Supported metallocene catalyst and preparation method and application thereof

Abstract

The invention discloses a supported metallocene catalyst and a preparation method and application thereof, and belongs to olefin coordination polymerization catalysts. According to the invention, the carrier is dispersed in the inert organic solvent, the metallocene catalyst is synthesized in situ in the inert organic solvent carrier, the metallocene catalyst is loaded in situ, the carrier is contacted with the metallocene catalyst, and the metallocene catalyst is firmly loaded on the surface of the carrier; the method comprises the following steps: adding an alkyl (oxy) aluminum solution with a novel structure, which is produced by a contact reaction of an alkyl aluminum solution and a toluene aqueous solution, into a carrier which is silica gel, magnesium dichloride and the like or a mixture of silica gel, magnesium dichloride and the like in any proportion, and enabling the alkyl (oxy) aluminum solution with the novel structure to be in contact with an in-situ supported metallocene catalyst to obtain the efficient supported metallocene catalyst. The activity of the prepared catalyst is adjustable in the range of 7000-25000gPE / (gcat.2 h), the suitable polymerization temperature ranges from 20 DEG C to 200 DEG C, even if the polymerization temperature reaches up to 170 DEG C, the catalyst still has high activity, and the thermal stability of the catalyst is high.

Description

Technical Field

[0001] The invention belongs to the field of olefin coordination polymerization catalyst, olefin coordination polymerization and polyolefin, and relates to a loading method of olefin coordination polymerization catalyst, a loaded catalyst, an application of the loaded catalyst, and polyolefin synthesized by the loaded catalyst, and specifically relates to a loading method of olefin coordination polymerization single-site catalyst, a loaded single-site catalyst, an application of the loaded single-site catalyst, and polyolefin synthesized by the loaded single-site catalyst, and more specifically relates to a loading method of olefin coordination polymerization metallocene catalyst, a loaded metallocene catalyst, an application of the loaded metallocene catalyst, and polyolefin synthesized by the loaded metallocene catalyst. Background Art

[0002] Polyolefin products are favored by people due to their abundant raw materials, low price, easy processing, long service life and excellent comprehensive performance. Currently, polyolefin products are widely used in packaging, electronics, automobiles, household appliances, agriculture and other fields.

[0003] According to the polymerization mechanism, metallocene catalysts or non-metallocene catalysts are called single-site catalysts. Therefore, supported metallocene catalysts or supported non-metallocene catalysts are collectively referred to as supported single-site catalysts.

[0004] At present, Dow Chemical Company almost monopolizes the international market of supported metallocene catalysts, and supported single-center catalysts are expensive, and there is no public preparation technology of supported metallocene catalysts. The catalytic activity of the company's supported metallocene catalyst can reach 8000gPE / (gcat.2h). According to domestic users, even the performance of imported supported metallocene catalysts is unstable, and the performance of supported metallocene catalysts of different batches varies greatly. And my country's relevant scientific research institutes and enterprises have been studying the preparation technology of supported metallocene catalysts in the past 30 years, but there is no breakthrough, and the catalytic activity of the prepared supported metallocene catalyst is less than 3000gPE / (gcat.2h), even only about 1000gPE / (gcat.2h), unstable performance, high production cost, high product ash content, and unstable product quality. Therefore, it is urgent to overcome the preparation technology of supported metallocene catalysts.

[0005] The inventor of the present invention, Huang Sihuang, proposed a new preparation method for a supported metallocene catalyst: a carrier is dispersed in an inert organic solvent, a metallocene catalyst is synthesized in situ in the inert organic solvent carrier, and the metallocene catalyst is loaded in situ, the carrier is in contact with the metallocene catalyst, and the metallocene catalyst is firmly loaded on the surface of the carrier; an alkyl (oxy) aluminum solution of a novel structure produced by the contact reaction of an alkyl aluminum solution with an aqueous toluene solution is added, and the alkyl (oxy) aluminum solution of the novel structure is in contact with the in situ loaded metallocene catalyst to obtain a high-efficiency supported metallocene catalyst, wherein the carrier is silica gel, magnesium dichloride, oxidized carbon tubes, oxidized carbon balls, graphite oxide, graphene oxide, alkoxy magnesium, MXene, fine coal powder particles, polymerized alumina or hydrotalcite or a mixture thereof in any proportion.

[0006] The supported metallocene catalyst preparation method disclosed at home and abroad uses a synthesized metallocene catalyst when loading the metallocene catalyst. The synthesized metallocene catalyst is the metallocene catalyst that has been synthesized before loading. The metallocene catalyst is purchased from the market or made by oneself. The supported metallocene catalyst prepared according to this idea has very low activity.

[0007] The present invention is based on the high-tech research and development foundation of the company, and accidentally discovered a new preparation method for a supported metallocene catalyst or a new preparation method for a supported single-site catalyst, and uses the supported metallocene catalyst or the supported single-site catalyst of the present invention to synthesize polyolefins with excellent performance. The supported metallocene catalyst disclosed in the present invention efficiently catalyzes olefin polymerization, and according to the requirements of the industrial production process, the activity is adjustable between 7000-25000 gPE / (gcat.2h), and the bulk density of the polyolefin is between 0.30-0.41 g / cm 3 The molecular weight of the polyolefin is 8000-8000000 g / mol, the polymerization temperature adapted to the catalyst is between 20-200°C, and the catalyst has high activity even at a polymerization temperature of up to 170°C. The thermal stability of the catalyst is significantly higher than that of other catalysts. The supported metallocene catalyst disclosed in the present invention has excellent copolymerization performance and is suitable for the polymerization of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, etc. The density of the polymer is 0.855-0.96 g / cm 3 The supported metallocene catalyst disclosed in the present invention is suitable for gas phase fluidized bed process, gas phase process, slurry process, loop process and combined process to produce high-performance polyolefin plastic materials and polyolefin elastic materials. The supported metallocene catalyst preparation technology disclosed in the present invention is a pioneering technology. The disclosure of the present invention shows the world that my country has achieved high-tech self-reliance in the field of supported metallocene catalysts and promoted the high-quality development of the polyolefin industry. Summary of the invention

[0008] The invention provides a new preparation method of a supported metallocene catalyst: a carrier is dispersed in an inert organic solvent, a metallocene catalyst is synthesized in situ in the inert organic solvent carrier, and the metallocene catalyst is loaded in situ, the carrier is in contact with the metallocene catalyst, and the metallocene catalyst molecules are firmly loaded on the surface of the carrier; an alkyl (oxy) aluminum solution with a novel structure produced by the contact reaction of an alkyl aluminum solution and a toluene aqueous solution is added, and the alkyl (oxy) aluminum solution with the novel structure is in contact with the in situ loaded metallocene catalyst to obtain a high-efficiency supported metallocene catalyst, wherein the carrier is silica gel, magnesium dichloride, oxidized carbon tubes, oxidized carbon balls, graphite oxide, graphene oxide, alkoxy magnesium, MXene, fine coal powder particles, polymerized aluminum oxide or hydrotalcite or a mixture thereof in any proportion.

[0009] The object of the present invention is to provide a method for preparing a supported metallocene catalyst, wherein a carrier is dispersed in an inert organic solvent, a metallocene catalyst is synthesized in situ in the inert organic solvent carrier, and the metallocene catalyst is in situ loaded, the carrier is in contact with the metallocene catalyst, and the metallocene catalyst is firmly loaded on the surface of the carrier, thereby obtaining a highly efficient supported metallocene catalyst;

[0010] The object of the present invention is to provide a method for preparing a supported metallocene catalyst. The method comprises the following steps: dispersing a carrier in an inert organic solvent, synthesizing a metallocene catalyst in situ in the inert organic solvent carrier, and loading the metallocene catalyst in situ. The carrier is in contact with the metallocene catalyst, and the metallocene catalyst is firmly loaded on the surface of the carrier. An alkyl (oxy) aluminum solution with a novel structure produced by the contact reaction of an alkyl aluminum solution with a toluene aqueous solution is added, and the alkyl (oxy) aluminum solution with the novel structure is in contact with the in situ loaded metallocene catalyst to obtain a high-efficiency supported metallocene catalyst.

[0011] Another object of the present invention is to provide a highly efficient supported metallocene catalyst, wherein the highly efficient supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an alk(oxy)aluminum.

[0012] Another object of the present invention is to advocate the use of supported metallocene catalysts, wherein the use of the supported metallocene catalyst is to catalyze the reaction of ethylene with C3-C 30 Olefin polymerization, the production density is 0.855-0.96g / cm 3 , molecular weight is 8000-8000000g / mol, bulk density is 0.30-0.41g / cm 3 Polyolefins between.

[0013] Another object of the present invention is to advocate the application of supported metallocene catalysts, wherein the application of supported metallocene catalysts is that the supported metallocene catalysts disclosed in the present invention are suitable for gas phase fluidized bed process, gas phase process, slurry process, loop process and combined process to produce high-performance polyolefin plastic materials and polyolefin elastic materials.

[0014] Another object of the present invention is to advocate the application of supported metallocene catalysts, wherein the application of the supported metallocene catalysts is to produce high-performance polyolefin plastic materials and polyolefin elastic materials, wherein the polyolefin plastic materials and polyolefin elastic materials are suitable for various existing processing technologies, and are also suitable for various new processing technologies to be developed in the future, specifically extrusion, blow molding, unidirectional (bidirectional) film drawing, wet (dry) film forming, foaming, rotational molding, casting and other processing technologies, as well as various uses suitable for processed products, wherein the various uses are mainly used for battery 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 furnishings, toys, aircraft and high-speed rail non-structural materials, vehicle interior decoration parts, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0015] The preparation method of the supported metallocene catalyst is as follows: a carrier is dispersed in an inert organic solvent, a metallocene catalyst is synthesized in situ in the inert organic solvent carrier, and the metallocene catalyst is loaded in situ, the carrier is contacted with the metallocene catalyst, the metallocene catalyst is firmly loaded on the surface of the carrier, an activator alkyl (oxy) aluminum solution of a new structure produced by the contact reaction of an alkyl aluminum solution and a toluene aqueous solution is added, and the activator alkyl (oxy) aluminum solution of the new structure is contacted with the in situ loaded metallocene catalyst to obtain a high-efficiency supported metallocene catalyst.

[0016] The supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an activator alkyl (oxy) aluminum, wherein the mass ratio of the transition metal of the metallocene catalyst to the carrier is (0.05-0.5):100; and the molar ratio of the activator alkoxy aluminum to the transition metal of the metallocene catalyst is (2-500):1.

[0017] The supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an activator alkylaluminoxane, and the carrier is a polyhydroxy solid, which means a solid compound with polyhydroxy groups or a solid material with polyhydroxy compounds or a solid material with polyhydroxy groups. The polyhydroxy solid is oxidized carbon tubes, oxidized carbon balls, oxidized graphite, silica gel, fine coal powder particles, polymerized alumina, hydrotalcite, polyhydroxy POSS, cellulose, polysaccharide, chitin, etc.; wherein the carrier is a magnesium halide, and the magnesium halide is selected from the general formula (1) of Mg(R) a X b At least one of the compounds of 20Aliphatic hydrocarbon group, C1~C 20 Fatty alkoxy, C3~C 20 Alicyclic or C6~C 20 an aromatic hydrocarbon group; X is selected from halogen, preferably Cl, Br, F; a=0 or 1, b=1 or 2, a+b=2, specifically selected from at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, methoxymagnesium chloride, ethoxymagnesium chloride, propoxymagnesium chloride, butoxymagnesium chloride, phenoxymagnesium chloride or butylmagnesium chloride, preferably magnesium dichloride or ethoxymagnesium, etc.; wherein the carrier is fine coal powder particles with an average particle size of 1-50μm; wherein the carrier is a carrier or a mixture of multiple carriers, preferably silica gel, magnesium dichloride, oxidized carbon tubes, oxidized carbon balls, graphite oxide, graphene oxide, MXene, fine coal powder particles, polymerized alumina or hydrotalcite or a mixture thereof, etc.

[0018] The supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an activator alkoxyaluminum. The carrier is silica gel, magnesium dichloride, alkoxymagnesium, oxidized carbon tubes, oxidized carbon balls, graphite oxide, graphene oxide, MXene, fine coal powder particles, polymerized alumina or hydrotalcite or a mixture thereof. It needs to be activated before being used as a carrier. The activation method is a general method. The specific operation is that the silica gel, oxidized carbon tubes, oxidized carbon balls, graphite oxide, graphene oxide, MXene, fine coal powder particles, polymerized alumina, hydrotalcite and other carriers need to be burned at 200-700° C. for 1-6 hours, and then protected by nitrogen after cooling and stored for standby; the magnesium dichloride is activated by dissolution-precipitation method, dissolution-granulation method or grinding method.

[0019] The supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an activator alkoxyaluminum, wherein the metallocene catalyst is a single metallocene catalyst, a double metallocene catalyst, a bridged metallocene catalyst, a CGC catalyst, a non-metallocene early transition metal catalyst or a non-metallocene late transition metal catalyst.

[0020] The supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an activator alkoxyaluminum, wherein the transition metal of the metallocene catalyst is Ti, Zr, Hf, V, Cr, Ni, Pd, Ru, Rh, Y, Nd, Sm or Sc, etc.

[0021] The supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an activator alkylaluminoxane, wherein the activator alkoxyaluminum is C1-C 20Alkyl(oxy)aluminum, preferably triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-nonylaluminum, diethylaluminum monochloride, dibutylaluminum monochloride, di-n-hexylaluminum monochloride, methylaluminoxane MAO or modified MAO or a mixture thereof; the molar ratio of the activator alkoxyaluminum to the transition metal of the metallocene catalyst is (2-500):1.

[0022] The supported metallocene catalyst is used to catalyze ethylene or C3-C 30 The density of the polyolefin produced by polymerization of olefins or their mixtures is 0.855-0.96g / cm 3 , molecular weight is 8000-8000000g / mol, bulk density is 0.30-0.41g / cm 3 , among which C3~C 30 The olefin is preferably propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, cyclopentene, 4-methyl-1-pentene, 1,3-butadiene, isoprene, styrene, methylstyrene, norbornene, ethylidene norbornene, 1,7-dioctene, 1,9-didecene, 9-decen-1-ol, butyl acrylate, ethyl acrylate, ethyl undecenoate or a mixture thereof.

[0023] The preparation method of the supported metallocene catalyst comprises the following steps:

[0024] (1) dispersing the carrier in an inert organic solvent at -20-50° C., wherein the molar ratio of the inert organic solvent to the carrier is (5-500):1, and stirring for 5 minutes to 5 hours;

[0025] (2) adding a transition metal salt to (1) at a temperature of -20-100° C., wherein the mass ratio of the transition metal salt to the carrier is (0.1-3000):100, stirring, contacting and reacting at -20-100° C. for 1-8 hours, filtering, and washing with an inert organic solvent; wherein the transition metal salt is TiCl4, ZrCl4, HfCl4, NiCl2, PdCl2, VCl3, YCl3, NdCl3, SmCl3, RuCl4 or RhCl4 or a mixture thereof;

[0026] (3) adding a metallocene catalyst ligand or a metallocene catalyst ligand salt to (2) at a temperature of -20-100°C, wherein the mass ratio of the metallocene catalyst ligand to the carrier is (0.001-5):1, stirring, and contacting and reacting at -20-100°C for 1-8 hours; wherein the metallocene catalyst ligand is a single metallocene catalyst ligand, a double metallocene catalyst ligand, a bridged metallocene catalyst ligand, a CGC catalyst ligand, a non-metallocene early transition metal catalyst ligand or a non-metallocene late transition metal catalyst ligand or a mixed ligand thereof or the ligand salt.

[0027] (4) filtering out the inert organic solvent in (3) at 0-80° C., vacuum drying, and washing with an inert organic solvent for 2-5 times; adding an inert organic solvent and an activator alkoxyaluminum solution, wherein the molar ratio of the alkoxyaluminum to the transition metal of the metallocene catalyst is (2-500):1, stirring, contacting and reacting at 0-80° C. for 10-120 minutes, and vacuum drying at 0-80° C. to obtain a high-efficiency supported metallocene catalyst.

[0028] (5) adding a supported metallocene catalyst to an olefin polymerization reactor, adding a cocatalyst, charging olefin, and reacting for 0.1-5 hours to obtain a polyolefin; the olefin partial pressure is 0.1-10 MPa, the hydrogen partial pressure is 0.001-0.1 MPa, the polymerization temperature is 20-200° C., and the polymerization time is 1 min-5 hours; wherein the cocatalyst is an alkyl aluminum or an alkoxy aluminum, preferably triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-nonyl aluminum, diethyl aluminum monochloride, dibutyl aluminum monochloride, di-n-hexyl aluminum monochloride, MAO, mMAO or a mixture thereof; the molar ratio of the alkyl aluminum to the transition metal of the supported metallocene catalyst is (2-1500):1; wherein the olefin is ethylene or C3-C 30 Olefins or mixtures thereof, wherein C3~C 30 The olefin is preferably propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, cyclopentene, 4-methyl-1-pentene, 1,3-butadiene, isoprene, styrene, methylstyrene, norbornene, ethylidene norbornene, 1,7-dioctene, 1,9-didecene, 9-decen-1-ol, butyl acrylate, ethyl acrylate, ethyl undecenoate or a mixture thereof.

[0029] Wherein, the inert organic solvent is selected from C5-C 20 Aliphatic alkanes or cycloalkanes, or C6–C 20 Aromatic hydrocarbons or their mixed solvents.

[0030] Further, the metallocene catalyst ligand or metallocene catalyst ligand salt is methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene, tetramethylcyclopentadiene, pentamethylcyclopentadiene, C5-C 30 Indene and its derivatives, C9-C 30 Fluorene and its derivatives, silicon-bridged dicyclopentadienyl ligands, ethyl-bridged dicyclopentadienyl ligands, tert-butylamino CGC ligands, aniline CGC ligands, halogenated aniline CGC ligands, α-diimine ligands, salicylaldehyde imine ligands, multidentate ligands or all-heterocyclic ligands or salts of the ligands, etc. Typical metallocene catalyst ligands are as follows:

[0031]

[0032] The metallocene catalyst ligand salt is a ligand salt of ligands 1-18, preferably a lithium salt of ligands 1-18, a magnesium salt of ligands 1-18, a potassium salt of ligands 1-18 or a sodium salt of ligands 1-18, etc. Typical metallocene catalyst ligand salts are as follows:

[0033]

[0034] Furthermore, the supported metallocene catalyst is applied in a gas phase fluidized bed process, a gas phase process, a slurry process, a loop process and a combined process to produce high-performance polyolefin plastic materials or polyolefin elastic materials.

[0035] Furthermore, the application of the supported metallocene catalyst is to produce high-performance polyolefin plastic materials and high-performance polyolefin elastic materials, wherein the polyolefin plastic materials and polyolefin elastic materials are suitable for various existing processing technologies, and are also suitable for various new processing technologies to be developed in the future, specifically extrusion, blow molding, unidirectional (bidirectional) film drawing, wet (dry) film forming, foaming, casting and other processing technologies, as well as various uses suitable for processed products, mainly used for battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, ship cables, fishing nets, agricultural films, drones, home furnishings, toys, non-structural materials for aircraft and high-speed railways, vehicle interior decoration parts, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0036] The present invention is further described below in conjunction with specific implementation modes, but the protection scope of the present invention is not limited to the following embodiments. DETAILED DESCRIPTION

[0037] Example 1

[0038] Preparation of supported metallocene catalysts:

[0039] After a 300 mL glass reaction bottle was fully replaced with nitrogen, 10 g of carrier SiO2 and 50 mL of inert organic solvent toluene were added to the reaction bottle at -5°C, and the mixture was stirred for 0.5 hour; 15 mL of transition metal salt TiCl4 was added, the temperature was raised to 25°C, and the mixture was stirred for 2 hours, filtered, and washed twice with hexane; 50 mL of toluene was added at 25°C, 0.06 g of metallocene catalyst ligand dimethylcyclopentadiene (3) was added, the mixture was stirred for 5 hours, filtered, and washed twice with hexane; 10.5 mL of activator MAO (10 wt% toluene solution) was added at 25°C, 30 mL of solvent toluene was added, the mixture was stirred for 0.5 hour, and the solvent was dried under vacuum at 40°C under stirring to obtain 12.55 g of supported catalyst, with a transition metal loading of 0.36 wt% on the metallocene catalyst.

[0040] Olefin polymerization:

[0041] After nitrogen is fully replaced in a 2-liter stainless steel autoclave, 1 L of n-hexane is added to the autoclave, 15 mg of the supported catalyst prepared in Example 1 is added, 0.5 mL of triethylaluminum (1.5 M hexane solution) as a cocatalyst, 3 mL of 1-hexene is added, 0.1 L of hydrogen is charged, and ethylene is charged to a pressure of 0.8 MPa. The reaction is stirred and maintained at 70° C. for 1 hour. 118 g of the polymer product is collected, and the bulk density BD=0.4 g / cm 3 , M W =352kg / mol, density ρ = 0.941g / cm 3 It is mainly used in battery films, temperature and pressure resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, ship cables, fishing nets, agricultural films, drones, home furnishings, toys, aircraft and high-speed rail non-structural materials, anti-nuclear radiation films, car interior decoration parts, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0042] Example 2

[0043] Preparation of supported metallocene catalysts:

[0044] After a 300 mL glass reaction bottle was fully replaced with nitrogen, 10 g of carrier hydrotalcite was added to the reaction bottle at 0°C, 60 mL of inert organic solvent toluene was added, and the mixture was stirred for 20 minutes; 20 mL of transition metal salt TiCl4 was added, the temperature was raised to 30°C, and the mixture was stirred for 3 hours, filtered, and washed twice with hexane; 80 mL of toluene was added at 20°C, 0.09 g of metallocene catalyst ligand tetramethylcyclopentadiene (4) was added, the temperature was raised to 50°C, and the mixture was stirred for 5 hours, filtered, and washed twice with hexane; 7.5 mL of activator MAO (10 wt% toluene solution) was added at 25°C, 40 mL of solvent toluene was added, and the mixture was stirred for 10 minutes. Under stirring, the solvent was dried under vacuum at 35°C to obtain 11.3 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.32 wt%.

[0045] Olefin polymerization:

[0046] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 800 mL of n-hexane was added to the autoclave, 10 mg of the supported catalyst prepared in Example 2 was added, 0.2 mL of MAO (10 wt% toluene solution) was added as a cocatalyst, 3 mL of 4-methyl-1-pentene was added, 0.01 L of hydrogen was charged, and ethylene was charged to a pressure of 0.9 MPa. The mixture was stirred and kept at 60° C. for 0.5 hour. 49 g of the polymerization product was collected, and the bulk density BD=0.36 g / cm 3 , M W =383kg / mol, density ρ = 0.895g / cm 3It is mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, agricultural films, home decorations, toys, non-structural materials for aircraft and high-speed railways, interior decoration parts of vehicles or linings of hydrogen storage tanks, etc.

[0047] Example 3

[0048] Preparation of supported metallocene catalysts:

[0049] After a 300 mL glass reaction bottle was fully replaced with nitrogen, 12 g of carrier magnesium chloride was added to the reaction bottle at 5°C, 90 mL of inert organic solvent toluene was added, and the mixture was stirred for 10 minutes; 30 mL of transition metal salt TiCl4 was added, the temperature was raised to 30°C, and the mixture was stirred for 3 hours, filtered, and washed with hexane for 4 times; 80 mL of toluene was added at 20°C, 0.15 g of metallocene catalyst ligand tert-butylamino CGC ligand (12) was added, the temperature was raised to 40°C, and the mixture was stirred for 6 hours, filtered, and washed with hexane for 2 times; 8 mL of activator MAO (10 wt% toluene solution) was added at 30°C, 50 mL of solvent toluene was added, and the mixture was stirred for 15 minutes. Under stirring, the solvent was dried under vacuum at 45°C to obtain 13.1 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.33 wt%.

[0050] Olefin polymerization:

[0051] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of n-hexane was added to the autoclave, 5 mg of the supported catalyst prepared in Example 3 was added, 0.2 mL (1.5 M) of triethylaluminum as a cocatalyst was added, 10 mL of 1-octene was added, 0.01 L of hydrogen was charged, and ethylene was charged to a pressure of 0.7 MPa. The mixture was stirred and kept at 70°C for 20 min. 131 g of the polymer product was collected, and the bulk density BD=0.34 g / cm 3 , M W =311kg / mol, density ρ = 0.881g / cm 3 . Mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, agricultural films, drones, home furnishings, toys, aircraft and high-speed rail non-structural materials, car interior parts, stab-proof gloves or hydrogen storage tank linings, etc.

[0052] Example 4

[0053] Preparation of supported metallocene catalysts:

[0054] After a 300 mL glass reaction bottle was fully replaced with nitrogen, 12 g of carrier magnesium chloride and 4 g of silica gel were added to the reaction bottle at 5°C, and 100 mL of inert organic solvent toluene was added, and stirred for 15 minutes; 75 mL of transition metal salt TiCl4 was added, the temperature was raised to 80°C and stirred for 3 hours, filtered, and washed with hexane 5 times; 80 mL of toluene was added at 20°C, 0.2 g of metallocene catalyst ligand aniline CGC ligand (11) was added, the temperature was raised to 50°C and stirred for 5 hours, filtered, and washed with hexane 3 times; 11.5 mL of activator MAO (10 wt% toluene solution) was added at 30°C, 50 mL of solvent toluene was added, and stirred for 15 minutes. Under stirring, the solvent was vacuum-evacuated at 35°C to obtain 19.6 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.31 wt%.

[0055] Olefin polymerization:

[0056] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of cyclohexane was added to the autoclave, 8 mg of the supported catalyst prepared in Example 4 was added, 0.2 mL of MAO (10 wt% toluene solution) was added as a cocatalyst, 10 mL of 1-octene was added, 0.01 L of hydrogen was charged, and ethylene was charged to a pressure of 0.8 MPa. The mixture was stirred and kept at 73°C for 2 hours. 186 g of the polymer product was collected, and the bulk density BD=0.39 g / cm 3 , M W =256kg / mol, density ρ = 0.912g / cm 3 Mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, ship cables, fishing nets, agricultural films, drones, home furnishings, toys, non-structural materials for aircraft and high-speed railways, interior trims, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0057] Example 5

[0058] Preparation of supported metallocene catalysts:

[0059] After a 300 mL glass reaction bottle was fully replaced with nitrogen, 12 g of carrier magnesium chloride and 3 g of MXene were added to the reaction bottle at 5°C, and 100 mL of inert organic solvent toluene was added, and stirred for 15 minutes; 95 mL of transition metal salt TiCl4 was added, and the temperature was raised to 80°C and stirred for 3 hours; 80 mL of toluene was added at 20°C, and 0.31 g of metallocene catalyst ligand aniline CGC ligand lithium salt (14) was added, and the temperature was raised to 50°C and stirred for 5 hours, filtered, and washed with hexane 5 times; 9.5 mL of activator MAO (10 wt% toluene solution) was added at 30°C, and 50 mL of solvent toluene was added, and stirred for 15 minutes. Under stirring, the solvent was vacuum-evacuated at 35°C to obtain 16.4 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.3 wt%.

[0060] Olefin polymerization:

[0061] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of cyclohexane was added to the autoclave, 8 mg of the supported catalyst prepared in Example 5 was added, 0.25 mL (1.5 M) of triisobutylaluminum as a co-catalyst was added, 10 g of 1-butene was added, 0.01 L of hydrogen was charged, and ethylene was charged to a pressure of 0.8 MPa. The reaction was stirred and maintained at 55° C. for 1 hour. 133 g of the polymerization product was collected, and the bulk density BD=0.37 g / cm 3 , M W =233kg / mol, density ρ = 0.923g / cm 3 Mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, ship cables, fishing nets, agricultural films, drones, home furnishings, toys, non-structural materials for aircraft and high-speed railways, interior trims, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0062] Example 6

[0063] Preparation of supported metallocene catalysts:

[0064] After a 300 mL glass reaction bottle was fully replaced with nitrogen, 5 g of carrier magnesium chloride and 3.5 g of MXene were added to the reaction bottle at 30°C, and 100 mL of inert organic solvent toluene was added, and stirred for 15 minutes; 15 g of transition metal salt NiCl2 was added, and the temperature was raised to 80°C and stirred for 4 hours; 80 ml of toluene was added at 20°C, and 0.52 g of non-metallocene catalyst ligand magnesium salt (13) was added, and the temperature was raised to 50°C and stirred for 6 hours, filtered, and washed with cyclohexane 3 times; 40.5 mL of activator TEA (1.5 M hexane solution) was added at 30°C, and 30 mL of solvent toluene was added, and stirred for 5 minutes. Under stirring, the solvent was vacuum-dried at 35°C to obtain 10.6 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.28 wt%.

[0065] Olefin polymerization:

[0066] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of cyclohexane was added to the autoclave, 8 mg of the supported catalyst prepared in Example 6 was added, 0.8 mL of MAO (10 wt% toluene solution) was added as a cocatalyst, 3 g of butyl acrylate was added, 0 L of hydrogen was charged, and ethylene was charged to a pressure of 0.8 MPa. The mixture was stirred and kept at 50° C. for 5 min. 108 g of the polymer product was collected, and the bulk density BD=0.34 g / cm 3 , M W =193kg / mol, density ρ = 0.947g / cm 3 Mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, ship cables, fishing nets, agricultural films, drones, home furnishings, toys, non-structural materials for aircraft and high-speed railways, interior trims, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0067] Example 7

[0068] Preparation of supported metallocene catalysts:

[0069] After a 300 mL glass reaction bottle was fully replaced with nitrogen, 5 g of carrier silica gel and 2 g of MXene were added to the reaction bottle at 30°C, and 100 mL of inert organic solvent toluene was added, and stirred for 15 minutes; 10 g of transition metal salt PdCl2 was added, and the temperature was raised to 80°C and stirred for 4 hours; 80 ml of toluene was added at 20°C, 0.8 g of non-metallocene catalyst ligand (15) was added, the temperature was raised to 50°C and stirred for 6 hours, filtered, and washed with heptane 3 times; 14.5 mL of activator MAO (10 wt% toluene solution) was added at 30°C, 30 mL of solvent hexane was added, and stirred for 5 minutes. Under stirring, the solvent was vacuum-dried at 35°C to obtain 7.6 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.29 wt%.

[0070] Olefin polymerization:

[0071] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of cyclohexane was added to the reactor, 10 mg of the supported catalyst prepared in Example 7 was added, 0.5 mL (1.5 M) of triethylaluminum as a cocatalyst, 3 g of ethyl undecylenate was added, 0 L of hydrogen was charged, and ethylene was charged to a pressure of 0.8 MPa. The mixture was stirred and kept at 50° C. for 0.5 hour. 63 g of the polymer product was collected, and the bulk density BD=0.33 g / cm 3 , M W =211kg / mol, density ρ = 0.945g / cm 3Mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, ship cables, fishing nets, agricultural films, drones, home furnishings, toys, non-structural materials for aircraft and high-speed railways, interior trims, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0072] Example 8

[0073] Preparation of supported metallocene catalysts:

[0074] After a 500 mL glass reaction bottle was fully replaced with nitrogen, 10 g of carrier graphite oxide and 110 mL of inert organic solvent toluene were added to the reaction bottle at 30° C., and the mixture was stirred for 15 minutes; 10 g of transition metal salt NdCl3 was added, and the temperature was raised to 80° C. and stirred for 4 hours; 80 ml of toluene was added at 20° C., 0.8 g of non-metallocene catalyst ligand potassium salt (16) was added, the temperature was raised to 50° C. and stirred for 6 hours, filtered, and washed with heptane 3 times; 15.5 mL of activator MAO (10 wt% toluene solution) was added at 30° C., 30 mL of solvent hexane was added, and the mixture was stirred for 5 minutes. Under stirring, the solvent was dried under vacuum at 35° C. to obtain 11.8 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.27 wt%.

[0075] Olefin polymerization:

[0076] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of cyclohexane was added to the autoclave, 10 mg of the supported catalyst prepared in Example 8 was added, 0.3 mL (1.5 M) of triethylaluminum as a cocatalyst was added, 3 g of 9-decene-1-ol was added, 0.01 L of hydrogen was charged, and ethylene was charged to a pressure of 0.8 MPa. The reaction was stirred and maintained at 55° C. for 0.5 hour. 48 g of the polymer product was collected, and the bulk density BD=0.36 g / cm 3 , M W =183kg / mol, density ρ = 0.935g / cm 3 Mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, ship cables, fishing nets, agricultural films, drones, home furnishings, toys, non-structural materials for aircraft and high-speed railways, interior trims, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0077] Example 9

[0078] Preparation of supported metallocene catalysts:

[0079] After a 500 mL glass reaction bottle was fully replaced with nitrogen, 10 g of carrier graphene oxide and 110 mL of inert organic solvent toluene were added to the reaction bottle at 30° C., and the mixture was stirred for 15 minutes; 10 g of transition metal salt RhCl3 was added, and the temperature was raised to 80° C. and stirred for 4 hours; 80 ml of toluene was added at 20° C., 0.8 g of non-metallocene catalyst ligand (17) was added, the temperature was raised to 50° C. and stirred for 6 hours, filtered, and washed with heptane 3 times; 12.5 mL of activator MAO (10 wt% toluene solution) was added at 30° C., 30 mL of solvent hexane was added, and the mixture was stirred for 5 minutes. Under stirring, the solvent was dried under vacuum at 35° C. to obtain 12.2 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.28 wt%.

[0080] Olefin polymerization:

[0081] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of cyclohexane was added to the autoclave, 10 mg of the supported catalyst prepared in Example 9 was added, 0.3 mL of the cocatalyst MAO (10 wt% toluene solution) was added, 3 g of 1,8-nonadiene was added, 0.01 L of hydrogen was charged, and ethylene was charged to a pressure of 0.8 MPa. The mixture was stirred and kept at 55° C. for 0.5 hour. 83 g of the polymerization product was collected, and the bulk density BD=0.35 g / cm 3 , M W =236kg / mol, density ρ = 0.928g / cm 3 Mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, ship cables, fishing nets, agricultural films, drones, home furnishings, toys, non-structural materials for aircraft and high-speed railways, interior trims, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0082] Example 10

[0083] Preparation of supported metallocene catalysts:

[0084] After a 500 mL glass reaction bottle was fully replaced with nitrogen, 10 g of carrier carbon nanospheres were added to the reaction bottle at 30°C, 110 mL of inert organic solvent toluene was added, and the mixture was stirred for 35 minutes; 10 g of transition metal salt HfCl4 was added, the temperature was raised to 80°C and stirred for 4 hours; 80 ml of toluene was added at 20°C, 0.8 g of non-metallocene catalyst ligand sodium salt (18) was added, the temperature was raised to 50°C and stirred for 6 hours, filtered, and washed with heptane 3 times; 12.5 mL of activator MAO (10 wt% toluene solution) was added at 30°C, 30 mL of solvent hexane was added, and the mixture was stirred for 5 minutes. Under stirring, the solvent was dried under vacuum at 35°C to obtain 13.3 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.31 wt%.

[0085] Olefin polymerization:

[0086] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of hexane was added to the autoclave, 10 mg of the supported catalyst prepared in Example 10, 0.15 mL of the cocatalyst MAO (10 wt% toluene solution), 3 g of 1,8-nonadiene, 50 g of propylene, 0.01 L of hydrogen, and ethylene were added to a pressure of 0.9 MPa. The mixture was stirred and kept at 60°C for 0.5 hours. 55 g of the polymerization product was collected, and the bulk density BD=0.32 g / cm 3 , M W =262kg / mol, density ρ = 0.922g / cm 3 Mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, ship cables, fishing nets, agricultural films, drones, home furnishings, toys, non-structural materials for aircraft and high-speed railways, interior trims, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0087] Embodiment 11

[0088] Preparation of supported metallocene catalysts:

[0089] After nitrogen is fully replaced in a 300 mL glass reaction bottle, 10 g of carrier silica gel and 80 mL of inert organic solvent toluene are added to the reaction bottle at 30° C., and the mixture is stirred for 30 minutes; 10 g of transition metal salt ZrCl4 is added, and the mixture is heated to 80° C. and stirred for 4 hours; 80 ml of toluene is added at 20° C., 2.5 g of metallocene catalyst ligand (8) is added, the mixture is heated to 50° C. and stirred for 6 hours, filtered, and washed with heptane 3 times; 15.5 mL of activator mMAO (10 wt% toluene solution) is added at 30° C., 30 mL of solvent hexane is added, and the mixture is stirred for 5 minutes. Under stirring, the solvent is dried under vacuum at 35° C. to obtain 13.7 g of supported catalyst, and the transition metal loading of the metallocene catalyst is 0.32 wt%.

[0090] Olefin polymerization:

[0091] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of hexane was added to the autoclave, 10 mg of the supported catalyst prepared in Example 11 was added, 0.2 mL of the cocatalyst MAO (10 wt% toluene solution) was added, 3 g of ethylidene norbornene was added, 50 g of propylene was added, 0.01 L of hydrogen was charged, and ethylene was charged to a pressure of 0.9 MPa. The mixture was stirred and kept at 60° C. for 0.5 hour. 73 g of the polymerization product was collected, and the bulk density BD=0.30 g / cm 3 , M W =266kg / mol, density ρ = 0.903g / cm 3Mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, ship cables, fishing nets, agricultural films, drones, home furnishings, toys, non-structural materials for aircraft and high-speed railways, interior trims, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0092] Example 12

[0093] Preparation of supported metallocene catalysts:

[0094] After a 300 mL glass reaction bottle was fully replaced with nitrogen, 10 g of carrier diethoxymagnesium was added to the reaction bottle at 30°C, 80 mL of inert organic solvent toluene was added, and the mixture was stirred for 30 minutes; 10 g of transition metal salt ZrCl4 was added, the temperature was raised to 80°C and stirred for 4 hours; 80 ml of toluene was added at 20°C, 2.5 g of metallocene catalyst ligand (10) was added, the temperature was raised to 50°C and stirred for 6 hours, filtered, and washed with heptane 3 times; 15.5 mL of activator MAO (10 wt% toluene solution) was added at 30°C, 30 mL of solvent hexane was added, the mixture was stirred for 5 minutes, and the solvent was dried under vacuum at 35°C under stirring to obtain 14.3 g of supported catalyst, with a transition metal loading of 0.33 wt% of the metallocene catalyst.

[0095] Olefin polymerization:

[0096] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of toluene was added to the autoclave, 10 mg of the supported catalyst prepared in Example 12 was added, 0.5 mL of the cocatalyst MAO (10 wt% toluene solution) was added, 3 g of ethylidene norbornene was added, 50 g of propylene was added, 0.01 L of hydrogen was charged, and ethylene was charged to a pressure of 0.9 MPa. The mixture was stirred and kept at 60° C. for 0.5 hour. 203 g of the polymerization product was collected, and the bulk density BD=0.30 g / cm 3 , M W =72kg / mol, density ρ = 0.893g / cm 3 . Mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, agricultural films, drones, home furnishings, toys, aircraft and high-speed rail non-structural materials, car interior parts, stab-proof gloves or hydrogen storage tank linings, etc.

[0097] Embodiment 13

[0098] Preparation of supported metallocene catalysts:

[0099] After a 300 mL glass reaction bottle was fully replaced with nitrogen, 10 g of carrier magnesium chloride and 80 mL of inert organic solvent toluene were added to the reaction bottle at 30°C, and the mixture was stirred for 30 minutes; 150 mL of transition metal salt TiCl4 was added, the temperature was raised to 80°C and stirred for 4 hours; 80 mL of toluene was added at 20°C, 2.5 g of metallocene catalyst ligand (14) was added, the temperature was raised to 50°C and stirred for 6 hours, filtered, and washed with heptane 3 times; 12.5 mL of activator MAO (10 wt% toluene solution) was added at 30°C, 30 mL of solvent hexane was added, and the mixture was stirred for 5 minutes. Under stirring, the solvent was dried under vacuum at 35°C to obtain 14.8 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.32 wt%.

[0100] Olefin polymerization:

[0101] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of toluene was added to the autoclave, 10 mg of the supported catalyst prepared in Example 13 was added, 0.3 mL of the cocatalyst MAO (10 wt% toluene solution) was added, 40 g of 1-octane was added, 0.01 L of hydrogen was charged, and ethylene was charged to a pressure of 4 MPa. The reaction was stirred and maintained at 140° C. for 0.5 hour. 228 g of the polymerization product was collected, M W =162kg / mol, density ρ = 0.863g / cm 3 . Mainly used in battery films, building materials, automotive materials, fitness equipment, ship cables, fishing nets, agricultural films, drones, home decorations, toys, aircraft and high-speed rail non-structural materials, car interior parts or hydrogen storage tank linings, etc.

[0102] Embodiment 14

[0103] Preparation of supported metallocene catalysts:

[0104] After a 300 mL glass reaction bottle was fully replaced with nitrogen, 10 g of carrier silica gel and 80 mL of inert organic solvent toluene were added to the reaction bottle at 30° C., and the mixture was stirred for 30 minutes; 150 mL of transition metal salt TiCl4 was added, the temperature was raised to 80° C., and the mixture was stirred for 4 hours, filtered, and washed with hexane three times; 80 mL of toluene was added at 20° C., 3.5 g of metallocene catalyst ligand (9) was added, the temperature was raised to 50° C., and the mixture was stirred for 6 hours, filtered, and washed with heptane three times; 16.5 mL of activator triethylaluminum (1.5 M) was added at 30° C., 30 mL of solvent hexane was added, and the mixture was stirred for 5 minutes. Under stirring, the solvent was dried under vacuum at 35° C. to obtain 15.2 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.33 wt%.

[0105] Olefin polymerization:

[0106] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of toluene was added to the autoclave, 10 mg of the supported catalyst prepared in Example 14 was added, 0.2 mL of the cocatalyst MAO (10 wt% toluene solution) was added, 50 g of 1-octene was added, 0.01 L of hydrogen was charged, and ethylene was charged to a pressure of 4 MPa. The reaction was stirred and maintained at 120° C. for 15 min. 83 g of the polymerization product was collected, M W =172kg / mol, density ρ = 0.864g / cm 3 . Mainly used in battery films, heat-resistant and pressure-resistant pipes, building materials, automotive materials, fitness equipment, agricultural films, drones, home decorations, toys, aircraft and high-speed rail non-structural materials, car interior parts or hydrogen storage tank linings, etc.

[0107] Embodiment 15

[0108] Preparation of supported metallocene catalysts:

[0109] After a 300 mL glass reaction bottle was fully replaced with nitrogen, 10 g of carrier magnesium chloride was added to the reaction bottle at 30° C., 80 mL of inert organic solvent toluene was added, and the mixture was stirred for 30 minutes; 200 mL of transition metal salt TiCl4 was added, the temperature was raised to 80° C. and stirred for 4 hours, filtered, and washed with hexane three times; 80 mL of toluene was added at 20° C., 4.5 g of metallocene catalyst ligand salt (14) was added, the temperature was raised to 50° C. and stirred for 6 hours, filtered, and washed with heptane three times; 17.5 mL of activator MAO (10 wt% toluene solution) was added at 30° C., 30 mL of solvent hexane was added, and the mixture was stirred for 5 minutes. Under stirring, the solvent was dried under vacuum at 35° C. to obtain 16.2 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.33 wt%.

[0110] Olefin polymerization:

[0111] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of toluene was added to the autoclave, 10 mg of the supported catalyst prepared in Example 15, 0.5 mL of the cocatalyst MAO (10 wt% toluene solution), 35 g of 1-octene, 0.01 L of hydrogen, and ethylene were added to a pressure of 4 MPa. The reaction was stirred and maintained at 170° C. for 10 min. 123 g of the polymerization product was collected, M W =142kg / mol, density ρ = 0.873g / cm 3 . Mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, agricultural films, drones, home decorations, toys, aircraft and high-speed rail non-structural materials, car interior parts, bulletproof vests or hydrogen storage tank linings, etc.

[0112] Example 16

[0113] Preparation of supported metallocene catalysts:

[0114] After a 300 mL glass reaction bottle was fully replaced with nitrogen, 10 g of carrier magnesium chloride and 80 mL of inert organic solvent toluene were added to the reaction bottle at 30° C., and the mixture was stirred for 30 minutes; 25 mL of transition metal salt TiCl4 was added, the temperature was raised to 80° C. and stirred for 4 hours; 80 mL of toluene was added at 20° C., 4.5 g of metallocene catalyst ligand salt (11) was added, the temperature was raised to 50° C. and stirred for 6 hours, filtered, and washed with heptane 4 times; 25.5 mL of activator MAO (10 wt% toluene solution) was added at 30° C., 30 mL of solvent hexane was added, and the mixture was stirred for 5 minutes. Under stirring, the solvent was dried under vacuum at 35° C. to obtain 16.2 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.33 wt%.

[0115] Olefin polymerization:

[0116] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of toluene was added to the autoclave, 10 mg of the supported catalyst prepared in Example 16, 0.5 mL of the cocatalyst MAO (10 wt% toluene solution), 30 g of 1-octene, 0.01 L of hydrogen, and ethylene were added to the autoclave until the pressure reached 4 MPa. The reaction was stirred and maintained at 170°C for 20 min. 198 g of the polymerization product was collected, M W =146kg / mol, density ρ = 0.871g / cm 3 . Mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, agricultural films, drones, home decorations, toys, aircraft and high-speed rail non-structural materials, car interior parts, stab-proof gloves, artificial grass or hydrogen storage tank linings, etc.

[0117] Embodiment 17

[0118] Preparation of supported metallocene catalysts:

[0119] After a 300 mL glass reaction bottle was fully replaced with nitrogen, 12 g of carrier magnesium chloride was added to the reaction bottle at 5°C, 90 mL of inert organic solvent toluene was added, and the mixture was stirred for 10 minutes; 30 mL of transition metal salt TiCl4 was added, the temperature was raised to 30°C and stirred for 3 hours, filtered, and washed with hexane 4 times; 80 mL of toluene was added at 20°C, 0.15 g of metallocene catalyst ligand 2,6-difluoroaniline CGC ligand (14) was added, the temperature was raised to 40°C and stirred for 6 hours, filtered, and washed with hexane 2 times; 60 mL of activator MAO (10 wt% toluene solution) was added at 30°C, 50 mL of solvent toluene was added, and the mixture was stirred for 15 minutes. Under stirring, the solvent was dried under vacuum at 45°C to obtain 14.8 g of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.31 wt%.

[0120] Olefin polymerization:

[0121] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of n-hexane was added to the autoclave, 10 mg of the supported catalyst prepared in Example 17 was added, 0.5 mL of the co-catalyst triethylaluminum (1.5 M hexane solution) was added, 3 mL of 1-octene was added, ethylene was charged to a pressure of 0.9 MPa, and the mixture was stirred and kept at 60°C for 2 hours. 251 g of the polymer product was collected, and the bulk density BD=0.38 g / cm 3 , M W =3530kg / mol, density ρ = 0.951g / cm 3 It is mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, creep-resistant ship cables, fishing nets, agricultural films, drones, home furnishings, toys, aircraft and high-speed rail non-structural materials, vehicle interiors, materials for high-altitude and deep-sea equipment, nuclear radiation protection materials, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0122] Embodiment 18

[0123] Preparation of supported metallocene catalysts:

[0124] After the 30L reaction bottle was fully replaced with nitrogen, 1.2kg of carrier magnesium chloride was added to the reaction bottle at 5°C, 12L of inert organic solvent toluene was added, and the mixture was stirred for 10 minutes; 9L of transition metal salt TiCl4 was added, the temperature was raised to 30°C and stirred for 3 hours, filtered, and washed with hexane 4 times; 8L of toluene was added at 20°C, 25g of metallocene catalyst ligand 2,6-difluoroanilino CGC ligand (14) was added, the temperature was raised to 40°C and stirred for 6 hours, filtered, and washed with hexane 2 times; 800mL of activator MAO (10wt% toluene solution) was added at 30°C, 50mL of solvent toluene was added, the mixture was stirred for 15 minutes, and the solvent was dried under vacuum at 45°C under stirring to obtain 1.26kg of supported catalyst, with a transition metal loading of 0.3wt% on the metallocene catalyst.

[0125] Olefin polymerization:

[0126] After nitrogen was fully replaced in a 2-liter stainless steel autoclave, 1 L of n-hexane was added to the autoclave, 10 mg of the supported catalyst prepared in Example 18 was added, 0.5 mL of the co-catalyst triethylaluminum (1.5 M hexane solution) was added, 3 mL of 1-octene was added, ethylene was charged to a pressure of 0.9 MPa, and the mixture was stirred and kept at 70°C for 2 hours to collect 239 g of the polymer product with a bulk density of BD = 0.39 g / cm 3 , M W =2876kg / mol, density ρ = 0.949g / cm 3It is mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, creep-resistant ship cables, fishing nets, agricultural films, drones, home furnishings, toys, non-structural materials for aircraft and high-speed railways, interior trims for vehicles, materials for high-altitude and deep-sea equipment, anti-nuclear radiation materials, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

[0127] Embodiment 19

[0128] Preparation of supported metallocene catalysts:

[0129] After nitrogen is fully replaced in a 500L reaction bottle, 21kg of carrier magnesium chloride and 9kg of silica gel are added to the reaction bottle at 5°C, and 100L of inert organic solvent toluene is added, and the mixture is stirred for 10 minutes; 100L of transition metal salt TiCl4 is added, the temperature is raised to 30°C and stirred for 3 hours, filtered, and washed with hexane 4 times; 110L of toluene is added at 20°C, 550g of metallocene catalyst ligand aniline CGC ligand (11) is added, the temperature is raised to 40°C and stirred for 6 hours, filtered, and washed with hexane 2 times; 2.5L of activator MAO (10wt% toluene solution) is added at 30°C, 50mL of solvent toluene is added, the mixture is stirred for 15 minutes, and the solvent is dried under vacuum at 45°C under stirring to obtain 31.3kg of supported catalyst, and the transition metal loading of the metallocene catalyst is 0.32wt%.

[0130] Olefin polymerization:

[0131] After nitrogen is fully replaced in a 2-liter stainless steel autoclave, 1 L of n-hexane is added to the autoclave, 10 mg of the supported catalyst prepared in Example 19 is added, 0.5 mL of triethylaluminum (1.5 M hexane solution) as a cocatalyst, 10 mL of 1-octene is added, 0.001 MPa of hydrogen is added, ethylene is introduced to a pressure of 0.9 MPa, the mixture is stirred, the temperature is maintained at 70°C, and the reaction is carried out for 2 hours. 273 g of the polymer product is collected, and the bulk density BD=0.39 g / cm 3 , M W =366kg / mol, density ρ = 0.941g / cm 3 It is mainly used in battery films, heat-resistant and pressure-resistant pipes, shoe materials, building materials, automotive materials, fitness equipment, creep-resistant ship cables, fishing nets, agricultural films, drones, home furnishings, toys, non-structural materials for aircraft and high-speed railways, interior trims for vehicles, materials for high-altitude and deep-sea equipment, anti-nuclear radiation materials, stab-proof gloves, bulletproof vests or hydrogen storage tank linings, etc.

Claims

1. A method for preparing a supported metallocene catalyst, characterized in that: The carrier is dispersed in an inert organic solvent, the metallocene catalyst is synthesized in situ in the inert organic solvent carrier, the metallocene catalyst is loaded in situ, and the metallocene catalyst is loaded on the carrier, comprising the following steps: (1) dispersing a carrier in an inert organic solvent at -20-50°C, wherein the molar ratio of the inert organic solvent to the carrier is (5-500):1, and stirring for 5 minutes to 5 hours; wherein the carrier is a polyhydroxy solid, which refers to a solid compound having polyhydroxy groups or a solid material with a polyhydroxy compound or a solid material having polyhydroxy groups, wherein the polyhydroxy solid is oxidized carbon tubes, oxidized carbon balls, oxidized graphite, silica gel, fine coal powder particles, polymerized alumina, hydrotalcite, polyhydroxy POSS, cellulose, polysaccharide or chitin; wherein the carrier is a magnesium halide, and the magnesium halide is selected from the general formula (1) of Mg(R) a X b At least one of the compounds of 20 Aliphatic hydrocarbon group, C1~C 20 Fatty alkoxy, C3~C 20 Alicyclic or C6~C 20 An aromatic hydrocarbon group; X is selected from halogen; a=0 or 1, b=1 or 2, a+b=2; wherein the carrier is a carrier or a mixture of multiple carriers, preferably silica gel, magnesium dichloride, oxidized carbon tubes, oxidized carbon balls, graphite oxide, graphene oxide, alkoxy magnesium, MXene, fine coal powder particles, polymerized alumina or hydrotalcite or a mixture thereof; (2) adding a transition metal salt to (1) at a temperature of -20-100° C., wherein the mass ratio of the added transition metal salt to the carrier is (0.1-3000):100, stirring, contacting and reacting at -20-100° C. for 1-8 hours, filtering, and washing with an inert organic solvent to remove excess transition metal salt; (3) adding a metallocene catalyst ligand or a metallocene catalyst ligand salt to (2) at a temperature of -20-100° C., wherein the mass ratio of the metallocene catalyst ligand to the carrier is (0.001-5):1, stirring, and reacting at -20-100° C. for 1-8 hours; wherein the metallocene catalyst ligand is a single metallocene catalyst ligand, a double metallocene catalyst ligand, a bridged metallocene catalyst ligand, a CGC catalyst ligand, a non-metallocene early transition metal catalyst ligand or a non-metallocene late transition metal catalyst ligand or a mixed ligand thereof or the ligand salt; (4) filtering out the inert organic solvent in (3) at 0-80° C., vacuum drying, and washing with an inert organic solvent for 2-5 times; adding an inert organic solvent and an activator alkoxyaluminum solution, wherein the molar ratio of the activator alkoxyaluminum to the metallocene catalyst transition metal is (2-500):1, stirring, contacting at 0-80° C. for 10-120 minutes, and vacuum drying at 0-80° C. to obtain a supported metallocene catalyst.

2. The preparation method according to claim 1, characterized in that: The metallocene catalyst ligand or metallocene catalyst ligand salt is methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene, tetramethylcyclopentadiene, pentamethylcyclopentadiene, C5-C 30 Indene and its derivatives, C9-C 30 Fluorene and its derivatives, silicon-bridged dicyclopentadienyl ligands, ethyl-bridged dicyclopentadienyl ligands, tert-butylamino CGC ligands, anilino CGC ligands, halogenated anilino CGC ligands, α-diimine ligands, salicylaldehyde imine ligands, multidentate ligands or all-heterocyclic ligands or ligand salts.

3. The preparation method according to claim 1, characterized in that: The transition metal salt is TiCl4, ZrCl4, HfCl4, NiCl2, PdCl2, VCl3, YCl3, NdCl3, SmCl3, RuCl4 or RhCl4 or a mixture thereof.

4. The preparation method according to claim 1, characterized in that: The activator alkoxyaluminum is C1-C 20 of aluminum alkoxide.

5. The preparation method according to claim 1, characterized in that: The transition metal in the metallocene catalyst is Ti, Zr, Hf, V, Cr, Ni, Pd, Ru, Rh, Y, Nd, Sm or Sc.

6. The preparation method according to claim 1, characterized in that: in, The inert organic solvent is selected from C5-C 20 Aliphatic alkanes or cycloalkanes, or C6–C 20 Aromatic hydrocarbons or their mixed solvents.

7. Use of the supported metallocene catalyst prepared by the preparation method according to claim 1.

8. The use according to claim 7, characterized in that: Put the supported metallocene catalyst into an olefin polymerization reactor, add a cocatalyst, charge olefin, and react for 1 min to 5 hours to obtain polyolefin; the olefin partial pressure is 0.1-10 MPa, the hydrogen partial pressure is 0.001-0.1 MPa, and the polymerization temperature is 20-200°C, wherein the olefin is ethylene or C3-C 30 The olefin or their mixture is polymerized, wherein the molar ratio of the cocatalyst to the supported metallocene catalyst transition metal is (5-1500): 1, wherein the cocatalyst is alkyl aluminum or alkoxy aluminum; wherein the olefin is ethylene or C3-C 30 olefins or mixtures thereof.

9. The use according to claim 8, characterized in that: It is applied to gas phase fluidized bed process, gas phase process, slurry process, loop pipe process or combined process to produce polyolefin plastic material or polyolefin elastic material.

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