Supported metallocene catalyst, preparation method therefor, and use thereof

Abstract

A supported metallocene catalyst, a preparation method therefor and the use thereof, belonging to the field of olefin coordination polymerization catalysts. In the present invention, a supporter is dispersed in an inert organic solvent, and in the inert organic solvent containing the supporter, a metallocene catalyst is synthesized in situ and is supported in situ, wherein the supporter is in contact with the metallocene catalyst, so that the metallocene catalyst is firmly supported on the surface of the supporter; an alkyl(alkoxyl)aluminum solution having a novel structure, which is produced by a contact reaction of an alkyl aluminum solution and an aqueous solution of toluene, is added, and said alkyl(alkoxyl)aluminum solution having the novel structure comes into contact with the in-situ-supported metallocene catalyst, so as to obtain an efficient supported metallocene catalyst, the supporter being silica gel, magnesium chloride and the like, or a mixture thereof in any ratio. The catalyst prepared by the present invention has regulatable activity within 7000-25000 gPE / (gcat.2h), is adaptive to a polymerization temperature of 20-200°C, and can possess relatively high activity even if the polymerization temperature is as high as 170°C, and achieves high thermal stability.

Description

Supported metallocene catalyst and its preparation method and application TECHNICAL FIELD

[0001] The present application belongs to the field of olefin coordination polymerization catalyst, olefin coordination polymerization and polyolefin, and relates to a loading method of an olefin coordination polymerization catalyst, a supported catalyst, application of the supported catalyst, and a polyolefin synthesized by the supported catalyst, in particular to a loading method of an olefin coordination polymerization single-site catalyst, a supported single-site catalyst, application of the supported single-site catalyst, and a polyolefin synthesized by the supported single-site catalyst, and more particularly to a loading method of an olefin coordination polymerization metallocene catalyst, a supported metallocene catalyst, application of the supported metallocene catalyst, and a polyolefin synthesized by the supported metallocene catalyst. BACKGROUND

[0002] Polyolefin products are favored by people due to their rich raw materials, low price, easy processing, long service life, and excellent comprehensive performance. At present, polyolefin products are widely used in packaging, electronics, automobiles, household appliances, agriculture and other fields. After years of development, although the industrial structure of plastic products in China has been strengthened, compared with western developed countries, the polyolefin industry in China gradually emerges structural short board: low-end product surplus, future competitiveness is worrying; due to the barrier of catalyst preparation technology, China still needs to rely on a large number of imports for high-end polyolefin products, and cannot achieve localization. Therefore, it is urgent to develop supported single-site catalyst preparation technology and high-performance polyolefin products. High-end polyolefin is an important pillar of the development of polyolefin industry, and is also an important strategic product of the national economy in developed countries. The new technology of foreign large multinational companies develops rapidly, and new product brands emerge in an endless stream, which occupies an absolute dominant position in high-tech content and high-value-added polyolefin products. The development of China's polyolefin industry is both a challenge and a driving force. High-performance polyolefin mainly refers to polyolefin products that can meet special application requirements, have unique performance and high added value, such as metallocene polyolefin and non-metallocene polyolefin. Many polyolefin synthesis processes, such as gas phase fluidized bed process, gas phase process, slurry process, loop process and combined process, require the use of supported catalysts, so it is necessary to find a new method to load metallocene catalysts or non-metallocene catalysts to prepare supported metallocene catalysts or supported non-metallocene catalysts.

[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 catalyst, the supported single-site catalyst is expensive, the company prohibits the sale of technology to China, and the preparation technology of the supported metallocene catalyst is not disclosed, and the catalytic activity of the supported metallocene catalyst of the company can reach 8000 gPE / (gcat.2h). According to the feedback of domestic users, even the imported supported metallocene catalyst is not stable in performance, and the performances of different batches of supported metallocene catalysts are quite different. In the past 30 years, relevant scientific research institutions and enterprises in China have been researching the preparation technology of supported metallocene catalyst, but no breakthrough has been made, the catalytic activity of the prepared supported metallocene catalyst is less than 3000 gPE / (gcat.2h), and even only about 1000 gPE / (gcat.2h), the performance is unstable, the production cost is high, the product ash content is high, and the product quality is unstable. Therefore, it is urgent to overcome the preparation technology of the supported metallocene catalyst.

[0005] The inventor Huang Shuang of the present application proposes a new preparation method of the supported metallocene catalyst: dispersing the carrier in an inert organic solvent, synthesizing the 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; a new structure of alkyl aluminum solution produced by contacting and reacting an alkyl aluminum solution with a toluene aqueous solution is added, the new structure of alkyl aluminum solution is in contact with the metallocene catalyst loaded in situ, and a high-efficiency supported metallocene catalyst is obtained, wherein the carrier is silica gel, magnesium dichloride, carbon oxide pipe, carbon oxide ball, graphite oxide, graphene oxide, alkyl magnesium, MXene, fine coal powder particles, polyaluminum oxide or hydrotalcite or a mixture of them in any proportion.

[0006] The preparation method of the supported metallocene catalyst disclosed at home and abroad adopts the synthesized metallocene catalyst when the metallocene catalyst is loaded, and the synthesized metallocene catalyst is synthesized before being loaded, and the metallocene catalyst is purchased from the market or self-made. The activity of the supported metallocene catalyst prepared according to this idea is very low.

[0007] The present application is based on the high-tech research and development of the company, and the new preparation method of the supported metallocene catalyst or the new preparation method of the supported single-site catalyst is accidentally discovered, and the polyolefin with excellent performance is synthesized by using the supported metallocene catalyst or the supported single-site catalyst of the present application. The supported metallocene catalyst disclosed in the present application catalyzes the polymerization of olefins efficiently, and the activity can be adjusted to 7000-25000 gPE / (gcat.2h) according to the needs of industrial production process, and the bulk density of the polyolefin is 0.30-0.41 g / cm 3, the molecular weight of the polyolefin is 8000-8000000 g / mol, the polymerization temperature adapted by the catalyst is between 20-200 DEG C, the catalyst has higher activity even if the polymerization temperature is as high as 170 DEG C, and the thermal stability of the catalyst is obviously higher than that of other catalysts; the supported metallocene catalyst disclosed in the application has excellent copolymerization performance, is suitable for polymerization of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene and the like, and the density of the polymer is adjustable between 0.855-0.96 g / cm 3 The supported metallocene catalyst disclosed in the application is suitable for gas phase fluidized bed process, gas phase process, slurry process, loop process and combined process, and is used for producing high-performance polyolefin plastic materials and polyolefin elastic materials. The preparation technology of the supported metallocene catalyst disclosed in the application is a pioneering technology, and the disclosure of the application indicates that China has realized high-tech self-reliance and self-strength in the field of supported metallocene catalysts, and promotes the high-quality development of the polyolefin industry. SUMMARY

[0008] The application provides a new preparation method of a supported metallocene catalyst, which comprises the following steps: dispersing a carrier in an inert organic solvent, in-situ synthesizing a metallocene catalyst in the inert organic solvent carrier, and in-situ loading the metallocene catalyst, contacting the carrier with the metallocene catalyst, and firmly loading the metallocene catalyst on the surface of the carrier to obtain a high-efficiency supported metallocene catalyst.

[0009] The application aims to provide a preparation method of a supported metallocene catalyst, which comprises the following steps: dispersing a carrier in an inert organic solvent, in-situ synthesizing a metallocene catalyst in the inert organic solvent carrier, and in-situ loading the metallocene catalyst, contacting the carrier with the metallocene catalyst, and firmly loading the metallocene catalyst on the surface of the carrier to obtain a high-efficiency supported metallocene catalyst.

[0010] The application aims to provide a preparation method of a supported metallocene catalyst, which comprises the following steps: dispersing a carrier in an inert organic solvent, in-situ synthesizing a metallocene catalyst in the inert organic solvent carrier, and in-situ loading the metallocene catalyst, contacting the carrier with the metallocene catalyst, and firmly loading the metallocene catalyst on the surface of the carrier to obtain a high-efficiency supported metallocene catalyst.

[0011] Yet another object of the present application is to provide a high-efficiency supported metallocene catalyst, wherein the high-efficiency supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an alkoxyaluminum.

[0012] Yet another object of the present application is to claim the use of the supported metallocene catalyst, wherein the use of the supported metallocene catalyst is to catalyze the polymerization of ethylene and C3-C 30 olefins to produce a polyolefin with a density of 0.855-0.96 g / cm 3 , a molecular weight of 8000-8000000 g / mol and a bulk density of 0.30-0.41 g / cm 3 .

[0013] Yet another object of the present application is to claim the use of the supported metallocene catalyst, wherein the use of the supported metallocene catalyst is to produce high-performance polyolefin plastic materials and polyolefin elastomeric materials using the supported metallocene catalyst disclosed in the present application in a gas-phase fluidized bed process, a gas-phase process, a slurry process, a loop process and a combined process.

[0014] Yet another object of the present application is to claim the use of the supported metallocene catalyst, wherein the use of the supported metallocene catalyst is to produce high-performance polyolefin plastic materials and polyolefin elastomeric materials, wherein the polyolefin plastic materials and polyolefin elastomeric materials are suitable for various existing processing processes and also suitable for various new processing processes developed in the future, specifically extrusion, blow molding, mono(bi)directional film stretching, wet(dry) film forming, foaming, rotational molding, casting and other processing processes, and various uses suitable for processing into products, which 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 furnishings, toys, aircraft and high-speed rail non-structural materials, interior trim parts, stab-resistant gloves, body armor or hydrogen storage tank liners, etc.

[0015] The preparation method of the supported metallocene catalyst is to disperse the carrier in an inert organic solvent, synthesize the metallocene catalyst in situ in the inert organic solvent carrier and load the metallocene catalyst in situ, contact the carrier with the metallocene catalyst, firmly load the metallocene catalyst on the surface of the carrier, add an activator alkoxyaluminum solution with a new structure produced by contacting and reacting an aluminum alkyl solution with a toluene aqueous solution, contact the activator alkoxyaluminum solution with the new structure with the metallocene catalyst loaded in situ, and obtain a high-efficiency supported metallocene catalyst.

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

[0017] The supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an activator alkoxy aluminum, wherein the mass ratio of the metallocene catalyst transition metal to the carrier is (0.05-0.5):100; and the molar ratio of the activator alkoxy aluminum to the metallocene catalyst transition metal is (2-500):1. a X b The supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an activator alkoxy aluminum, wherein the mass ratio of the metallocene catalyst transition metal to the carrier is (0.05-0.5):100; and the molar ratio of the activator alkoxy aluminum to the metallocene catalyst transition metal is (2-500):1. 20 The supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an activator alkoxy aluminum, wherein the mass ratio of the metallocene catalyst transition metal to the carrier is (0.05-0.5):100; and the molar ratio of the activator alkoxy aluminum to the metallocene catalyst transition metal is (2-500):1. 20 The supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an activator alkoxy aluminum, wherein the mass ratio of the metallocene catalyst transition metal to the carrier is (0.05-0.5):100; and the molar ratio of the activator alkoxy aluminum to the metallocene catalyst transition metal is (2-500):1. 20 The supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an activator alkoxy aluminum, wherein the mass ratio of the metallocene catalyst transition metal to the carrier is (0.05-0.5):100; and the molar ratio of the activator alkoxy aluminum to the metallocene catalyst transition metal is (2-500):1. 20 The supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an activator alkoxy aluminum, wherein the mass ratio of the metallocene catalyst transition metal to the carrier is (0.05-0.5):100; and the molar ratio of the activator alkoxy aluminum to the metallocene catalyst transition metal is (2-500):1.

[0018] The supported metallocene catalyst is composed of a carrier, a metallocene catalyst and an activator alkoxy aluminum, wherein the mass ratio of the metallocene catalyst transition metal to the carrier is (0.05-0.5):100; and the molar ratio of the activator alkoxy aluminum to the metallocene catalyst transition metal is (2-500):1.

[0019] wherein the supported metallocene catalyst is composed of a support, a metallocene catalyst and an activator aluminoxane, wherein the metallocene catalyst is a single metallocene catalyst, a bis-metallocene catalyst, a bridged metallocene catalyst, a CGC catalyst, a non-metallocene pre-transition metal catalyst or a non-metallocene post-transition metal catalyst.

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

[0021] wherein the supported metallocene catalyst is composed of a support, a metallocene catalyst and an activator aluminoxane, wherein the activator aluminoxane is C1-C 20 alkylaluminoxane, preferably triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-nonylaluminum, diethylaluminum chloride, dibutylaluminum chloride, di-n-hexylaluminum chloride, methylaluminoxane MAO or modified MAO or their mixture, etc.; the molar ratio of the activator aluminoxane to the metallocene catalyst transition metal is (2-500): 1.

[0022] The application of the supported metallocene catalyst is to catalyze the polymerization of ethylene or C3-C 30 olefins or their mixture, and the produced polyolefin has a density of 0.855-0.96 g / cm 3 , a molecular weight of 8000-8000000 g / mol, and a bulk density of 0.30-0.41 g / cm 3 , wherein the C3-C 30 olefins are 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-decene-1-ol, butyl acrylate, ethyl acrylate, ethyl undecylenate or their mixture, etc.

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

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

[0025] (2) at -20-100℃, to (1) add transition metal salt, the mass ratio of transition metal salt to carrier is (0.1-3000):100, stirring, contact reaction at -20-100℃ for 1-8 hours, filtration, inert organic solvent washing; wherein the transition metal salt is TiCl4, ZrCl4, HfCl4, NiCl2, PdCl2, VCl3, YCl3, NdCl3, SmCl3, RuCl4 or RhCl4 or their mixture, etc.;

[0026] (3) at -20-100℃, to (2) add metallocene catalyst ligand or metallocene catalyst ligand salt, the mass ratio of metallocene catalyst ligand to carrier is (0.001-5):1, stirring, contact reaction at -20-100℃ for 1-8 hours; wherein the metallocene catalyst ligand is single metallocene catalyst ligand, double metallocene catalyst ligand, bridged metallocene catalyst ligand, CGC catalyst ligand, non-metallocene front transition metal catalyst ligand or non-metallocene rear transition metal catalyst ligand or their mixed ligand or the ligand salt.

[0027] (4) at 0-80℃, filter out the inert organic solvent in (3), vacuum dry, wash 2-5 times with inert organic solvent; add inert organic solvent, add activated agent alkyl aluminum solution, the molar ratio of alkyl aluminum to metallocene catalyst transition metal is (2-500):1, stirring, contact reaction at 0-80℃ for 10-120min, vacuum dry at 0-80℃, obtain high efficiency supported metallocene catalyst.

[0028] (5) take the supported metallocene catalyst into olefin polymerization reactor, add cocatalyst, fill in olefin, react for 0.1-5 hours, obtain polyolefin; the partial pressure of olefin is 0.1-10MPa, the partial pressure of hydrogen is 0.001-0.1MPa, the polymerization temperature is 20-200℃, the polymerization time is 1min-5 hours; wherein, the cocatalyst is alkyl aluminum or alkyl aluminum, preferably triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-nonyl aluminum, diethyl aluminum chloride, dibutyl aluminum chloride, di-n-hexyl aluminum chloride, MAO, mMAO or their mixture; the molar ratio of alkyl aluminum to supported metallocene catalyst transition metal is (2-1500):1; wherein, the olefin is ethylene or C3~C 30 alkene or their mixture, wherein C3~C 30 alkene 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-decadiene, 9-decene-1-ol, butyl acrylate, ethyl acrylate, ethyl undecylenate or their mixture, etc.

[0029] wherein the inert organic solvent is selected from C5-C 20 aliphatic or cycloaliphatic hydrocarbons, 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 bis-cyclopentadienyl ligand, ethyl-bridged bis-cyclopentadienyl ligand, tert-butylamine-based CGC ligand, aniline-based CGC ligand, halogenated aniline-based CGC ligand, α-diimine ligand, salicylaldimine ligand, polydentate ligand, or a full heterocyclic ligand, or the ligand salt thereof, and the like, and the typical metallocene catalyst ligand is as follows:

[0031] 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, and the like, and the typical metallocene catalyst ligand salt is as follows:

[0032] Further, the application of the supported metallocene catalyst is 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 elastomeric materials.

[0033] Further, wherein the application of the supported metallocene catalyst is to produce high-performance polyolefin plastic materials and high-performance polyolefin elastomeric materials, wherein the polyolefin plastic materials and polyolefin elastomeric materials are suitable for existing various processing processes, and also suitable for various new processing processes developed in the future, specifically extrusion, blow molding, mono (bi) directional film stretching, wet (dry) film forming, foaming, casting, and other processing processes, and various uses suitable for processing into products, mainly used for battery adhesive film, temperature and pressure resistant pipe material, shoe material, building material, automotive material, fitness equipment, ship cable, fishing net, agricultural film, unmanned aerial vehicle, home decoration, toy, aircraft and high-speed rail non-structural material, interior trim, stab-resistant gloves, body armor, or hydrogen storage tank liner, and the like.

[0034] The application will be further described in conjunction with the specific embodiments below, but the protection scope of the application is not limited to the following examples. DETAILED DESCRIPTION

[0035] Example 1

[0036] Preparation of the supported metallocene catalyst:

[0037] A 300 mL glass reaction bottle was sufficiently replaced by nitrogen, and 10 grams of a support, hydrotalcite, was added to the reaction bottle at 0°C. Then, 60 mL of an inert organic solvent, toluene, was added, and stirring was performed for 20 minutes. Then, 20 mL of a transition metal salt, TiCl4, was added, and the temperature was increased to 30°C. Stirring was performed for 3 hours, and filtration was performed. Hexane washing was performed twice. Then, 80 mL of toluene was added at 20°C. Then, 0.09 grams of a metallocene catalyst ligand, tetramethylcyclopentadiene (4), was added, and the temperature was increased to 50°C. Stirring was performed for 5 hours, and filtration was performed. Hexane washing was performed twice. Then, 7.5 mL of an activator, MAO (10 wt% toluene solution), was added at 25°C. Then, 40 mL of a solvent, toluene, was added, and stirring was performed for 10 minutes. Under stirring, the solvent was vacuum-dried at 35°C, and 11.3 grams of a supported catalyst was obtained. The transition metal loading of the metallocene catalyst was 0.32 wt%.

[0038] Olefin polymerization:

[0039] A 2 L stainless steel autoclave was sufficiently replaced by nitrogen, and 1 L of n-hexane was added to the reaction kettle. Then, 15 mg of a supported catalyst prepared in Example 1 was added. Then, 0.5 mL of a cocatalyst, triethylaluminum (1.5 M hexane solution), was added. Then, 3 mL of 1-hexene was added. Then, 0.1 L of hydrogen was filled. Then, ethylene was filled until the pressure was 0.8 MPa. Stirring was performed, and the temperature was maintained at 70°C. Reaction was performed for 1 hour, and 118 grams of a polymerization product was collected. The bulk density BD = 0.4 g / cm 3 , M W = 352 kg / mol, and the density p = 0.941 g / cm 3 It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, ship cable, fishing net, agricultural film, unmanned aerial vehicle, home decoration, toy, airplane and high-speed rail non-structural material, nuclear radiation protection film, interior trim, anti-stabbing glove, body armor, or hydrogen storage tank liner, etc.

[0040] Example 2

[0041] Preparation of a supported metallocene catalyst:

[0042] A 300 mL glass reaction bottle was sufficiently replaced by nitrogen, and 10 grams of a support, hydrotalcite, was added to the reaction bottle at 0°C. Then, 60 mL of an inert organic solvent, toluene, was added, and stirring was performed for 20 minutes. Then, 20 mL of a transition metal salt, TiCl4, was added, and the temperature was increased to 30°C. Stirring was performed for 3 hours, and filtration was performed. Hexane washing was performed twice. Then, 80 mL of toluene was added at 20°C. Then, 0.09 grams of a metallocene catalyst ligand, tetramethylcyclopentadiene (4), was added, and the temperature was increased to 50°C. Stirring was performed for 5 hours, and filtration was performed. Hexane washing was performed twice. Then, 7.5 mL of an activator, MAO (10 wt% toluene solution), was added at 25°C. Then, 40 mL of a solvent, toluene, was added, and stirring was performed for 10 minutes. Under stirring, the solvent was vacuum-dried at 35°C, and 11.3 grams of a supported catalyst was obtained. The transition metal loading of the metallocene catalyst was 0.32 wt%.

[0043] Olefin polymerization:

[0044] After the 2 liter stainless steel autoclave was sufficiently replaced with nitrogen, n-hexane 800 mL was added to the reactor, 10 mg of the supported catalyst prepared in Example 2 was added, 0.2 mL of MAO (10 wt% in toluene) 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 temperature was maintained at 60°C and the reaction was carried out for 0.5 hours. The polymerization product was collected as 49 grams, and the bulk density BD = 0.36 g / cm 3 , M W = 383 kg / mol, density p = 0.895 g / cm 3 It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, agricultural film, home decoration, toy, airplane and high-speed rail non-structural material, interior trim or hydrogen storage tank liner, etc.

[0045] Example 3

[0046] Preparation of supported metallocene catalyst:

[0047] After the 300 mL glass reaction bottle was sufficiently replaced with nitrogen, 12 grams of the carrier magnesium chloride was added to the reaction bottle at 5°C, 90 mL of the inert organic solvent toluene was added, and stirring was carried out for 10 minutes. 30 milliliters of the transition metal salt TiCl4 was added, the temperature was raised to 30°C, and stirring was carried out for 3 hours. Filtration and hexane washing were carried out 4 times. At 20°C, 80 milliliters of toluene was added, 0.15 grams of the metallocene catalyst ligand tert-butylamine-based CGC ligand (12) was added, the temperature was raised to 40°C, and stirring was carried out for 6 hours. Filtration and hexane washing were carried out 2 times. At 30°C, 8 mL of MAO (10 wt% in toluene) was added as an activator, 50 mL of the solvent toluene was added, stirring was carried out for 15 minutes, and the solvent was vacuum-dried at 45°C under stirring conditions. Supported catalyst 13.1 grams was obtained, and the transition metal loading of the metallocene catalyst was 0.33 wt%.

[0048] Olefin polymerization:

[0049] After the 2 liter stainless steel autoclave was sufficiently replaced with nitrogen, n-hexane 1 L was added to the reactor, 5 mg of the supported catalyst prepared in Example 3 was added, 0.2 mL of triethylaluminum (1.5 M) 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 0.7 MPa. The temperature was maintained at 70°C and the reaction was carried out for 20 min. The polymerization product was collected as 131 grams, and the bulk density BD = 0.34 g / cm 3 , M W = 311 kg / mol, density p = 0.881 g / cm 3It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, agricultural film, unmanned aerial vehicle, home decoration, toy, aircraft and high-speed rail non-structural material, interior trim, stab-resistant glove or hydrogen storage tank liner, etc.

[0050] Example 4

[0051] Preparation of supported metallocene catalyst:

[0052] After the 300 mL glass reaction bottle was sufficiently replaced by nitrogen, 12 grams of carrier magnesium chloride and 4 grams of silica gel were added to the reaction bottle at 5°C, 100 mL of inert organic solvent toluene was added, and stirring was performed for 15 minutes; 75 milliliters of transition metal salt TiCl4was added, the temperature was raised to 80°C, and stirring was performed for 3 hours; filtration was performed, and hexane washing was performed 5 times; at 20°C, 80 milliliters of toluene was added, 0.2 grams of metallocene catalyst ligand aniline-based CGC ligand (11) was added, the temperature was raised to 50°C, and stirring was performed for 5 hours; filtration was performed, and hexane washing was performed 3 times; at 30°C, 11.5 mL of activator MAO (10 wt% toluene solution) was added, 50 mL of solvent toluene was added, stirring was performed for 15 minutes, and the solvent was vacuum-dried under stirring at 35°C, thereby obtaining 19.6 grams of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.31 wt%.

[0053] Olefin polymerization:

[0054] After the 2-liter stainless steel autoclave was sufficiently replaced by nitrogen, 1 liter of cyclohexane was added to the reaction kettle, 8 milligrams of the supported catalyst prepared in Example 4 was added, 0.2 milliliters of cocatalyst MAO (10 wt% toluene solution) was added, 10 milliliters of 1-octene was added, 0.01 liters of hydrogen was filled, ethylene was filled to a pressure of 0.8 MPa, stirring was performed, the temperature was maintained at 73°C, and reaction was performed for 2 hours, thereby obtaining 186 grams of polymerization product, and the bulk density BD was 0.39 g / cm 3 , M W = 256 kg / mol, and the density p was 0.912 g / cm 3 It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, agricultural film, unmanned aerial vehicle, home decoration, toy, aircraft and high-speed rail non-structural material, interior trim, stab-resistant glove or hydrogen storage tank liner, etc.

[0055] Example 5

[0056] Preparation of supported metallocene catalyst:

[0057] A 300 mL glass reaction bottle was thoroughly replaced with nitrogen, and 12 grams of carrier magnesium chloride and 3 grams of MXene were added to the reaction bottle at 5°C. 100 mL of inert organic solvent toluene was added, and stirred for 15 minutes. 95 milliliters of transition metal salt TiCl4 was added, and the temperature was raised to 80°C and stirred for 3 hours. 80 milliliters of toluene was added at 20°C, and 0.31 grams of metallocene catalyst ligand aniline-based CGC ligand lithium salt (14) was added, and the temperature was raised to 50°C and stirred for 5 hours. Filtration and hexane washing were performed 5 times. At 30°C, 9.5 mL of activator MAO (10wt% toluene solution) was added, 50 mL of solvent toluene was added, and stirred for 15 minutes. The solvent was vacuum dried at 35°C under stirring conditions to obtain 16.4 grams of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.3wt%.

[0058] Olefin polymerization:

[0059] A 2 liter stainless steel autoclave was thoroughly replaced with nitrogen, and 1L of cyclohexane was added to the reaction kettle. 8 milligrams of supported catalyst prepared in Example 5 was added, and 0.25 mL (1.5M) of cocatalyst triisobutylaluminum was added. 10 grams of 1-butene was added, and 0.01L of hydrogen was charged. The pressure was charged to 0.8 MPa with ethylene, and the temperature was maintained at 55°C for 1 hour. The polymerization product was collected, and the bulk density BD was 0.37 g / cm 3 , M W = 233 kg / mol, and the density p = 0.923 g / cm 3 It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, ship cable, fishing net, agricultural film, unmanned aerial vehicle, home decoration, toy, aircraft and high-speed rail non-structural material, interior trim, stab-resistant gloves, body armor, or hydrogen storage tank liner, etc.

[0060] Example 6

[0061] Preparation of supported metallocene catalyst:

[0062] A 300 mL glass reaction bottle was thoroughly replaced with nitrogen, and 5 grams of carrier magnesium chloride and 3.5 grams of MXene were added to the reaction bottle at 30°C. 100 mL of inert organic solvent toluene was added, and stirred for 15 minutes. 15 grams of transition metal salt NiCl2 was added, and the temperature was raised to 80°C and stirred for 4 hours. 80 milliliters of toluene was added at 20°C, and 0.52 grams of non-metallocene catalyst ligand magnesium salt (13) was added, and the temperature was raised to 50°C and stirred for 6 hours. Filtration and cyclohexane washing were performed 3 times. At 30°C, 40.5 mL of activator TEA (1.5M hexane solution) was added, 30 mL of solvent toluene was added, and stirred for 5 minutes. The solvent was vacuum dried at 35°C under stirring conditions to obtain 10.6 grams of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.28wt%.

[0063] Olefin polymerization:

[0064] After the 2 liter stainless steel autoclave was sufficiently replaced by nitrogen, 1 L of cyclohexane was added to the reaction kettle, 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 grams of butyl acrylate was added, 0 L of hydrogen was filled, ethylene was filled to a pressure of 0.8 MPa, stirring was performed, the temperature was maintained at 50°C for 5 min, and 108 grams of polymerization product was collected, the bulk density BD = 0.34 g / cm 3 , M W = 193 kg / mol, density p = 0.947 g / cm 3 It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, ship cable, fishing net, agricultural film, unmanned aerial vehicle, home decoration, toy, high-speed rail non-structural material of airplane, interior trim, stab-resistant gloves, body armor or hydrogen storage tank liner, etc.

[0065] Example 7

[0066] Preparation of supported metallocene catalyst:

[0067] After the 300 mL glass reaction bottle was sufficiently replaced by nitrogen, 5 grams of carrier silica gel and 2 grams of MXene were added to the reaction bottle at 30°C, 100 mL of inert organic solvent toluene was added, and stirring was performed for 15 min; 10 grams of transition metal salt PdCl2 was added, the temperature was raised to 80°C, and stirring was performed for 4 hours; 80 mL of toluene was added at 20°C, 0.8 grams of non-metallocene catalyst ligand (15) was added, the temperature was raised to 50°C, and stirring was performed for 6 hours; filtration and heptane washing were performed 3 times; 14.5 mL of MAO (10 wt% toluene solution) was added as an activator at 30°C, 30 mL of solvent hexane was added, stirring was performed for 5 min, and the solvent was vacuum-dried under stirring at 35°C, to obtain 7.6 grams of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.29 wt%.

[0068] Olefin polymerization:

[0069] After the 2 liter stainless steel autoclave was sufficiently replaced by nitrogen, 1 L of cyclohexane was added to the reaction kettle, 10 mg of the supported catalyst prepared in Example 7 was added, 0.5 mL of triethylaluminum (1.5 M) was added as a cocatalyst, 3 grams of ethyl undecenoate was added, 0 L of hydrogen was filled, ethylene was filled to a pressure of 0.8 MPa, stirring was performed, the temperature was maintained at 50°C for 0.5 hours, and 63 grams of polymerization product was collected, the bulk density BD = 0.33 g / cm 3 , M W = 211 kg / mol, density p = 0.945 g / cm 3It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, ship cable, fishing net, agricultural film, unmanned aerial vehicle, home decoration, toy, aircraft and high-speed rail non-structural material, interior trim, stab-resistant glove, bulletproof vest or hydrogen storage tank liner, etc.

[0070] Example 8

[0071] Preparation of supported metallocene catalyst:

[0072] After the 500 mL glass reaction bottle was sufficiently replaced by nitrogen, 10 grams of carrier graphite oxide was added to the reaction bottle at 30°C, 110 mL of inert organic solvent toluene was added, and stirring was performed for 15 minutes; 10 grams of transition metal salt NdCl3 was added, the temperature was raised to 80°C, and stirring was performed for 4 hours; 80 milliliters of toluene was added at 20°C, 0.8 grams of non-metallocene catalyst ligand potassium salt (16) was added, the temperature was raised to 50°C, and stirring was performed for 6 hours, then filtration and heptane washing were performed three times; 15.5 mL of activator MAO (10 wt% toluene solution) was added at 30°C, 30 mL of solvent hexane was added, stirring was performed for 5 minutes, and the solvent was vacuum dried under stirring at 35°C, thereby obtaining 11.8 grams of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.27 wt%.

[0073] Olefin polymerization:

[0074] After the 2 liter stainless steel autoclave was sufficiently replaced by nitrogen, 1 L of cyclohexane was added to the reaction kettle, 10 mg of the supported catalyst prepared in Example 8 was added, 0.3 mL (1.5 M) of cocatalyst triethylaluminum was added, 3 grams of 9-decene-1-ol was added, 0.01 L of hydrogen was filled, ethylene was filled to a pressure of 0.8 MPa, stirring was performed, the temperature was maintained at 55°C, and the reaction was performed for 0.5 hours, thereby collecting 48 grams of polymerization product, and the bulk density BD = 0.36 g / cm 3 , M W = 183 kg / mol, and the density p = 0.935 g / cm 3 It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, ship cable, fishing net, agricultural film, unmanned aerial vehicle, home decoration, toy, aircraft and high-speed rail non-structural material, interior trim, stab-resistant glove, bulletproof vest or hydrogen storage tank liner, etc.

[0075] Example 9

[0076] Preparation of supported metallocene catalyst:

[0077] A 500 mL glass reaction flask was sufficiently replaced by nitrogen, and then 10 grams of graphene oxide as a carrier was added into the flask at 30 °C, 110 mL of inert organic solvent toluene was added, and stirred for 15 minutes; 10 grams 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 grams of non-metallocene catalyst ligand (17) was added, the temperature was raised to 50 °C and stirred for 6 hours, and then filtered and washed with heptane for 3 times; 12.5 mL of activator MAO (10 wt% toluene solution) was added at 30 °C, 30 mL of solvent hexane was added, stirred for 5 minutes, and then the solvent was vacuum dried at 35 °C under stirring to obtain 12.2 grams of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.28 wt%.

[0078] Olefin polymerization:

[0079] A 2 liter stainless steel autoclave was sufficiently replaced by nitrogen, and then 1 L of cyclohexane was added into the reactor, 10 mg of supported catalyst prepared in Example 9 was added, 0.3 mL of cocatalyst MAO (10 wt% toluene solution) was added, 3 grams of 1,8-nonadiene was added, 0.01 L of hydrogen was filled, and then ethylene was filled to a pressure of 0.8 MPa, and then stirred and kept at a temperature of 55 °C for 0.5 hours, and then 83 grams of polymerization product was collected, and the bulk density BD = 0.35 g / cm3. 3 , M W = 236 kg / mol, density p = 0.928 g / cm 3 It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, ship cable, fishing net, agricultural film, unmanned aerial vehicle, home decoration, toy, high-speed rail non-structural material of airplane, interior trim, stab-resistant gloves, body armor or hydrogen storage tank liner, etc.

[0080] Example 10

[0081] Preparation of supported metallocene catalyst:

[0082] A 500 mL glass reaction flask was sufficiently replaced by nitrogen, and then 10 grams of graphene oxide as a carrier was added into the flask at 30 °C, 110 mL of inert organic solvent toluene was added, and stirred for 15 minutes; 10 grams 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 grams of non-metallocene catalyst ligand (17) was added, the temperature was raised to 50 °C and stirred for 6 hours, and then filtered and washed with heptane for 3 times; 12.5 mL of activator MAO (10 wt% toluene solution) was added at 30 °C, 30 mL of solvent hexane was added, stirred for 5 minutes, and then the solvent was vacuum dried at 35 °C under stirring to obtain 12.2 grams of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.28 wt%.

[0083] Olefin polymerization:

[0084] A 2 liter stainless steel autoclave was sufficiently replaced with nitrogen, and then 1 L of hexane was added to the reactor, 10 mg of the supported catalyst prepared in Example 10 was added, 0.15 mL of cocatalyst MAO (10 wt% toluene solution) was added, 3 g of 1,8-nonadiene was added, 50 g of propylene was added, 0.01 L of hydrogen was filled, 0.9 MPa of ethylene was filled, and stirring was performed while maintaining the temperature at 60°C for 0.5 hours. The polymerization product was collected in an amount of 55 g, and the bulk density BD was 0.32 g / cm 3 , M W = 262 kg / mol, density p = 0.922 g / cm 3 It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, ship cable, fishing net, agricultural film, unmanned aerial vehicle, home decoration, toy, high-speed rail non-structural material of airplane, interior trim, stab-resistant gloves, body armor, or hydrogen storage tank liner, etc.

[0085] Example 11

[0086] Preparation of supported metallocene catalyst:

[0087] A 300 mL glass reaction bottle was sufficiently replaced with nitrogen, and then 10 g of the carrier silica gel was added to the reaction bottle at 30°C, 80 mL of the inert organic solvent toluene was added, and stirring was performed for 30 minutes. 10 g of the transition metal salt ZrCl4was added, and the temperature was increased to 80°C and stirring was performed for 4 hours. 80 mL of toluene was added at 20°C, 2.5 g of the metallocene catalyst ligand (8) was added, the temperature was increased to 50°C and stirring was performed for 6 hours, and then filtration and heptane washing were performed three times. 15.5 mL of the activator mMAO (10 wt% toluene solution) was added at 30°C, 30 mL of the solvent hexane was added, stirring was performed for 5 minutes, and then the solvent was vacuum-dried under stirring at 35°C. The supported catalyst was obtained in an amount of 13.7 g, and the transition metal loading amount of the metallocene catalyst was 0.32 wt%.

[0088] Olefin polymerization:

[0089] A 2 liter stainless steel autoclave was sufficiently replaced with nitrogen, and then 1 L of hexane was added to the reactor, 10 mg of the supported catalyst prepared in Example 10 was added, 0.15 mL of cocatalyst MAO (10 wt% toluene solution) was added, 3 g of 1,8-nonadiene was added, 50 g of propylene was added, 0.01 L of hydrogen was filled, 0.9 MPa of ethylene was filled, and stirring was performed while maintaining the temperature at 60°C for 0.5 hours. The polymerization product was collected in an amount of 55 g, and the bulk density BD was 0.32 g / cm 3 , M W = 266 kg / mol, density p = 0.903 g / cm 3It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, ship cable, fishing net, agricultural film, unmanned aerial vehicle, home decoration, toy, aircraft and high-speed rail non-structural material, interior trim, stab-resistant gloves, body armor or hydrogen storage tank liner, etc.

[0090] Example 12

[0091] Preparation of supported metallocene catalyst:

[0092] After the 300 mL glass reaction bottle was sufficiently replaced by nitrogen, 10 grams of carrier diethoxy magnesium was added to the reaction bottle at 30°C, 80 mL of inert organic solvent toluene was added, and stirred for 30 minutes; 10 grams of transition metal salt ZrCl4 was added, and the temperature was raised to 80°C and stirred for 4 hours; 80 mL of toluene was added at 20°C, 2.5 grams of metallocene catalyst ligand (10) was added, the temperature was raised to 50°C and stirred for 6 hours, and then filtered and washed with heptane for 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 stirred for 5 minutes; the solvent was vacuum dried at 35°C under stirring conditions, and 14.3 grams of supported catalyst was obtained, and the transition metal loading of the metallocene catalyst was 0.33 wt%.

[0093] Olefin polymerization:

[0094] After the 2 liter stainless steel autoclave was sufficiently replaced by nitrogen, 1 L of toluene was added to the reaction kettle, 10 mg of the supported catalyst prepared in Example 12 was added, 0.5 mL of cocatalyst MAO (10 wt% toluene solution) was added, 3 grams of ethylidene norbornene was added, 50 grams of propylene was added, 0.01 L of hydrogen was filled, 0.9 MPa of ethylene was filled, and stirred, and the temperature was maintained at 60°C for 0.5 hours, and 203 grams of polymerization product was collected, and the bulk density BD = 0.30 g / cm 3 , M W = 72 kg / mol, density p = 0.893 g / cm 3 It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, agricultural film, unmanned aerial vehicle, home decoration, toy, aircraft and high-speed rail non-structural material, interior trim, stab-resistant gloves or hydrogen storage tank liner, etc.

[0095] Example 13

[0096] Preparation of supported metallocene catalyst:

[0097] A 300 mL glass reaction flask was sufficiently replaced by nitrogen, and 10 grams of carrier magnesium chloride was added to the flask at 30°C, 80 mL of inert organic solvent toluene was added, and stirred for 30 minutes; 150 mL of transition metal salt TiCl4 was added, and the temperature was raised to 80°C and stirred for 4 hours; 80 mL of toluene was added at 20°C, 2.5 grams of metallocene catalyst ligand (14) was added, the temperature was raised to 50°C and stirred for 6 hours, and then filtered and washed with heptane for 3 times; 12.5 mL of activator MAO (10wt% toluene solution) was added at 30°C, 30 mL of solvent hexane was added, and stirred for 5 minutes, and then the solvent was vacuum dried at 35°C under stirring to obtain 14.8 grams of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.32wt%.

[0098] Olefin polymerization:

[0099] A 2 liter stainless steel autoclave was sufficiently replaced by nitrogen, and 1L of toluene was added to the reactor, 10 mg of supported catalyst prepared in Example 13 was added, 0.3 mL of cocatalyst MAO (10wt% toluene solution) was added, 40 grams of 1-octane was added, 0.01L of hydrogen was filled, and ethylene was filled to a pressure of 4 MPa, and then stirred, and the temperature was maintained at 140°C for 0.5 hours, and then the polymerization product was collected, and the Mw=162 kg / mol, the density p=0.863 g / cm W 3 It is mainly used for battery adhesive film, building materials, automotive materials, fitness equipment, ship cables, fishing nets, agricultural films, unmanned aerial vehicles, home furnishings, toys, aircraft and high-speed rail non-structural materials, interior trim parts, or hydrogen storage tank liners, etc.

[0100] Example 14

[0101] Preparation of supported metallocene catalyst:

[0102] A 300 mL glass reaction flask was sufficiently replaced by nitrogen, and 10 grams of carrier magnesium chloride was added to the flask at 30°C, 80 mL of inert organic solvent toluene was added, and stirred for 30 minutes; 150 mL of transition metal salt TiCl4 was added, and the temperature was raised to 80°C and stirred for 4 hours, and then filtered and washed with heptane for 3 times; 80 mL of toluene was added at 20°C, 3.5 grams of metallocene catalyst ligand (9) was added, the temperature was raised to 50°C and stirred for 6 hours, and then filtered and washed with heptane for 3 times; 16.5 mL of activator triethylaluminum (1.5M) was added at 30°C, 30 mL of solvent hexane was added, and stirred for 5 minutes, and then the solvent was vacuum dried at 35°C under stirring to obtain 15.2 grams of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.33wt%.

[0103] Olefin polymerization:

[0104] ​A 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, and then 1 L of toluene, 10 mg of the supported catalyst prepared in Example 14, 0.2 mL of cocatalyst MAO (10 wt% toluene solution), 50 g of 1-octene, 0.01 L of hydrogen, and ethylene were sequentially added to the reactor. The temperature was maintained at 120°C for 15 min while stirring, and the pressure was maintained at 4 MPa. The polymerization product was collected, and the molecular weight was measured. The results are shown in Table 1. W Mn= 172 kg / mol, density p = 0.864 g / cm3 3 Mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, building material, automotive material, fitness equipment, agricultural film, unmanned aerial vehicle, home decoration, toy, aircraft and high-speed rail non-structural material, interior trim or hydrogen storage tank liner, etc.

[0105] Example 15

[0106] Preparation of the supported metallocene catalyst:

[0107] A 300-mL glass reaction bottle was sufficiently replaced with nitrogen, and then 10 g of the carrier magnesium chloride, 80 mL of the inert organic solvent toluene, and 200 mL of the transition metal salt TiCl4 were sequentially added to the reactor at 30°C. The temperature was increased to 80°C for 4 hours while stirring, and then the mixture was filtered and washed with hexane three times. Then, 80 mL of toluene, 4.5 g of the metallocene catalyst ligand salt (14), and 30 mL of the solvent hexane were sequentially added to the reactor at 20°C. The temperature was increased to 50°C for 6 hours while stirring, and then the mixture was filtered and washed with heptane three times. Then, 17.5 mL of the activator MAO (10 wt% toluene solution) and 30 mL of the solvent hexane were sequentially added to the reactor at 30°C. The mixture was stirred for 5 min, and then the solvent was vacuum-dried at 35°C while stirring. The supported catalyst was obtained, and the transition metal loading of the metallocene catalyst was 0.33 wt%.

[0108] Olefin polymerization:

[0109] A 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, and then 1 L of toluene, 10 mg of the supported catalyst prepared in Example 15, 0.5 mL of cocatalyst MAO (10 wt% toluene solution), 35 g of 1-octene, 0.01 L of hydrogen, and ethylene were sequentially added to the reactor. The temperature was maintained at 170°C for 10 min while stirring, and the pressure was maintained at 4 MPa. The polymerization product was collected, and the molecular weight was measured. The results are shown in Table 1. W Mn= 142 kg / mol, density p = 0.873 g / cm3 3 Mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, automotive material, fitness equipment, agricultural film, unmanned aerial vehicle, home decoration, toy, aircraft and high-speed rail non-structural material, interior trim, body armor, or hydrogen storage tank liner, etc.

[0110] Example 16

[0111] Preparation of supported metallocene catalyst:

[0112] After the 300 mL glass reaction bottle was sufficiently replaced by nitrogen, 10 grams of carrier magnesium chloride was added to the reaction bottle, 80 mL of inert organic solvent toluene was added, and stirring was performed for 30 minutes; 25 mL of transition metal salt TiCl4 was added, the temperature was increased to 80°C, and stirring was performed for 4 hours; 80 mL of toluene was added at 20°C, 4.5 grams of metallocene catalyst ligand salt (11) was added, the temperature was increased to 50°C, and stirring was performed for 6 hours; filtration was performed, and heptane washing was performed 4 times; 25.5 mL of activator MAO (10 wt% toluene solution) was added at 30°C, 30 mL of solvent hexane was added, stirring was performed for 5 minutes, and the solvent was vacuum dried under stirring at 35°C, thereby obtaining 16.2 grams of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.33 wt%.

[0113] Olefin polymerization:

[0114] After the 2 liter stainless steel autoclave was sufficiently replaced by nitrogen, 1 L of toluene was added to the reaction kettle, 10 mg of the supported catalyst prepared in Example 16 was added, 0.5 mL of cocatalyst MAO (10 wt% toluene solution) was added, 30 grams of 1-octene was added, 0.01 L of hydrogen was filled, 4 MPa of ethylene was filled, stirring was performed, the temperature was maintained at 170°C, and reaction was performed for 20 min, thereby collecting 198 grams of polymerization product, Mw=146 kg / mol, and the density p=0.871 g / cm3. W 3 It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, agricultural film, unmanned aerial vehicle, home decoration, toy, airplane and high-speed rail non-structural material, interior trim, stab-resistant gloves, artificial grass, or hydrogen storage tank liner, etc.

[0115] Example 17

[0116] Preparation of supported metallocene catalyst:

[0117] After the 300 mL glass reaction bottle was sufficiently replaced by nitrogen, 12 grams of carrier magnesium chloride was added to the reaction bottle at 5°C, 90 mL of inert organic solvent toluene was added, and stirring was performed for 10 minutes; 30 mL of transition metal salt TiCl4 was added, the temperature was increased to 30°C, and stirring was performed for 3 hours; filtration was performed, and hexane washing was performed 4 times; 80 mL of toluene was added at 20°C, 0.15 grams of metallocene catalyst ligand 2,6-difluoroanilino CGC ligand (14) was added, the temperature was increased to 40°C, and stirring was performed for 6 hours; filtration was performed, and hexane washing was performed 2 times; 60 mL of activator MAO (10 wt% toluene solution) was added at 30°C, 50 mL of solvent toluene was added, stirring was performed for 15 minutes, and the solvent was vacuum dried under stirring at 45°C, thereby obtaining 14.8 grams of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.31 wt%. ​

[0118] Olefin polymerization:

[0119] After the 2 liter stainless steel autoclave was sufficiently replaced with nitrogen, 1 L of n-hexane was added to the reactor, 10 mg of the supported catalyst prepared in Example 17 was added, 0.5 mL of triethylaluminum (1.5 M hexane solution) was added as a cocatalyst, 3 mL of 1-octene was added, and ethylene was charged to a pressure of 0.9 MPa, and the temperature was maintained at 60°C for 2 hours while stirring. The polymerization product was collected as 251 grams, and the bulk density BD = 0.38 g / cm 3 , M W = 3530 kg / mol, density p = 0.951 g / cm 3 It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, automotive material, fitness equipment, anti-creep ship cable, fishing net, agricultural film, unmanned aerial vehicle, home decoration, toy, high-speed rail non-structural material of airplane, interior trim, high-altitude and deep-sea equipment material, anti-nuclear radiation material, anti-stab gloves, body armor or hydrogen storage tank liner, etc.

[0120] Example 18

[0121] Preparation of supported metallocene catalyst:

[0122] After the 30 L reaction bottle was sufficiently replaced with nitrogen, 1.2 kg of the carrier magnesium chloride was added to the reaction bottle at 5°C, 12 L of the inert organic solvent toluene was added, and stirring was performed for 10 minutes; 9 liters of the transition metal salt TiCl4 was added, the temperature was raised to 30°C, and stirring was performed for 3 hours, filtration was performed, and hexane washing was performed 4 times; 8 L of toluene was added at 20°C, 25 grams of the metallocene catalyst ligand 2,6-difluoroanilino CGC ligand (14) was added, the temperature was raised to 40°C, and stirring was performed for 6 hours, filtration was performed, and hexane washing was performed 2 times; 800 mL of the activator MAO (10 wt% toluene solution) was added at 30°C, 50 mL of the solvent toluene was added, stirring was performed for 15 minutes, and the solvent was vacuum-dried at 45°C under stirring to obtain 1.26 kg of the supported catalyst, and the transition metal loading of the metallocene catalyst was 0.3 wt%.

[0123] Olefin polymerization:

[0124] After the 2 liter stainless steel autoclave was sufficiently replaced with nitrogen, 1 L of n-hexane was added to the reactor, 10 mg of the supported catalyst prepared in Example 18 was added, 0.5 mL of triethylaluminum (1.5 M hexane solution) was added as a cocatalyst, 3 mL of 1-octene was added, and ethylene was charged to a pressure of 0.9 MPa, and the temperature was maintained at 70°C for 2 hours while stirring. The polymerization product was collected as 239 grams, and the bulk density BD = 0.39 g / cm 3 , M W = 2876 kg / mol, density p = 0.949 g / cm 3It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, anti-creep ship cable, fishing net, agricultural film, unmanned aerial vehicle, home decoration, toy, aircraft and high-speed rail non-structural material, interior trim, high-altitude and deep-sea equipment material, nuclear radiation resistant material, stab-resistant glove, body armor or hydrogen storage tank liner, etc.

[0125] Example 19

[0126] Preparation of supported metallocene catalyst:

[0127] After the 500L reaction bottle was sufficiently replaced with nitrogen, the carrier magnesium chloride 21kg and silica gel 9kg were added to the reaction bottle at 5°C, 100L of inert organic solvent toluene was added, and stirring was performed for 10 minutes; 100 liters of transition metal salt TiCl4 was added, the temperature was raised to 30°C, and stirring was performed for 3 hours, then filtration and hexane washing were performed 4 times; 110L of toluene was added at 20°C, 550 grams of metallocene catalyst ligand aniline-based CGC ligand (11) was added, the temperature was raised to 40°C, and stirring was performed for 6 hours, then filtration and hexane washing were performed 2 times; 2.5L of activator MAO (10wt% toluene solution) was added at 30°C, 50mL of solvent toluene was added, stirring was performed for 15 minutes, and under stirring conditions, the solvent was vacuum dried at 45°C to obtain 31.3kg of supported catalyst, and the transition metal loading of the metallocene catalyst was 0.32wt%.

[0128] Olefin polymerization:

[0129] After the 2L stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 10mg of the supported catalyst prepared in Example 19 was added, 0.5mL of cocatalyst triethylaluminum (1.5M hexane solution) was added, 10mL of 1-octene was added, 0.001MPa of hydrogen was added, ethylene was filled to a pressure of 0.9MPa, stirring was performed, the temperature was maintained at 70°C, and reaction was performed for 2 hours, then 273 grams of polymerization product was collected, the bulk density BD = 0.39g / cm 3 , M W = 366kg / mol, density p = 0.941g / cm 3 It is mainly used for battery adhesive film, temperature-resistant and pressure-resistant pipe material, shoe material, building material, vehicle material, fitness equipment, anti-creep ship cable, fishing net, agricultural film, unmanned aerial vehicle, home decoration, toy, aircraft and high-speed rail non-structural material, interior trim, high-altitude and deep-sea equipment material, nuclear radiation resistant material, stab-resistant glove, body armor or hydrogen storage tank liner, etc.

Claims

1. A process for the preparation of 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 supported in situ on the carrier, comprising the following steps: (1) dispersing a carrier in an inert organic solvent at -20-50℃, the molar ratio of the inert organic solvent to the carrier is (5-500):1, stirring for 5 minutes-5 hours; wherein the carrier is a multi-hydroxyl solid, which refers to a solid compound with multi-hydroxyl or a solid material with multi-hydroxyl compound or a solid material with multi-hydroxyl itself, wherein the multi-hydroxyl solid is carbon oxide tube, carbon oxide ball, graphite oxide, silica gel, fine coal particles, polymeric alumina, hydrotalcite, multi-hydroxyl POSS, cellulose, polysaccharide or chitin; wherein the carrier is magnesium halide, the magnesium halide is selected from at least one of the compounds of general formula (1) Mg(R) a X b , R is selected from C1-C 20 aliphatic hydrocarbon group, C1-C 20 aliphatic alkoxy group, C3-C 20 alicyclic group or C6-C 20 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, carbon oxide tube, carbon oxide ball, graphite oxide, graphene oxide, alkoxy magnesium, MXene, fine coal particles, polymeric alumina or hydrotalcite or their mixture; (2) at -20-100℃, the transition metal salt is added to (1), the mass ratio of the added transition metal salt to the carrier is (0.1-3000):100, stirring, contacting and reacting at -20-100℃ for 1-8 hours, filtering, inert organic solvent washing, and washing away the excess transition metal salt; (3) at -20-100℃, the metallocene catalyst ligand or the metallocene catalyst ligand salt is added to (2), the mass ratio of the metallocene catalyst ligand to the carrier is (0.001-5):1, stirring, reacting at -20-100℃ 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 pre-transition metal catalyst ligand, or a non-metallocene post-transition metal catalyst ligand, or a mixed ligand thereof or the ligand salt; (4) at 0-80℃, the inert organic solvent in (3) is filtered out, vacuum dried, washed with inert organic solvent for 2-5 times; inert organic solvent is added, an alkyl aluminum solution is added as an activator, the molar ratio of the activator alkyl aluminum to the metallocene catalyst transition metal is (2-500):1, stirring, contacting at 0-80℃ for 10-120min, vacuum drying at 0-80℃, and obtaining a supported metallocene catalyst.

2. The production method according to claim 1, characterized by, wherein the metallocene catalyst ligand or metallocene catalyst ligand salt is methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene, tetramethylcyclopentadiene, pentamethylcyclopentadiene, C5-C 30 indene and derivatives thereof, C9-C 30 fluorene and derivatives thereof, silicon bridged bis-metallocene ligands, ethyl bridged bis-metallocene ligands, t-butylamine based CGC ligands, aniline based CGC ligands, halogenated aniline based CGC ligands, alpha-diimine ligands, salicylaldimine ligands, polydentate 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 method of claim 1, wherein, The activator aluminum alkoxide is a C1-C 20 alkoxide of aluminum.

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 method of claim 1, wherein, 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 supported in situ on the carrier, comprising the following steps: The inert organic solvent is selected from a C5-Ci2aliphatic or cycloaliphatic hydrocarbon, or a C6-Ci2aromatic hydrocarbon, or a mixture solvent thereof. 20 The inert organic solvent is selected from a C5-Ci2aliphatic or cycloaliphatic hydrocarbon, or a C6-Ci2aromatic hydrocarbon, or a mixture solvent thereof. 20 The inert organic solvent is selected from a C5-Ci2aliphatic or cycloaliphatic 7. The use of the supported metallocene catalyst prepared by the preparation method of claim 1.

8. Use according to claim 7, characterized in that: The supported metallocene catalyst is put into an olefin polymerization reactor, a cocatalyst is added, and an olefin is charged, and the reaction is carried out for 1 minute to 5 hours to obtain a polyolefin; the partial pressure of the olefin is 0.1-10 MPa, the partial pressure of hydrogen is 0.001-0.1 MPa, and the polymerization temperature is 20-200°C, wherein the olefin is ethylene or C3-C 30 alkene or a mixture thereof, and the molar ratio of the cocatalyst to the transition metal of the supported metallocene catalyst is (5-1500):1, wherein the cocatalyst is an alkyl aluminum or an alkoxy aluminum; and wherein the olefin is ethylene or C3-C 30 alkene or a mixture thereof.

9. Use according to claim 8, characterized in that The supported metallocene catalyst is used in a gas phase fluidized bed process, a gas phase process, a slurry process, a loop process, or a combined process, to produce polyolefin plastic materials or polyolefin elastic materials.

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