly added to the product 1 solution, and the mixture was stirred for 3 hours. After removing the solvent, the product was washed with n-hexane and filtered to obtain 1.45 g of product, with a yield of 68.7%. 1H NMR (400MHz, C6D6): δ8.17(d,J=5.2Hz,1H),7.28(dd,J=7.0,2.4Hz,1H),7.27(m,1H),7.23(d,J=1.9Hz,1H),7.21(s,1H),7.19(s,1H ),7.17(d,J=1.7Hz,1H),7.04(d,J=1.1Hz,1H),7.02(m,1H),6.98(m,1H),6.93(ddd,J=8.6,7.2,1.6Hz,1H),6.72(td,J=7.9,1.6Hz,1 H),6.51–6.43(m,3H),6.19(t,J=6.4Hz,1H),5.13(q,J=6.9Hz,1H),3.93(p,J=6.8Hz,1H),3.65(p,J=6.8Hz,1H),2.16(s,3H),1.41( d,J=6.7Hz,3H),1.36(d,J=2.2Hz,3H),1.34(d,J=2.4Hz,3H),1.25(d,J=6.8Hz,3H),1.10(d,J=6.9Hz,3H),0.33(d,J=9.8Hz,6H)ppm. 13 C NMR (100MHz, C6D6): δ168.37,160.05,150.24,149.90,146.90,145.29,137.71,133.69,130.81,129.36,129.58,124.86,124.52,124.33 ,124.14,121.58,121.06,117.52,117.48,70.63,54.77,53.54,27.77,27.26,26.03,25.87,25.76,24.92,23.26,22.60ppm.Anal.Calcd for C 34 H 43 N3SHf:C,57.98;H,6.15;N,5.97.Found:C,57.88;H,6.08;N,5.91.

[0034] Example 2: Preparation of catalyst C2

[0035]

[0036] Hafnium tetrachloride (7.62 g, 23.8 mmol) was weighed and added to 60 mL of anhydrous toluene. The mixture was then slowly added to a 38.1 mL / 114.0 mmol methyl magnesium bromide solution (3 M) at -40 °C (acetonitrile-liquid nitrogen bath), and stirred for 2 hours. Ligand L2 (5 g / 23.8 mmol) was then added, and the mixture was reacted at -40 °C in the dark for 2 hours, followed by a 12-hour reaction at room temperature. After the reaction was complete, the solvent was removed, and the mixture was extracted with toluene and filtered to obtain the target product 2. Under a nitrogen atmosphere, product 2 (1.35 g, 3 mmol) was weighed and added to 15 mL of anhydrous toluene. Simultaneously, ligand L3 (0.65 g, 3 mmol) was weighed in another Shrek flask and added to 15 mL of anhydrous toluene. The L3 solution was slowly added to the product 2 solution, and the mixture was stirred for 1 hour. The solvent was removed, the mixture was washed with n-hexane, and filtered to obtain 1.23 g of product, with a yield of 63.44%. 1 H NMR (400MHz, C6D6): δ8.60(m,1H),7.29(d,J=4.3Hz,4H),7.23–7.19(m,3H),7.12(dd,J=8 .0,1.6Hz,1H),7.07(td,J=8.1,7.5,4.7Hz,2H),6.95(ddd,J=8.5,7.5,1.6Hz,1H),6.72(t d,J=7.8,1.6Hz,1H),6.52(m,1H),6.47–6.44(m,2H),6.21(m,1H),4.98(q,J=6.8Hz,1H),2 .60(s,3H),2.35(s,3H),2.15(s,3H),1.26(d,J=6.8Hz,3H),0.36(s,3H),0.29(s,3H)ppm. 13 CNMR (100MHz, C6D6): δ170.24,161.77,149.53,148.28,138.00,137.47,135.65,134.11,130.76,130.30,129.89,129.12,12 4.81,124.14,121.72,121.41,119.91,117.16,116.81,69.39,53.53,53.48,24.20,22.18,21.12,18.84ppm.Anal.Calcdfor C 30 H 35 N3SHf:C,55.59;H,5.44;N,6.48.Found:C,55.55;H,5.39;N,6.42.

[0037] Example 3: Preparation of catalyst C3

[0038]

[0039] Hafnium tetrachloride (7.62 g, 23.8 mmol) was weighed and added to 60 mL of anhydrous toluene. Under conditions of -40 °C (acetonitrile-liquid nitrogen bath), 38.1 mL / 114.0 mmol methyl magnesium bromide solution (3 M) was slowly added, and the mixture was stirred for 2 hours. Then, ligand L2 (5 g / 23.8 mmol) was added, and the mixture was reacted at -40 °C in the dark for 2 hours, then allowed to return to room temperature for another 12 hours. After the reaction was complete, the solvent was removed, and the product was extracted with toluene and filtered to obtain the target product 2. Under a nitrogen atmosphere, product 2 (0.45 g, 1 mmol) was weighed and added to 15 mL of anhydrous toluene. Simultaneously, ligand L4 (0.28 g, 1 mmol) was weighed in another Shrek flask and added to 15 mL of anhydrous toluene. The L4 solution was slowly added to the product 2 solution, and the mixture was stirred for 3 hours. After removing the solvent, the product was washed with n-hexane and filtered to obtain 0.48 g of the product, with a yield of 67.6%. 1 H NMR (400MHz, C6D6): δ8.71(m,1H),7.32(dd,J=8.3,1.3Hz,2H),7.29–7.25(m,2H), 7.14–7.11(m,4H),7.08–7.01(m,2H),6.96(m,1H),6.93–6.83(m,3H),6.83–6.76(m ,2H),6.60–6.54(m,2H),6.40–6.36(td,J=7.6,1.3Hz,1H),6.28–6.24(m,1H),4.99 (q,J=6.8Hz,1H),2.49(s,3H),2.33(s,3H),1.32(d,J=6.8Hz,3H),0.21(s,6H)ppm. 13 C NMR (100MHz, C6D6): δ171.15,162.62,149.10,148.06,138.04,137.94,137.32,136.26,135.58,131.24,130.79,129.97,129.10,128.9 0,128.71,126.95,125.16,124.30,121.69,121.45,117.83,117.75,117.44,69.13,55.15,54.36,21.99,21.36,18.95ppm.Anal.Calcd forC 35 H 37 N3SHf:C,59.19;H,5.25;N,5.92.Found:C,59.11;H,5.19;N,5.87.

[0040] Example 4: C1-catalyzed ethylene polymerization

[0041] A 100 mL steel reactor equipped with a magnetic induction device was used for the polymerization reaction. 50 mL of toluene was injected using a syringe, and the reactor contents were heated to 80 °C. The reactor was then saturated with 40 atm ethylene. In a glove box, 5 μmol of catalyst C1, 0.25 mmol of methylaluminoxane (MAO), and 6 μmol of triphenylmethyltetra(pentafluorophenyl)borate were added, dissolved in toluene, and transferred to a catalyst storage tube through a stainless steel pipe. Nitrogen gas (above 45 atm) was then pressurized into the reactor. During polymerization, the reaction pressure was maintained at 40 atm by continuously introducing ethylene gas. After the set reaction time of 2 minutes, 2 mL of ethanol was pressurized into the reactor under nitrogen (above 45 atm). The reactor was cooled and vented. The contents of the reactor were poured into a large amount of ethanol, causing polymer precipitation. The polymer was obtained by filtration, washed with a small amount of ethanol, and finally vacuum dried overnight before weighing. Polymerization activity: 28200 kg·mol⁻¹ -1 ·h -1 Polymer M w =98.4×10 4 g·mol -1 M w / M n =2.7.

[0042] Example 5: C1-catalyzed ethylene polymerization

[0043] The polymerization process and reaction conditions were the same as in Example 5, with a selected temperature of 100°C and a C1 catalyst used. Polymerization activity: 22500 kg·mol⁻¹ -1 ·h -1 Polymer M w =64.1×10 4 g·mol -1 M w / M n =2.4.

[0044] Example 6: C1-catalyzed ethylene polymerization

[0045] The polymerization process and reaction conditions were the same as in Example 5, with a selected temperature of 120°C and a C1 catalyst used. Polymerization activity: 17940 kg·mol⁻¹ -1 ·h -1 Polymer M w =27.5×10 4 g·mol -1 M w / M n =2.2.

[0046] Example 7: C2-catalyzed ethylene polymerization

[0047] The polymerization process and reaction conditions were the same as in Example 5, and the catalyst used was C2. Polymerization activity: 22980 kg·mol⁻¹ -1 ·h -1 Polymer M w =31.5×10 4 g·mol -1 M w / M n =2.6.

[0048] Example 8: C2-catalyzed ethylene polymerization

[0049] The polymerization process and reaction conditions were the same as in Example 5, with a selected temperature of 100°C and a C2 catalyst used. Polymerization activity: 19980 kg·mol⁻¹ -1 ·h -1 Polymer M w =26.8×10 4 g·mol -1 M w / M n =2.4.

[0050] Example 9: C2-catalyzed ethylene polymerization

[0051] The polymerization process and reaction conditions were the same as in Example 5, with a selected temperature of 120°C and a C2 catalyst used. Polymerization activity: 16020 kg·mol⁻¹ -1 ·h -1 Polymer M w =20.1×10 4 g·mol -1 M w / M n =2.0.

[0052] Example 10: C3-catalyzed ethylene polymerization

[0053] The polymerization process and reaction conditions were the same as in Example 5, and the catalyst used was C3. Polymerization activity: 19080 kg·mol⁻¹ -1 (Hf)·h -1 Polymer M w =57.6×10 4 g·mol -1 M w / M n =2.0.

[0054] Example 11: C3-catalyzed ethylene polymerization

[0055] The polymerization process and reaction conditions were the same as in Example 5, with a selected temperature of 100°C and a C3 catalyst used. Polymerization activity: 17220 kg·mol⁻¹ -1(Hf)·h -1 Polymer M w =32.4×10 4 g·mol -1 M w / M n =2.1.

[0056] Example 12: C3-catalyzed ethylene polymerization

[0057] The polymerization process and reaction conditions were the same as in Example 5, with a selected temperature of 120°C and a C3 catalyst used. Polymerization activity: 13980 kg·mol⁻¹ -1 (Hf)·h -1 Polymer M w =28.5×10 4 g·mol -1 M w / M n =2.1.

[0058] Example 13: C1-catalyzed copolymerization of ethylene / 1-octene

[0059] A 100 mL steel reactor equipped with a magnetic induction chamber was used for the polymerization reaction. A mixture of 26 mL toluene and 24 mL 1-octene (total 50 mL) was injected using a syringe. The reactor contents were heated to 100 °C, and the reactor was saturated with ethylene at 20 atm. In a glove box, 5 μmol of catalyst C1, 0.25 mmol of methylaluminoxane MAO, and 6 μmol of triphenylmethyltetra(pentafluorophenyl)borate were added, dissolved in toluene, and transferred to a catalyst storage tube through a stainless steel pipe. Nitrogen gas (above 25 atm) was then pressurized into the reactor. During polymerization, the reaction pressure was maintained at 20 atm by continuously introducing ethylene gas. After the set reaction time of 2 minutes, 2 mL of ethanol was pressurized into the reactor under nitrogen (above 25 atm). After the reactor cooled and the atmosphere was vented, the contents were poured into a large amount of ethanol, causing polymer precipitation. The polymer was obtained by filtration, washed with a small amount of ethanol, and finally vacuum dried overnight and weighed. Polymerization activity: 27900 kg·mol⁻¹ -1 ·h -1 Polymer M w =13.7×10 4 g·mol -1 M w / M n =2.1, the content of 1-octene in the copolymer is 7.9 mol%.

[0060] Example 14: C1-catalyzed copolymerization of ethylene / 1-octene

[0061] The polymerization process and conditions were the same as in Example 12, except that the amount of 1-octene was changed to 16 mL, the selected temperature was 80 °C, and the catalyst used was C1. Polymerization activity: 21120 kg·mol⁻¹ -1 (Hf)·h -1 Polymer M w =31.2×10 4 g·mol -1 M w / M n =3.3, the content of 1-octene in the copolymer is 3.0 mol%.

[0062] Example 15: C1-catalyzed copolymerization of ethylene / 1-octene

[0063] The polymerization process and reaction conditions were the same as in Example 12, with a selected temperature of 80°C and a C1 catalyst used. Polymerization activity: 25200 kg·mol⁻¹ -1 ·h -1 Polymer M w =20.6×10 4 g·mol -1 M w / M n =2.7, the content of 1-octene in the copolymer is 5.9 mol%.

[0064] Example 16: C1-catalyzed copolymerization of ethylene / 1-octene

[0065] The polymerization process and reaction conditions were the same as in Example 12, with a selected temperature of 120°C and a C1 catalyst used. Polymerization activity: 25020 kg·mol⁻¹ -1 (Hf)·h -1 Polymer M w =15.0×10 4 g·mol -1 M w / M n =1.9, the content of 1-octene in the copolymer is 6.2 mol%.

[0066] Example 17: C2-catalyzed copolymerization of ethylene / 1-octene

[0067] The polymerization process and reaction conditions were the same as in Example 12, and the catalyst used was C2. Polymerization activity: 24660 kg·mol⁻¹ -1 (Hf)·h -1 Polymer M w =15.8×10 4 g·mol -1 M w / M n =2.3, the content of 1-octene in the copolymer is 6.3 mol%.

[0068] Example 18: C3-catalyzed copolymerization of ethylene / 1-octene

[0069] The polymerization process and reaction conditions were the same as in Example 12, and the catalyst used was C3. Polymerization activity: 19800 kg·mol⁻¹ -1 (Hf)·h -1 Polymer M w =15.3×10 4 g·mol -1 M w / M n =2.2, the content of 1-octene in the copolymer is 5.8 mol%.

Claims

1. A class of pyridine amine and thioether amine hybrid coordinated titanium zirconium hafnium metal catalysts, the structure of which is shown in formula (I): Where M is selected from titanium, zirconium, and hafnium; R 1 Selected from C1-C8 alkyl, isopropyl, fluorine, chlorine, and bromine; R 2 Selected from C1-C8 alkyl, phenyl, and substituted phenyl groups.

2. The preparation method of the pyridine amine and thioether amine hybrid coordinated titanium zirconium hafnium metal catalyst according to claim 1 comprises the following steps: dissolving the metal salt MCl4 in 30-100 mL of anhydrous solvent, adding 4.0-5.0 molar equivalents of methyl magnesium bromide, stirring at low temperature for 2 hours under nitrogen protection, then adding 1 molar equivalent of pyridineimine ligand, and continuing stirring for 5 hours; removing the solvent under reduced pressure, and extracting with a good solvent to obtain the pyridine amine coordinated titanium zirconium hafnium metal catalyst; dissolving the pyridine amine coordinated titanium zirconium hafnium metal catalyst in 20-80 mL of anhydrous solvent under a nitrogen atmosphere, adding 1 molar equivalent of thioether amine ligand, reacting for 1-6 hours, removing the solvent under reduced pressure, and extracting with a good solvent to obtain the pyridine amine and thioether amine hybrid coordinated titanium zirconium hafnium metal catalyst according to claim 1.

3. The preparation method according to claim 2, characterized in that: The metal salt MCl4 is selected from one of TiCl4, ZrCl4, and HfCl4.

4. The preparation method according to claim 2, characterized in that: The anhydrous solvent is selected from benzene, toluene, xylene, and n-hexane; The preferred solvent is selected from n-hexane, n-pentane, n-heptane, cyclohexane, and toluene.

5. A method for carrying out an olefin polymerization reaction, characterized in that: The catalyst for the reaction is the pyridine amine and thioether amine hybrid coordinated titanium zirconium hafnium metal catalyst as described in claim 1.

6. The method according to claim 5, characterized in that: The olefin is one or more of ethylene, propylene, styrene, 1-butene, 1-hexene, 1-octene, and norbornene.

7. The method according to claim 5, characterized in that: The catalyst also contains a co-catalyst, which is one or more of triphenylpentafluorophenylborone, triphenylcarbazide tetra(pentafluorophenyl)borate, aluminoxane, alkylaluminum and alkylaluminum chloride.

8. The method according to claim 7, characterized in that: The aluminum oxane is methylaluminoxane, ethylaluminoxane, or isobutylaluminoxane; the alkylaluminum is trimethylaluminum, triethylaluminum, triisobutylaluminum, or tri-n-hexylaluminum; and the alkylaluminum chloride is diethylaluminum chloride, sesqui-diethylaluminum chloride, or ethylaluminum dichloride.

9. The method according to claim 5, characterized in that: The polymerization temperature is 0-200℃, the polymerization pressure is 0.1-5MPa, and the polymerization solvent is one or more of toluene, hexane, and heptane.

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