Semi-metallocene catalyst as well as synthesis method and application thereof

Abstract

A semi-metallocene catalyst and a synthetic method and application thereof belong to the field of chemical engineering. The invention discloses a novel semi-metallocene catalyst which is stable in structure and excellent in heat resistance, and in the presence of a cocatalyst alkoxy aluminum or alkyl aluminum or organic boride, the heat resistance of the semi-metallocene catalyst is greatly improved. Ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar olefin monomer copolymerization, propylene and polar olefin monomer copolymerization or non-polar olefin monomer and polar olefin monomer multi-component copolymerization are efficiently catalyzed at a high polymerization temperature to efficiently prepare a high-end copolymerization olefin material. And synthesizing high-end propenyl elastomers and plastomers, vinyl elastomers and plastomers, styryl copolymers and the like. The method is simple in preparation process, safe, low in cost, convenient to operate, low in equipment requirement, small in energy consumption and small in environmental pollution.

Description

Technical Field

[0001] The present invention belongs to the fields of chemical products and chemical product reaction engineering, and relates to olefin coordination polymerization catalysts, catalyst synthesis and applications, specifically to half-metallocene catalysts, half-metallocene catalyst synthesis methods, polyolefins synthesized from such half-metallocene catalysts, applications of the obtained polyolefins, and metallocene polyolefin material synthesis processes. Background Art

[0002] High-end polyolefin materials (including metallocene polyolefins, ultra-clean polyolefins, medical polyolefins, thermoplastic elastomers, functional group copolymerized olefins, high-end pipes, etc.) are an important pillar in the development of the polyolefin industry. The key technology lies in olefin coordination polymerization catalysts. The reaction conditions for free radical polymerization of olefins initiated by initiators such as peroxides are demanding. Only at high temperatures (200–350 °C) and high pressures (200–300 MPa) can ethylene polymerize to prepare LDPE. Even more difficult is that propylene cannot achieve a propylene polymerization reaction even under high temperature and high pressure conditions. The DuPont-Dow Elastomets company uses a constrained geometry metallocene catalyst, which has high catalytic activity in the polymerization temperature range of 90 - 180 °C, and the obtained polyolefins have high molecular weights. Mitsui Petrochemical Industries, Ltd. of Japan [EP0495099 A1] uses an ethyl half-metallocene catalyst to catalyze the copolymerization of ethylene and α-olefins to synthesize the polyolefin elastomer Tafmer. Propylene-based elastomers are a new type of high-end polyolefin material, with strict requirements for catalysts. Currently, there are relatively few reports on catalysts suitable for synthesizing propylene-based elastomers, polymerization processes, and propylene-based elastomer products. Patent ZL201410132466.7 discloses a high-efficiency catalyst for synthesizing high-end propylene-based elastomers by solution polymerization process at a relatively high polymerization temperature.

[0003] Huang Sihuang, the inventor of the present invention, accidentally discovered a new type of half-metallocene catalyst. The catalyst has a stable structure and excellent heat resistance. In the presence of cocatalysts such as alkoxyaluminum or alkylaluminum or organic borides, it can efficiently catalyze the homopolymerization of ethylene, the homopolymerization of propylene, the copolymerization of ethylene and α-olefins, the copolymerization of propylene and α-olefins, the copolymerization of ethylene and polar olefin monomers, the copolymerization of propylene and polar olefin monomers, or the multiple copolymerization of non-polar olefin monomers and polar olefin monomers at a relatively high polymerization temperature, efficiently preparing high-end copolymerized olefin materials, synthesizing high-end propylene-based elastomers and plastics, vinyl elastomers and plastics, styrene-based copolymers, etc. The preparation process of the present invention is simple, safe, low-cost, convenient to operate, requires low equipment, has low energy consumption, and causes little environmental pollution. Summary of the Invention

[0004] The object of the present invention is to provide a half-metallocene catalyst, and the half-metallocene catalyst is a compound conforming to General Formula 1 or General Formula 2:

[0005]

[0006] In General Formula 1 or General Formula 2, where R1, R2 or R3 is H, a C1-C 30 alkane, a C3-C 30 alkane cycloalkane, a C6-C 30 aromatic hydrocarbon or a C6-C 30 haloaromatic hydrocarbon; where X is a halogen, a C1-C 30 alkane, a C3-C 30 alkane cycloalkane, a C6-C 30 aromatic hydrocarbon, a C6-C 30 haloaromatic hydrocarbon, a C6-C 30 nitroaromatic hydrocarbon or a C6-C 30 alkoxyaromatic hydrocarbon, where the halogen is Cl, Br, F, etc.; where M is a transition metal or a rare earth metal, selected from Ti, Zr, Hf, Ni, Pd, Ru, Rh, Fe, Co, Cr(III), Nd, Y, Sc, Sm, V, etc. The preparation process of this preparation method is simple, safe, low-cost, easy to operate, requires low equipment, consumes little energy, and causes little environmental pollution; the half-metallocene catalyst has good thermal stability and still has high activity at a polymerization temperature of 120-200 °C, and is suitable for solution polymerization, gas-phase bulk polymerization, gas-phase melt bulk polymerization or combined polymerization processes.

[0007] Another object of the present invention is to provide a synthesis method of a half-metallocene catalyst, and the synthesis method of the half-metallocene catalyst is to synthesize a half-metallocene catalyst conforming to General Formula 1 or General Formula 2.

[0008] Another object of the present invention is to provide an application of a half-metallocene catalyst, and the application of the half-metallocene catalyst is: in the presence of a cocatalyst, using the half-metallocene catalyst to catalyze the polymerization of ethylene or α-olefin, or the copolymerization of ethylene and α-olefin, or the copolymerization of propylene and α-olefin, where the α-olefin monomer is a C3-C 30 olefin, where the C3-C 30 is a C3-C 30 olefin, a C6-C 30 diene, a C3-C 30 olefin containing an oxygen atom; where C3-C 30The olefins are propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, norbornene, dicyclopentadiene or a mixture thereof; wherein the temperature of the polymerization or copolymerization is 30 - 200 °C, the time of the polymerization or copolymerization is 5 - 120 min, and the pressure of the polymerization or copolymerization is 0.05 - 40 MPa; wherein the process of the polymerization or copolymerization is a solution polymerization process, a gas phase polymerization process, a liquid phase bulk polymerization process, a slurry polymerization process, a loop polymerization process or a combined polymerization process; wherein the cocatalyst is an alkyl aluminum, an alkoxy aluminum or an organic boride, and the molar ratio of the cocatalyst to the half-metallocene catalyst is (50 - 2000):1.

[0009] Half-metallocene catalyst, characterized in that: the half-metallocene catalyst is a compound conforming to General Formula 1 or General Formula 2; wherein in General Formula 1 or General Formula 2, R1, R2 or R3 is H, C1-C 30 alkane, C3-C 30 alkane cycloalkane, C6-C 30 aromatic hydrocarbon or C6-C 30 haloaromatic hydrocarbon; wherein X is a halogen, C1-C 30 alkane, C3-C 30 alkane cycloalkane, C6-C 30 aromatic hydrocarbon, C6-C 30 haloaromatic hydrocarbon, C6-C 30 nitroaromatic hydrocarbon or C6-C 30 alkoxyaromatic hydrocarbon, wherein the halogen is Cl, Br, etc.; wherein M is a transition metal or a rare earth metal, selected from Ti, Zr, Hf, Ni, Pd, Ru, Rh, Fe, Co, Cr(III), Nd, Y, Sc, Sm or V, etc.

[0010] Synthesis method of half-metallocene catalyst, characterized in that: the synthesis method of the half-metallocene catalyst is to synthesize a half-metallocene catalyst conforming to General Formula 1. Specifically, General Formula 1 or General Formula 2 is not limited, but typical half-metallocene catalysts (1) to (16) are as follows:

[0011]

[0012]

[0013] Half-metallocene catalyst and synthesis method, characterized in that: the synthesis method of the half-metallocene catalyst includes the following steps:

[0014] (1) Add C4-C 30 organic amine or C4-C 30An organic alcohol is stirred at -70 to 100 °C, a dehydrogenating reagent is added, and the reaction is carried out for 20 hours. Then, filtration is performed, and the filter residue is washed with hexane 2 to 4 times. The filter residue is dried under vacuum, and then the filter residue is dissolved or dispersed in an organic solvent to obtain an organic amine salt or organic alcohol salt organic solvent solution in step (1); wherein the C4-C 30 organic amine or C4-C 30 The molar ratio of the organic alcohol to the dehydrogenating reagent is 1:(0.90 - 5.0), and the dehydrogenating reagent is n-butyllithium, Grignard reagent, sodium metal, potassium metal, lithium metal, etc.

[0015] (2) At -30 to 100 °C, a haloindene or haloindene derivative is added to the organic amine salt or organic alcohol salt organic solvent solution in step (1), stirred, and the reaction is carried out for 0.5 to 20 hours. Then, filtration is performed, and the organic solvent in the filtrate is removed under vacuum to obtain a ligand. The ligand is dissolved in an organic solvent to obtain a ligand organic solvent solution; wherein the molar ratio of the haloindene or haloindene derivative to the organic amine salt or organic alcohol salt is 1:(0.95 - 2.0), and the haloindene or haloindene derivative has a halogen substituent on the aryl group, and the halogen substituent is Br or Cl; typical ligands (1) to (16) are as follows:

[0016]

[0017] (3) A dehydrogenating reagent is added to the ligand organic solvent solution, stirred at -70 to 100 °C, and the reaction is carried out for 0.5 to 12 hours. Then, filtration is performed, and the filter residue is washed with hexane 2 to 4 times. The filter residue is dried under vacuum. Then, the filter residue is dissolved or dispersed in an organic solvent to obtain a ligand salt organic solvent solution in step (3). The molar ratio of the ligand to the dehydrogenating reagent is 1:(0.90 - 5.0);

[0018] (4) At -70 to 100 °C, a transition metal salt is added to the ligand salt organic solvent solution, stirred, and the reaction is carried out for 0.5 to 12 hours. Then, filtration is performed, and the organic solvent in the filtrate is removed under vacuum to obtain a half-metallocene catalyst solid powder of general formula 1 or general formula 2; wherein the molar ratio of the ligand salt to the transition metal salt is 1:(0.9 - 5.0).

[0019] Among them, the organic solvent is selected from saturated hydrocarbons of C5 to C 30 alicyclic hydrocarbons of C5 to C 30 aromatic hydrocarbons of C6 to C 30 saturated heterocyclic hydrocarbons of C3 to C 20 or paraffin oil or their mixed solvents, and toluene, xylene, dioxane, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane, or hexadecane, or their mixed solvents are selected;

[0020] Among them, the transition metal salt is a halide salt, alkyl salt, alkoxide salt, cycloalkyl salt or aryl salt of transition metals such as Ti, Zr, Hf, Ni, Pd, Ru, Rh, Fe, Co, Cr(III), Nd, Y, Sc, Sm or V;

[0021] Semi-metallocene catalyst and synthesis method and application thereof, characterized in that: the application of the semi-metallocene catalyst is: in the presence of a co-catalyst, using the semi-metallocene catalyst to catalyze the polymerization of ethylene or α-olefin, or the copolymerization of ethylene and α-olefin, or the copolymerization of propylene and α-olefin, where the α-olefin monomer is C3-C 100 olefin, where the C3-C 100 is an olefin of C3 to C 30 a diene of C6 to C 30 an olefin containing an oxygen atom of C3 to C 100 an olefin containing a nitrogen atom of C3 to C 100 or an olefin containing a halogen atom of C3 to C 100 or an olefin containing a functional group element of C3 to C 100 ; among them, the olefin of C3 to C 30 is propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, norbornene, dicyclopentadiene or a mixture thereof; where the temperature of the polymerization or copolymerization is 30 - 200 °C, the time of the polymerization or copolymerization is 5 - 300 min, and the pressure of the polymerization or copolymerization is 0.05 - 40 MPa; where the polymerization or copolymerization process is a solution polymerization process, a gas phase polymerization process, a liquid phase bulk polymerization process, a slurry polymerization process, a loop tube polymerization process or a combined polymerization process; where the co-catalyst is an alkyl aluminum, an alkoxy aluminum or an organic boride, and the molar ratio of the co-catalyst to the semi-metallocene catalyst is (5 - 2000):1.

[0022] It includes the following steps:

[0023] (1) Add an organic solvent, a semi-metallocene catalyst and a co-catalyst to the polymerization reactor, and the co-catalyst is an alkyl aluminum, an alkoxy aluminum or a mixture thereof; classic co-catalysts such as: trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-tert-butyl aluminum, trioctyl aluminum, monochloro diethyl aluminum, dichloroethyl aluminum, sesquiethyl aluminum chloride, MAO or modified MAO, etc., can be used alone or several co-catalysts can be used in combination, where the molar ratio of the semi-metallocene catalyst to the co-catalyst is 1:(5 - 2000), at 10 to 100 °C, stir for 5 - 30 min.

[0024] (2) Add ethylene or α-olefin for polymerization in a polymerization reactor. The polymerization temperature is 30 - 200 °C, the copolymerization time is 5 - 100 min, and the copolymerization pressure is 0.05 - 40 MPa; wherein the α-olefin is an olefin of C3 - C 30 or an olefin containing an oxygen atom of C3 - C 30 , wherein the olefin of C3 - C 30 is preferably propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 3-methyl-1-butene, cyclopentene, 4-methyl-1-pentene, 1,3-butadiene, isoprene, styrene, methylstyrene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, norbornene, ethylidene norbornene or its derivatives, halogenated olefins, hydroxy olefins, carboxy olefins, ester group olefins or their blends. Among them, the olefin containing an oxygen atom of C3 - C 30 is an olefin containing a hydroxyl group, an ester group or a carboxyl group; wherein the organic solvent is selected from saturated hydrocarbons of C5 - C 30 , alicyclic hydrocarbons of C5 - C 30 , aromatic hydrocarbons of C6 - C 30 or saturated heterocyclic hydrocarbons of C3 - C 20 or paraffin oil or their mixed solvents, and toluene, xylene, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane or hexadecane, or their mixed solvents are selected.

[0025] The application of the half-metallocene catalyst is to catalyze olefin polymerization to produce high-performance polyolefin plastic materials and polyolefin elastic materials. Among them, the polyolefin plastic materials and polyolefin elastic materials are suitable for various existing processing technologies, and are also suitable for various new processing technologies developed in the future. Specifically, there are extrusion, blow molding, single (double)-directional stretching film, wet (dry) film forming, foaming, rotational molding, casting and other processing technologies, as well as various uses suitable for processing into products. The various uses are mainly used for battery adhesive films, temperature and pressure resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, anti-creep materials, ship cables, fishing nets, agricultural films, unmanned aerial vehicles, home decorations, toys, non-structural materials for airplanes and high-speed trains, automotive interior parts, stab-resistant gloves, bulletproof vests or linings for hydrogen storage tanks, etc.

[0026] The following further illustrates the present invention in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the following embodiments. Specific Embodiments

[0027] Example 1

[0028] Preparation of the half-metallocene catalyst (1)

[0029]

[0030] (1) Add 80 mL of toluene, 1.83 grams of tertiary amine and n-butyllithium equimolar to the tertiary amine, stir at -50 °C for 2 hours, then raise the temperature to 50 °C and react for 5 hours. Filter, wash the filter residue with hexane twice (50 mL of hexane each time), and vacuum-dry the filter residue. Then dissolve or disperse the filter residue in 60 mL of toluene solvent to obtain the toluene solution of the tertiary amine salt in step (1);

[0031] (2) Add 4.87 grams of 7-bromoindene to the toluene solution of the tertiary amine salt in step (1), stir and react at -20 °C for 1 hour, raise the temperature to 70 °C and react for 15 hours. Filter, and vacuum-remove the toluene solvent in the filtrate to obtain 4.66 grams of ligand (1). The molecular formula of the ligand is C 13 H 16 N, Fm 186. Elemental analysis: C 83.80, H 8.63, N 7.57; Dissolve the ligand in toluene to obtain the toluene solution of ligand (1);

[0032] (3) Add n-butyllithium with a molar ratio twice that of the ligand to the toluene solution of the ligand, stir and react at -40 °C for 1 hour, raise the temperature to 50 °C and react for 10 hours. Filter, wash the filter residue with hexane twice, and vacuum-dry the filter residue. Then dissolve or disperse the filter residue in toluene to obtain the toluene solution of the ligand salt in step (3);

[0033] (4) At -20 °C, add 4.75 grams of transition metal salt TiCl4 to the toluene solution of the ligand salt, stir and react for 1 hour, raise the temperature to 50 °C, and react for 8 hours. Filter, and vacuum-remove the toluene solvent in the filtrate to obtain 6.43 grams of solid powder of half-metallocene catalyst (1), with a yield of 85%. The molecular formula is C 13 H 14 Cl2NTi, Fm 303. Elemental analysis: C 51.48, H 4.65, Cl 23.40, N 4.70, Ti 15.77.

[0034] Propylene polymerization

[0035] (1) At 25 °C, add 5 mL of MAO solution in toluene, 120 mL of toluene, and 5 mg of solid powder of half-metallocene catalyst (1) to a 300 mL polymerization kettle, and stir for 15 min.

[0036] (2) At 120 °C, propylene monomer was charged into the polymerization kettle, the pressure was maintained at 0.3 MPa, and stirring was carried out for 0.5 hours to obtain 12.6 g of polyolefin. The weight-average molecular weight of the polyolefin was 317,000, and the melting point was 155.6 °C; the products specifically included extrusion, blow molding, single (double) - direction stretching film, wet (dry) method film formation, foaming, rotational molding, casting, and other processing technologies, as well as various uses suitable for processing into products. The various uses were mainly for battery adhesive films, temperature and pressure resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, anti - creep materials, ship cables, fishing nets, agricultural films, unmanned aerial vehicles, home decorations, toys, non - structural materials for airplanes and high - speed trains, car interior trims, stab - proof gloves, bulletproof vests, or inner linings of hydrogen storage tanks, etc.

[0037] Example 2

[0038] Preparation of half - metallocene catalyst (2)

[0039]

[0040] (1) 100 mL of toluene was added, 2.33 g of aniline and n - butyllithium with a molar amount 1.3 times that of aniline were added, and stirring was carried out at - 50 °C for 2 hours. Then the temperature was raised to 50 °C and the reaction was carried out for 5 hours. After filtration, the filter residue was washed with hexane twice (50 mL of hexane was used each time), and the filter residue was dried under vacuum. Then the filter residue was dissolved or dispersed in 70 mL of toluene solvent to obtain the toluene solution of aniline salt in step (1);

[0041] (2) 4.85 g of 4 - bromoindene was added to the toluene solution of aniline salt in step (1), and stirring and reaction were carried out at - 10 °C for 1 hour. Then the temperature was raised to 80 °C and the reaction was carried out for 12 hours. After filtration, the toluene solvent in the filtrate was removed under vacuum to obtain 5.16 g of ligand (2). The molecular formula of the ligand is C 15 H 12 N, Fm 206. Elemental analysis: C 87.38, H 5.81, N 6.81; The ligand was dissolved in toluene to obtain the toluene solution of ligand (2);

[0042] (3) Methylmagnesium chloride (0.050 mol) with a molar ratio 2 times that of the ligand was added to the toluene solution of the ligand, and stirring and reaction were carried out at - 40 °C for 1 hour. Then the temperature was raised to 50 °C and the reaction was carried out for 10 hours. After filtration, the filter residue was washed with hexane twice, and the filter residue was dried under vacuum. Then the filter residue was dissolved or dispersed in toluene to obtain the toluene solution of ligand salt in step (3);

[0043] (4) At - 20 °C, 5.8 g of transition metal salt TiCl4 was added to the toluene solution of ligand salt, and stirring and reaction were carried out for 1 hour. Then the temperature was raised to 60 °C and the reaction was carried out for 8 hours. After filtration, the toluene solvent in the filtrate was removed under vacuum to obtain 6.86 g of solid powder of half - metallocene catalyst (2), with a yield of 85%. The molecular formula is C 15 H 10Cl2NTi, Fm 323, Elemental analysis: C 55.75, H 3.12, Cl 21.78, N 4.35, Ti 15.00.

[0044] Olefin polymerization

[0045] (1) At 25 °C, add 10 mL of toluene in the MAO solution, 200 mL of toluene, and 10 mg of the half-metallocene catalyst (2) solid powder to a 500 mL polymerization kettle, and stir for 15 min.

[0046] (2) At 120 °C, fill the polymerization kettle with ethylene and propylene monomers, maintain the pressure at 0.3 MPa, the ethylene and propylene are isobaric, stir for 0.5 hours, and obtain 11.6 g of polyolefin. The weight-average molecular weight of the polyolefin is 362,000; the products specifically include extrusion, blow molding, single (double)-directional stretching film, wet (dry) film forming, foaming, rotational molding, casting, and other processing techniques, as well as various uses suitable for processing into products. The various uses are mainly for battery adhesive films, temperature and pressure resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, anti-creep materials, ship ropes, fishing nets, agricultural films, drones, home decorations, toys, non-structural materials for airplanes and high-speed trains, car interior parts, stab-resistant gloves, bulletproof vests, or linings for hydrogen storage tanks, etc.

[0047] Example 3

[0048] Preparation of the half-metallocene catalyst (3)

[0049]

[0050] (1) Add 100 mL of toluene, add 3.22 g of 2,6-difluoroaniline and methylmagnesium chloride which is 1.1 times the molar amount of 2,6-difluoroaniline, stir at -50 °C, react for 2 hours, then raise the temperature to 50 °C and react for 6 hours, filter, wash the filter residue with hexane 2 times (50 mL of hexane each time), and vacuum dry the filter residue. Then dissolve or disperse the filter residue in 70 mL of toluene solvent to obtain the toluene solution of 2,6-difluoroaniline salt in step (1);

[0051] (2) Add 4.85 g of 7-bromoindene to the aniline salt toluene solution in step (1), stir and react at -10 °C for 1 hour, raise the temperature to 80 °C and react for 12 hours, filter, and vacuum remove the toluene solvent in the filtrate to obtain 5.16 g of ligand (3). The ligand molecular formula is C 15 H 10 F2N, Fm 242, Elemental analysis: C 74.41, H 4.15, F 15.63, N 5.81; Dissolve the ligand in toluene to obtain the toluene solution of ligand (3);

[0052] (3) Add methylmagnesium chloride with a molar ratio 2.2 times that of the ligand to the toluene solution of the ligand, stir and react at -40 °C for 1 hour, raise the temperature to 50 °C and react for 10 hours, filter, wash the filter residue with hexane twice, and vacuum-dry the filter residue. Then dissolve or disperse the filter residue in toluene to obtain the toluene solution of the ligand salt in step (3);

[0053] (4) At -20 °C, add 6.5 g of the transition metal salt TiCl4 to the toluene solution of the ligand salt, stir and react for 1 hour, raise the temperature to 60 °C and react for 8 hours, filter, and vacuum-remove the toluene solvent in the filtrate to obtain 7.93 g of the solid powder of the half-metallocene catalyst (3), with a yield of 88%, and the molecular formula C 15 H9Cl2F2NTi, Fm 360, elemental analysis: C 49.88, H 2.22, Cl 19.63, F 10.50, N 4.55, Ti 13.22.

[0054] Olefin polymerization

[0055] (1) At 25 °C, add 11 mL of MAO solution in toluene, 200 mL of dodecane, and 10 mg of the solid powder of the half-metallocene catalyst (3) to a 500 mL polymerization kettle, and stir for 15 min.

[0056] (2) At 170 °C, add 10 mL of 1-octene to the polymerization kettle, fill with ethylene, maintain the pressure at 0.3 MPa, and stir for 20 min to obtain 16.6 g of polyolefin, with a weight-average molecular weight of 157,000 for the polyolefin; the product specifically has various processing techniques such as extrusion, blow molding, single (double)-directional stretching film, wet (dry) film forming, foaming, rotational molding, casting, and other processing techniques, as well as various uses suitable for processing into products. The various uses are mainly used for battery adhesive films, temperature-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, creep-resistant materials, ship ropes, fishing nets, agricultural films, drones, home decorations, toys, non-structural materials for airplanes and high-speed trains, car interior parts, stab-resistant gloves, bulletproof vests, or linings for hydrogen storage tanks, etc.

[0057] Example 4

[0058] Preparation of half-metallocene catalyst (4)

[0059]

[0060] (1) Add 100 mL of toluene, 3.22 g of 2,6-difluoroaniline, and methylmagnesium chloride equimolar to 2,6-difluoroaniline, stir at -50 °C and react for 2 hours, then raise the temperature to 50 °C and react for 6 hours, filter, wash the filter residue with hexane twice (50 mL of hexane each time), and vacuum-dry the filter residue. Then dissolve or disperse the filter residue in 70 mL of toluene solvent to obtain the toluene solution of 2,6-difluoroaniline salt in step (1);

[0061] (2) Add 4.78 g of 5-phenyl-7-bromoindene to the toluene solution of aniline salt in step (1), stir and react at -10 °C for 1 hour, raise the temperature to 80 °C and react for 12 hours, filter, and vacuum-remove the toluene solvent in the filtrate to obtain 7.93 g of ligand (4). The molecular formula of the ligand is C 21 H 14 F2N,Fm 318. Elemental analysis: C 79.26, H 4.41, F 11.85, N 4.48; Dissolve the ligand in toluene to obtain a toluene solution of ligand (4);

[0062] (3) Add methylmagnesium chloride with a molar ratio 2.5 times that of the ligand to the toluene solution of the ligand, stir and react at -40 °C for 1 hour, raise the temperature to 60 °C and react for 10 hours, filter, wash the filter residue with hexane twice, and vacuum-dry the filter residue. Then dissolve or disperse the filter residue in toluene to obtain a toluene solution of the ligand salt in step (3);

[0063] (4) At -20 °C, add 6.5 g of transition metal salt TiCl4 to the toluene solution of the ligand salt, stir and react for 1 hour, raise the temperature to 60 °C, and react for 8 hours, filter, and vacuum-remove the toluene solvent in the filtrate to obtain 9.03 g of solid powder of half-metallocene catalyst (4) with a yield of 83%. The molecular formula is C 21 H 12 Cl2F2NTi,Fm 435. Elemental analysis: C 57.96, H 2.76, Cl 16.30, F 8.70, N 3.25, Ti 11.03.

[0064] Olefin polymerization

[0065] (1) At 15 °C, add 4 mL of toluene solution of MAO, 1 L of cyclohexane, and 4 mg of solid powder of half-metallocene catalyst (4) to a 2 L polymerization kettle, and stir for 20 min.

[0066] (2) At 170 °C, add 10 mL of 1-octene to the polymerization kettle, fill with ethylene, maintain the pressure at 3.5 MPa, and stir for 20 min to obtain 165.6 g of polyolefin. The weight-average molecular weight of the polyolefin is 165,000; The product specifically has various processing processes such as extrusion, blow molding, single (double)-directional stretching film, wet (dry) film forming, foaming, rotational molding, casting, and other processing processes, as well as various uses suitable for processing into products. The various uses are mainly used for battery adhesive films, temperature-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, anti-creep materials, ship cables, fishing nets, agricultural films, drones, home decorations, toys, non-structural materials for airplanes and high-speed trains, car interior parts, stab-resistant gloves, bulletproof vests, or linings for hydrogen storage tanks, etc.

[0067] Example 5

[0068] Preparation of Half - metallocene Catalyst (5)

[0069]

[0070] (1) The same operation as in Example 1 was carried out to obtain the toluene solution of the tertiary amine salt in step (1).

[0071] (2) 6.11 g of 9 - bromofluorene was added to the toluene solution of the aniline salt in step (1), stirred and reacted at - 10 °C for 1 hour, then the temperature was raised to 80 °C and reacted for 12 hours. After filtration, the toluene solvent in the filtrate was removed by vacuum pumping to obtain 5.95 g of ligand (5). The molecular formula of the ligand is C 17 H 18 N,Fm 236. Elemental analysis: C 86.46, H 7.63, N 5.91. The ligand was dissolved in toluene to obtain the toluene solution of ligand (5).

[0072] (3) n - butyllithium (0.063 mol) with a molar ratio 2.5 times that of the ligand was added to the toluene solution of the ligand, stirred and reacted at 10 °C for 1 hour, then the temperature was raised to 60 °C and reacted for 10 hours. After filtration, the filter residue was washed twice with hexane (60 mL each time), and then dried under vacuum. The filter residue was then dissolved or dispersed in THF to obtain the THF solution of the ligand salt in step (3).

[0073] (4) At - 20 °C, 5.9 g of the transition metal salt ZrCl4 was added to the THF solution of the ligand salt, stirred and reacted for 1 hour, then the temperature was raised to 60 °C and reacted for 8 hours. After filtration, the THF solvent in the filtrate was removed by vacuum pumping to obtain 8.61 g of solid powder of half - metallocene catalyst (5) with a yield of 87%. The molecular formula is C 17 H 16 Cl2NZr,Fm 396. Elemental analysis: C 51.53, H 4.06, Cl 17.86, N 3.62, Zr 22.93.

[0074] Olefin Polymerization

[0075] (1) At 30 °C, 5 mL of MAO solution in toluene, 100 mL of heptane and 8 mg of solid powder of half - metallocene catalyst (5) were added to a 300 mL polymerization kettle and stirred for 10 min.

[0076] (2) At 70 °C, 5 mL of norbornene was added to the polymerization kettle, ethylene and propylene were charged, the pressure was maintained at 0.5 MPa, the ethylene and propylene had the same partial pressure, and stirring was carried out for 30 min to obtain 9.6 g of polyolefin. The weight-average molecular weight of the polyolefin was 357,000; the products specifically included extrusion, blow molding, single (double) - oriented film stretching, wet (dry) film forming, foaming, rotational molding, casting, and other processing techniques, as well as various uses suitable for processing into products. The various uses were mainly for battery adhesive films, temperature - and pressure - resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, creep - resistant materials, ship cables, fishing nets, agricultural films, unmanned aerial vehicles, home decorations, toys, non - structural materials for airplanes and high - speed trains, automotive interior parts, stab - proof gloves, bulletproof vests, or linings for hydrogen storage tanks, etc.

[0077] Example 6

[0078] Preparation of half - metallocene catalyst (6)

[0079]

[0080] (1) The same operation as in Example 2 was carried out to obtain the toluene solution of aniline salt in step (1).

[0081] (2) The same operation as in Example 2 was carried out to obtain the toluene solution of ligand (6).

[0082] (3) The same operation as in Example 2 was carried out to obtain the toluene solution of ligand salt in step (3).

[0083] (4) At - 20 °C, 8 g of transition metal salt HfCl4 was added to the toluene solution of ligand salt, stirred and reacted for 1 h, the temperature was raised to 60 °C, and the reaction was carried out for 8 h. After filtration, the toluene solvent in the filtrate was removed by vacuum pumping to obtain 9.76 g of solid powder of half - metallocene catalyst (6), with a yield of 86%. The molecular formula was C 15 H 11 Cl2NHf, Fm 454, elemental analysis: C 39.66, H 2.43, Cl 15.61, N 3.10, Hf 39.20.

[0084] Olefin polymerization

[0085] (1) At 25 °C, 10 mL of MAO solution in toluene, 200 mL of toluene, and 10 mg of solid powder of half - metallocene catalyst (6) were added to a 500 mL polymerization kettle and stirred for 15 min.

[0086] (2) At 120 °C, 10 mL of 1-hexene was added to the polymerization kettle, propylene monomer was charged, the pressure was maintained at 0.3 MPa, and it was stirred for 20 min to obtain 8.4 g of polyolefin. The weight-average molecular weight of the polyolefin was 283,000; the products specifically included extrusion, blow molding, single (double) -directional stretching film, wet (dry) film forming, foaming, rotational molding, casting, and other processing techniques, as well as various uses suitable for being processed into products. The various uses were mainly for battery adhesive films, temperature and pressure resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, anti-creep materials, ship cables, fishing nets, agricultural films, unmanned aerial vehicles, home decorations, toys, non-structural materials for airplanes and high-speed rails, automotive interior parts, stab-resistant gloves, bulletproof vests, or linings for hydrogen storage tanks, etc.

[0087] Example 7

[0088] Preparation of half-metallocene catalyst (7)

[0089]

[0090] (1) The operation was the same as in Example 3 to obtain the toluene solution of 2,6-difluoroaniline salt in step (1);

[0091] (2) The operation was the same as in Example 3 to obtain the toluene solution of ligand (7);

[0092] (3) The operation was the same as in Example 3 to obtain the toluene solution of ligand salt in step (3);

[0093] (4) At -20 °C, 6.5 g of transition metal salt TiCl4 was added to the toluene solution of ligand salt, stirred and reacted for 1 hour, then the temperature was raised to 60 °C and reacted for 8 hours; 3.8 g of TMA was added, stirred, and the temperature was maintained at 30 °C and reacted for 6 hours; filtered, and the toluene solvent in the filtrate was removed by vacuum pumping to obtain 7.02 g of solid powder of half-metallocene catalyst (7) with a yield of 88%. The molecular formula was C 17 H 15 F2NTi, Fm 319, elemental analysis: C 63.96, H 4.71, F 11.87, N 4.51, Ti 14.95.

[0094] Olefin polymerization

[0095] (1) At 25 °C, 6 mL of MAO solution in toluene, 200 mL of toluene, and 8 mg of solid powder of half-metallocene catalyst (7) were added to a 500 mL polymerization kettle and stirred for 15 min.

[0096] (2) At 110 °C, 2 mL of ethyl undecenoate and 10 mL of 1-octene were added to a polymerization kettle, ethylene was charged, the pressure was maintained at 0.2 MPa, and stirring was carried out for 20 min to obtain 5.6 g of polyolefin with a weight-average molecular weight of 1.238 million; the product specifically has extrusion, blow molding, mono (bi) axial stretching film, wet (dry) film forming, foaming, rotational molding, casting and other processing processes, as well as various uses suitable for processing into products, and the various uses are mainly used for battery adhesive films, temperature and pressure resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, anti-creep materials, ship ropes, fishing nets, agricultural films, drones, home decorations, toys, non-structural materials for airplanes and high-speed rails, car interior trims, stab-resistant gloves, bulletproof vests or linings for hydrogen storage tanks, etc.

[0097] Example 8

[0098] Preparation of half-metallocene catalyst (8)

[0099]

[0100] (1) The operation was the same as in Example 3 to obtain a toluene solution of 2,4,6-trifluoroaniline salt in step (1);

[0101] (2) The operation was the same as in Example 3 to obtain a toluene solution of ligand (8);

[0102] (3) The operation was the same as in Example 3 to obtain a toluene solution of ligand salt in step (3);

[0103] (4) At -20 °C, 4.9 g of transition metal salt YCl3 was added to the toluene solution of ligand salt, stirred and reacted for 1 hour, the temperature was raised to 60 °C, and the reaction was carried out for 8 hours; 2.5 g of TMA was added, stirred, and the temperature was maintained at 30 °C for 6 hours; filtered, and the toluene solvent in the filtrate was removed by vacuum pumping to obtain 7.61 g of solid powder of half-metallocene catalyst (8) with a yield of 84%, and the molecular formula is C 16 H 11 F3NY, Fm 362.5, elemental analysis: C 52.98, H 3.05, F 15.71, N 3.91, Y 24.35.

[0104] Olefin polymerization

[0105] (1) At 25 °C, 6 mL of MAO solution in toluene, 200 mL of toluene, and 8 mg of solid powder of half-metallocene catalyst (8) were added to a 500 mL polymerization kettle and stirred for 15 min.

[0106] (2) At 90 °C, 2 mL of 1,7-decadiene and 10 mL of 1-octene were added to the polymerization kettle, ethylene and propylene were charged, and the pressure was maintained at 0.3 MPa. The partial pressures of ethylene and propylene were the same. After stirring for 20 min, 7.3 g of polyolefin was obtained, and the weight-average molecular weight of the polyolefin was 272,000. The products specifically include extrusion, blow molding, single (double) -directional stretching film, wet (dry) film forming, foaming, rotational molding, casting, and other processing technologies, as well as various uses suitable for processing into products. The various uses are mainly used for battery adhesive films, temperature and pressure resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, creep-resistant materials, ship cables, fishing nets, agricultural films, unmanned aerial vehicles, home decorations, toys, non-structural materials for airplanes and high-speed trains, car interior trims, stab-resistant gloves, bulletproof vests, or linings for hydrogen storage tanks, etc.

[0107] Example 9

[0108] Preparation of half-metallocene catalyst (9)

[0109]

[0110] (1) The operation was the same as in Example 5 to obtain the toluene solution of the tertiary amine salt in step (1).

[0111] (2) The operation was the same as in Example 5 to obtain the toluene solution of ligand (9).

[0112] (3) The operation was the same as in Example 5 to obtain the THF solution of the ligand salt in step (3).

[0113] (4) At -20 °C, 7.16 g of transition metal salt NdCl4 was added to the THF solution of the ligand salt, stirred and reacted for 1 hour, then the temperature was raised to 60 °C and reacted for 13 hours. After filtration, the THF solvent in the filtrate was removed by vacuum pumping to obtain 9.23 g of solid powder of half-metallocene catalyst (9), with a yield of 82%. The molecular formula is C 17 H 17 NCl2Nd, Fm 450, elemental analysis: C 45.38, H 3.80, Cl 15.73, N 3.21, Nd 31.88.

[0114] Olefin polymerization

[0115] (1) At 30 °C, 5 mL of MAO solution in toluene, 100 mL of heptane, and 5 mg of solid powder of half-metallocene catalyst (9) were added to a 300 mL polymerization kettle and stirred for 10 min.

[0116] (2) At 70 °C, 8 mL of 4-methyl-1-pentene was added to the polymerization kettle, ethylene and propylene were charged, and the pressure was maintained at 0.3 MPa. The ethylene and propylene had the same partial pressure. After stirring for 20 min, 7.3 g of polyolefin was obtained, and the weight-average molecular weight of the polyolefin was 315,000; the products specifically include extrusion, blow molding, single (double)-directional stretching film, wet (dry) film forming, foaming, rotational molding, casting, and other processing processes, as well as various uses suitable for processing into products. The various uses are mainly used for battery adhesive films, temperature and pressure resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, anti-creep materials, ship cables, fishing nets, agricultural films, drones, home decorations, toys, non-structural materials for airplanes and high-speed trains, car interior parts, stab-proof gloves, bulletproof vests, or linings for hydrogen storage tanks, etc.

[0117] Example 10

[0118] Preparation of half-metallocene catalyst (10)

[0119]

[0120] (1) The same operation as in Example 2 was carried out to obtain the toluene solution of aniline salt in step (1);

[0121] (2) The same operation as in Example 2 was carried out to obtain the toluene solution of ligand (10);

[0122] (3) The same operation as in Example 2 was carried out to obtain the toluene solution of ligand salt in step (3);

[0123] (4) At -20 °C, 4.83 g of transition metal salt VCl4 was added to the toluene solution of ligand salt, stirred and reacted for 1 hour, the temperature was raised to 60 °C, and the reaction was carried out for 15 hours. After filtration, the toluene solvent in the filtrate was removed by vacuum pumping to obtain 7.05 g of solid powder of half-metallocene catalyst (10), with a yield of 86%, and the molecular formula C 15 H 11 Cl2NV,Fm 327, elemental analysis: C 55.09, H 3.39, Cl 21.68, N 4.31, V 15.53.

[0124] Olefin polymerization

[0125] (1) At 25 °C, 5 mL of MAO solution in toluene, 100 mL of toluene, and 10 mg of solid powder of half-metallocene catalyst (10) were added to a 300 mL polymerization kettle and stirred for 15 min.

[0126] (2) At 120 °C, 10 mL of 1-octene was added to the polymerization kettle, propylene monomer was charged, the pressure was maintained at 0.3 MPa, and it was stirred for 20 min to obtain 12.6 g of polyolefin with a weight-average molecular weight of 297,000 for the polyolefin; the product specifically has extrusion, blow molding, single (double) -directional stretching film, wet (dry) film forming, foaming, rotational molding, casting, and other processing techniques, as well as various uses suitable for processing into products. The various uses are mainly for battery adhesive films, temperature- and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, creep-resistant materials, ship cables, fishing nets, agricultural films, drones, home decorations, toys, non-structural materials for airplanes and high-speed trains, car interior trims, stab-resistant gloves, bulletproof vests, or linings for hydrogen storage tanks, etc.

[0127] Example 11

[0128] Preparation of half-metallocene catalyst (11)

[0129]

[0130] (1) 100 mL of toluene was added, 3.05 g of 2,6-dimethylaniline and methylmagnesium chloride equimolar to 2,6-dimethylaniline were added, stirred at -50 °C for 2 h, then the temperature was raised to 50 °C and reacted for 8 h, filtered, and the filter residue was washed with hexane twice (50 mL of hexane each time), and the filter residue was dried under vacuum. Then the filter residue was dissolved or dispersed in 70 mL of toluene solvent to obtain the toluene solution of 2,6-dimethylaniline salt in step (1);

[0131] (2) 5.21 g of 5-methyl-4-bromoindene was added to the toluene solution of 2,6-dimethylaniline salt in step (1), stirred and reacted at -10 °C for 1 h, the temperature was raised to 80 °C and reacted for 15 h, filtered, and the toluene solvent in the filtrate was removed under vacuum to obtain 6.21 g of ligand (11). The molecular formula of the ligand is C 18 H 18 N, Fm 248, elemental analysis: C 87.09, H 6.85, N 6.06; the ligand was dissolved in toluene to obtain the toluene solution of ligand (11);

[0132] (3) Phenylmagnesium chloride (0.063 mol) with a molar ratio 2.5 times that of the ligand was added to the toluene solution of the ligand, stirred and reacted at 10 °C for 1 h, the temperature was raised to 60 °C and reacted for 10 h, filtered, and the filter residue was washed with hexane twice (60 mL of hexane each time), and the filter residue was dried under vacuum. Then the filter residue was dissolved or dispersed in toluene to obtain the toluene solution of the ligand salt in step (3);

[0133] (4) At -20 °C, 4.5 g of transition metal salt PdCl2 was added to the toluene solution of the ligand salt, stirred and reacted for 1 hour, then the temperature was raised to 60 °C and reacted for 12 hours; 2.5 g of TMA was added, stirred, and the temperature was maintained at 30 °C and reacted for 8 hours; filtered, and the toluene solvent in the filtrate was removed by vacuum pumping to obtain 7.6 g of solid powder of the half-metallocene catalyst (11), with a yield of 86%, and the molecular formula C 18 H 17 NPd, Fm 353, elemental analysis: C 61.20, H 4.83, N 3.99, Pd 29.98.

[0134] Olefin polymerization

[0135] (1) At 20 °C, 4 mL of MAO solution in toluene, 100 mL of toluene, and 6 mg of solid powder of the half-metallocene catalyst (11) were added to a 300 mL polymerization kettle and stirred for 15 min.

[0136] (2) At 100 °C, 5 mL of norbornene and 8 mL of 1-octene were added to the polymerization kettle, ethylene and propylene were charged, and the pressure was maintained at 0.5 MPa. Ethylene and propylene had the same partial pressure, and stirred for 20 min to obtain 11.8 g of polyolefin. The weight-average molecular weight of the polyolefin was 326,000; the product specifically had various processing processes such as extrusion, blow molding, single (double)-directional stretching film, wet (dry) film forming, foaming, rotational molding, casting, and other processing processes, as well as various uses suitable for processing into products. The various uses were mainly used for battery adhesive films, temperature and pressure resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, anti-creep materials, ship ropes, fishing nets, agricultural films, unmanned aerial vehicles, home decorations, toys, non-structural materials for airplanes and high-speed trains, car interior parts, stab-resistant gloves, bulletproof vests, or linings for hydrogen storage tanks, etc.

[0137] Example 12

[0138] Preparation of half-metallocene catalyst (12)

[0139]

[0140] (1) The operation was the same as in Example 3 to obtain the toluene solution of 2,6-difluoroaniline salt in step (1);

[0141] (2) The operation was the same as in Example 3 to obtain the toluene solution of ligand (12);

[0142] (3) The operation was the same as in Example 3 to obtain the toluene solution of the ligand salt in step (3);

[0143] (4) At -20 °C, 3.8 g of transition metal salt ScCl3 was added to the toluene solution of the ligand salt, stirred and reacted for 1 hour, the temperature was raised to 60 °C, and the reaction was carried out for 8 hours; 2.1 g of TMA was added, stirred, and the temperature was maintained at 30 °C for 6 hours; filtered, and the toluene solvent in the filtrate was removed by vacuum pumping to obtain 6.51 g of solid powder of the half-metallocene catalyst (12), with a yield of 87%, and the molecular formula C 16 H 12 F2NSc, Fm 299.5, elemental analysis: C 64.13, H 4.02, F 12.67, N 4.68, Sc 14.50.

[0144] Olefin polymerization

[0145] (1) At 25 °C, 5 mL of MAO solution in toluene, 200 mL of toluene, and 7 mg of solid powder of the half-metallocene catalyst (12) were added to a 500 mL polymerization kettle and stirred for 15 min.

[0146] (2) At 90 °C, 10 mL of styrene was added to the polymerization kettle, ethylene was charged, and the pressure was maintained at 0.3 MPa. The partial pressures of ethylene and propylene were the same. Stirred for 20 min to obtain 6.8 g of polyolefin, and the weight-average molecular weight of the polyolefin was 267,000; the products specifically include extrusion, blow molding, single (double) -directional stretching film, wet (dry) film forming, foaming, rotational molding, casting, and other processing techniques, as well as various uses suitable for processing into products. The various uses are mainly for battery adhesive films, temperature and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, anti-creep materials, ship ropes, fishing nets, agricultural films, drones, home decorations, toys, non-structural materials for airplanes and high-speed trains, car interior parts, stab-resistant gloves, bulletproof vests, or linings for hydrogen storage tanks, etc.

[0147] Example 13

[0148] Preparation of the half-metallocene catalyst (13)

[0149]

[0150] (1) 80 mL of toluene was added, 1.86 g of tert-butanol and metallic sodium which was 0.95 moles of tert-butanol were added, stirred at -50 °C for 2 hours, then the temperature was raised to 50 °C and reacted for 8 hours, filtered, and the filter residue was washed with hexane 2 times (50 mL of hexane was used each time), and the filter residue was dried by vacuum pumping. Then the filter residue was dissolved or dispersed in 60 mL of toluene solvent to obtain the toluene solution of tert-butoxide in step (1).;

[0151] (2) The operation was the same as in Example 5 to obtain 5.93 g of ligand (13), and the molecular formula of the ligand was C 17 H 17O, Fm 237, Elemental analysis: C 86.08, H 7.16, O 21.06; The ligand was dissolved in toluene to obtain a toluene solution of the ligand (13);

[0152] (3) Phenylmagnesium chloride with a molar ratio 2.5 times that of the ligand was added to the toluene solution of the ligand (13), stirred and reacted at 10 °C for 1 hour, then the temperature was raised to 60 °C and reacted for 10 hours, filtered, and the filter residue was washed twice with hexane (60 mL of hexane each time), and the filter residue was dried under vacuum. Then the filter residue was dissolved or dispersed in toluene to obtain a toluene solution of the ligand salt in step (3);

[0153] (4) At -20 °C, 4.78 g of the transition metal salt TiCl4 was added to the toluene solution of the ligand salt, stirred and reacted for 1 hour, then the temperature was raised to 60 °C and reacted for 13 hours, filtered, and the toluene solvent in the filtrate was removed under vacuum to obtain 7.36 g of a solid powder of the half-metallocene catalyst (13) with a yield of 83%, and the molecular formula was C 17 H 16 OCl2Ti, Fm 355, Elemental analysis: C 57.49, H 4.52, Cl 19.97, O 4.57, Ti 13.45.

[0154] Olefin polymerization

[0155] (1) At 30 °C, 5 mL of a toluene solution of MAO, 100 mL of decane, and 5 mg of the solid powder of the half-metallocene catalyst (13) were added to a 300 mL polymerization kettle and stirred for 10 min.

[0156] (2) At 120 °C, 8 mL of 1-octene and 5 mL of 9-decen-1-ol were added to the polymerization kettle, ethylene and propylene were charged, and the pressure was maintained at 0.3 MPa with the same partial pressures of ethylene and propylene, and stirred for 20 min to obtain 5.13 g of polyolefin with a weight average molecular weight of 326,000 for the polyolefin; The products specifically include extrusion, blow molding, single (double) -directional stretching film, wet (dry) film forming, foaming, rotational molding, casting, and other processing techniques, as well as various uses suitable for processing into products, and the various uses are mainly for battery adhesive films, temperature and pressure resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, anti-creep materials, ship ropes, fishing nets, agricultural films, drones, home decorations, toys, non-structural materials for airplanes and high-speed trains, automotive interior parts, stab-resistant gloves, bulletproof vests, or inner linings for hydrogen storage tanks, etc.

[0157] Example 14

[0158] Preparation of the half-metallocene catalyst (14)

[0159]

[0160] (1) The operation was the same as in Example 13, except that phenol was added instead of tert-butanol;

[0161] (2) The operation was the same as that in Example 13, and 7.08 g of ligand (14) was obtained. The molecular formula of the ligand was C 21 H 15 O, Fm 283. Elemental analysis: C 86.08, H 7.16, O 21.06. The ligand was dissolved in toluene to obtain a toluene solution of ligand (14);

[0162] (3) The operation was the same as that in Example 13 to obtain a toluene solution of the ligand salt in step (3);

[0163] (4) The operation was the same as that in Example 13. 5.83 g of transition metal salt ZrCl4 was added to obtain 9.1 g of solid powder of half-metallocene catalyst (14) with a yield of 82%. The molecular formula was C 21 H 14 OCl2Zr, Fm 444. Elemental analysis: C 56.78, H 3.18, Cl 15.87, O 3.77, Zr 20.40.

[0164] Olefin polymerization

[0165] (1) At 30 °C, 5 mL of MAO solution in toluene, 100 mL of toluene, and 8 mg of solid powder of half-metallocene catalyst (14) were added to a 300 mL polymerization kettle and stirred for 10 min.

[0166] (2) At 120 °C, 8 mL of 1-octene was added to the polymerization kettle, ethylene and propylene were charged, and the pressure was maintained at 0.3 MPa. The partial pressures of ethylene and propylene were the same. Stirring was carried out for 20 min to obtain 17.13 g of polyolefin. The weight-average molecular weight of the polyolefin was 371,000. The products specifically included extrusion, blow molding, single (double) -directional stretching film, wet (dry) film forming, foaming, rotational molding, casting, and other processing techniques, as well as various uses suitable for processing into products. The various uses were mainly for battery adhesive films, temperature and pressure resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, creep-resistant materials, ship cables, fishing nets, agricultural films, unmanned aerial vehicles, home decorations, toys, non-structural materials for airplanes and high-speed trains, automotive interior parts, stab-resistant gloves, bulletproof vests, or linings for hydrogen storage tanks, etc.

[0167] Example 15

[0168] Preparation of half-metallocene catalyst (15)

[0169]

[0170] (1) The operation was the same as that in Example 13, except that phenol was added instead of tert-butanol;

[0171] (2) The operation was the same as that in Example 13, and 5.88 g of ligand (15) was obtained. The molecular formula of the ligand was C17 H 16 O, Fm 236, Elemental analysis: C 86.45, H 6.76, O 6.79; Dissolve the ligand in toluene to obtain a toluene solution of the ligand (15).

[0172] (3) The operation is the same as that in Example 13 to obtain a toluene solution of the ligand salt in step (3).

[0173] (4) The operation is the same as that in Example 12. Add 4.45 g of the transition metal salt PdCl2, stir and react for 1 hour, then raise the temperature to 60 °C and react for 10 hours; add 2.5 g of TMA, stir, maintain the temperature at 30 °C and react for 8 hours; filter, and vacuum-remove the toluene solvent in the filtrate to obtain 7.83 g of solid powder of the half-metallocene catalyst (16) with a yield of 88%, and the molecular formula is C 18 H 18 OPd, Fm356, Elemental analysis: C 60.70, H 5.07, O 4.67, Pd 29.56.

[0174] Olefin polymerization

[0175] (1) At 30 °C, add 5 mL of MAO solution in toluene, 100 mL of decane, and 7 mg of solid powder of the half-metallocene catalyst (15) to a 300 mL polymerization kettle and stir for 10 min.

[0176] (2) At 120 °C, add ethylene to the polymerization kettle, maintain the pressure at 0.3 MPa, stir for 20 min to obtain 17.5 g of polyolefin with a weight-average molecular weight of 316,000 for the polyolefin; The products specifically include extrusion, blow molding, single (double)-directional stretching film, wet (dry) film forming, foaming, rotational molding, casting, and other processing techniques, as well as various uses suitable for processing into products, and the various uses are mainly used for battery adhesive films, temperature-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, anti-creep materials, ship cables, fishing nets, agricultural films, drones, home decorations, toys, non-structural materials for airplanes and high-speed trains, car interior parts, stab-resistant gloves, bulletproof vests, or linings for hydrogen storage tanks, etc.

[0177] Example 16

[0178] Preparation of the half-metallocene catalyst (16)

[0179]

[0180] (1) The operation is the same as that in Example 13, except that phenol is added instead of tert-butanol.

[0181] (2) The operation is the same as that in Example 13 to obtain 6.6 g of the ligand (16), and the molecular formula of the ligand is C 19 H 19O, Fm 263, Elemental analysis: C 86.69, H 7.22, O 6.08; The ligand was dissolved in toluene to obtain a toluene solution of the ligand (16).

[0182] (3) The same operation as in Example 13 was carried out to obtain a toluene solution of the ligand salt in step (3).

[0183] (4) The same operation as in Example 12 was carried out, and 3.78 g of the transition metal salt ScCl3 was added to obtain 6.63 g of the solid powder of the half-metallocene catalyst (16) with a yield of 82%. The molecular formula is C 20 H 23 OSc, Fm 323.5, Elemental analysis: C 74.20, H 7.11, O 5.13, Sc 13.56.

[0184] Olefin polymerization

[0185] (1) At 30 °C, 5 mL of the MAO solution in toluene, 100 mL of decane, and 5 mg of the solid powder of the half-metallocene catalyst (16) were added to a 300 mL polymerization kettle and stirred for 10 min.

[0186] (2) At 120 °C, 10 mL of 1-octene was added to the polymerization kettle, ethylene and propylene were charged, and the pressure was maintained at 0.4 MPa. The partial pressures of ethylene and propylene were the same. After stirring for 20 min, 21.2 g of polyolefin was obtained, and the weight-average molecular weight of the polyolefin was 305,000; The products specifically include extrusion, blow molding, single (double) -directional stretching film, wet (dry) film forming, foaming, rotational molding, casting, and other processing techniques, as well as various uses suitable for processing into products. The various uses are mainly used for battery adhesive films, temperature and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, anti-creep materials, ship cables, fishing nets, agricultural films, unmanned aerial vehicles, home decorations, toys, non-structural materials for airplanes and high-speed trains, automotive interior parts, stab-resistant gloves, bulletproof vests, or linings for hydrogen storage tanks, etc.

Claims

1. A half-metallocene catalyst, characterized in that, The semi-metallocene catalyst is a semi-metallocene catalyst conforming to Formula 1 or Formula 2, In General Formula 1 or General Formula 2, wherein said R1, R2 or R3 is H, C1-C 30 alkane, C3-C 30 alkane cycloalkane, C6-C 30 aromatic hydrocarbon or C6-C 30 haloaromatic hydrocarbon; wherein said X is a halogen, C1-C 30 alkane, C3-C 30 alkane cycloalkane, C6-C 30 aromatic hydrocarbon, C6-C 30 haloaromatic hydrocarbon, C6-C 30 nitroaromatic hydrocarbon or C6-C 30 alkoxyaromatic hydrocarbon, wherein said halogen is Cl, Br or F; wherein said M is a transition metal or a rare earth metal, selected from Ti, Zr, Hf, Ni, Pd, Ru, Rh, Fe, Co, Cr(III), Nd, Y, Sc, Sm or V.

2. The half-metallocene catalyst according to claim 1, wherein The semi-metallocene catalyst structural formulas are as follows (1) to (16):

3. The half-metallocene catalyst according to claim 1, characterized in that, The ligand structural formula of the semi-metallocene catalyst is as follows:

4. A method for synthesizing the half-metallocene catalyst according to claim 1 or 2, characterized in that, The following steps are involved: (1) Add an organic amine with C4 - C 30 or an organic alcohol with C4 - C 30 to an inert organic solvent, stir at -70 - 100 °C, add a dehydrogenating reagent, react for 20 hours, filter, wash the filter residue with hexane 2 - 4 times, vacuum-dry the filter residue, and then dissolve or disperse the filter residue in an organic solvent to obtain an organic amine salt or organic alcohol salt organic solvent solution in step (1); wherein the molar ratio of the organic amine with C4 - C 30 or the organic alcohol with C4 - C 30 to the dehydrogenating reagent is 1:(0.90 - 5.0), and the dehydrogenating reagent is n-butyllithium, Grignard reagent, sodium metal, potassium metal, lithium metal, etc.; (2) adding a halogenated indene or a halogenated indene derivative to the organic amine salt or organic alcohol salt organic solvent solution of step (1) at -30-100° C., stirring, reacting for 0.5-20 hours, filtering, vacuum-evacuating the organic solvent in the filtrate to obtain a ligand, and dissolving the ligand in an organic solvent to obtain a ligand organic solvent solution; wherein the molar ratio of the halogenated indene or the halogenated indene derivative to the organic amine salt or the organic alcohol salt is 1:(0.90-5.0), wherein the halogenated indene or the halogenated indene derivative has a halogen substituent on the aromatic group, and wherein the halogen substituent is Br or Cl; (3) adding a dehydrogenation agent to the ligand organic solvent solution, stirring at -70-100° C., reacting for 0.5-12 hours, filtering, washing the filter residue with hexane 2-4 times, and vacuum-drying the filter residue; then dissolving or dispersing the filter residue in an organic solvent to obtain the ligand salt organic solvent solution of step (3); wherein the molar ratio of the ligand to the dehydrogenation agent is 1:(0.90-5.0); (4) adding a transition metal salt to an organic solvent solution of a ligand salt at -70-100° C., stirring, reacting for 0.5-12 hours, filtering, and removing the organic solvent from the filtrate under vacuum to obtain a semi-metallocene catalyst solid powder of Formula 1 or Formula 2; wherein the molar ratio of the ligand salt to the transition metal salt is 1:(0.9-5.0); Among them, the organic solvent is selected from saturated hydrocarbons with C5 to C 30 , alicyclic hydrocarbons with C5 to C 30 , aromatic hydrocarbons with C6 to C 30 , saturated heterocyclic hydrocarbons with C3 to C 20 , paraffin oil or their mixed solvents, and toluene, xylene, dioxane, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane or hexadecane, or their mixed solvents are selected; Wherein, the transition metal salt is a halide, alkyl salt, alkoxy salt, cycloalkyl salt or aryl salt of transition metal Ti, Zr, Hf, Ni, Pd, Ru, Rh, Fe, Co, Cr(III), Nd, Y, Sc, Sm or V.

5. Use of the half-metallocene catalyst according to claim 1, characterized in that: In the presence of a cocatalyst, the semi-metallocene catalyst is used to catalyze the polymerization of ethylene or α-olefin, or the copolymerization of ethylene and α-olefin, or the copolymerization of propylene and α-olefin, wherein the α-olefin monomer is C3-C 100 olefin, wherein the C3-C 100 is C3-C 30 olefin, C6-C 30 diene, C3-C 100 olefin containing an oxygen atom, C3-C 100 olefin containing a nitrogen atom or C3-C 100 olefin containing a halogen atom or C3-C 100 olefin containing a functional group; wherein the C3-C 30 olefin is propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, norbornene, dicyclopentadiene or a mixture thereof; wherein the temperature of the polymerization or copolymerization is 30-200 °C, the time of the polymerization or copolymerization is 5-300 min, and the pressure of the polymerization or copolymerization is 0.05-40 MPa; wherein the polymerization or copolymerization process is a solution polymerization process, a gas-phase bulk polymerization process, a gas-phase melt bulk polymerization process, a liquid-phase bulk polymerization process, a slurry polymerization process, a loop polymerization process or a combined polymerization process; wherein the cocatalyst is an alkyl aluminum, an alkoxy aluminum or an organic boride, and the molar ratio of the cocatalyst to the semi-metallocene catalyst is (5-2000):1; The following steps are involved: (1) adding an organic solvent, a semi-metallocene catalyst and a co-catalyst into a polymerization reaction kettle, wherein the co-catalyst is an alkyl aluminum, an alkoxy aluminum or an organic boron compound or a mixture thereof; a classical co-catalyst such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-tert-butyl aluminum, trioctylaluminum, diethyl aluminum monochloride, ethyl aluminum dichloride, sesquiethyl aluminum chloride, MAO or modified MAO, used alone or in combination with several co-catalysts, wherein the molar ratio of the semi-metallocene catalyst to the co-catalyst is 1:(5-2000), stirring at 10 to 100° C. for 5 to 30 minutes; (2) Add ethylene or α-olefin to the polymerization reactor for polymerization. The polymerization temperature is 30 - 200 °C, the copolymerization time is 5 - 100 min, and the copolymerization pressure is 0.05 - 40 MPa; wherein the α-olefin is an olefin of C3 - C 30 or an olefin containing oxygen atom of C3 - C 30 . Among them, the olefin of C3 - C 30 is preferably propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 3-methyl-1-butene, cyclopentene, 4-methyl-1-pentene, 1,3-butadiene, isoprene, styrene, methylstyrene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, norbornene, ethylidene norbornene or its derivatives, halogenated olefin, hydroxy olefin, carboxy olefin, ester group olefin or their blends; wherein the olefin containing oxygen atom of C3 - C 30 is an olefin containing hydroxyl group, ester group or carboxyl group; wherein the organic solvent is selected from saturated hydrocarbons of C5 - C 30 , cycloaliphatic hydrocarbons of C5 - C 30 , aromatic hydrocarbons of C6 - C 30 or saturated heterocyclic hydrocarbons of C3 - C 20 or paraffin oil or their mixed solvents, and toluene, xylene, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane or hexadecane, or their mixed solvents are selected.

6. Use of the half-metallocene catalyst according to claim 1, characterized in that, Catalytic olefin polymerization produces polyolefin plastic materials or polyolefin elastic materials, wherein the polyolefin plastic materials and polyolefin elastic materials are suitable for various processing techniques, including extrusion, blow molding, unidirectional (bidirectional) film drawing, wet (dry) film forming, foaming, rotational molding or casting; used for battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, creep-resistant materials, ship cables, fishing nets, agricultural films, drones, home furnishings, toys, non-structural materials for airplanes and high-speed railways, car interior decoration parts, stab-proof gloves, bulletproof vests, hydrogen storage tank linings, 5G / 6G communication materials or intelligent robots.

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