Environmentally friendly catalysts and their use in the preparation of ultrahigh molecular weight polyolefin film materials

Abstract

The present application relates to the technical field of catalysts, in particular to an environment-friendly catalyst and application thereof to preparation of ultra-high molecular weight polyolefin film material.The catalyst comprises a carrier and an active component loaded on the carrier; wherein the active component comprises a metal complex and an aluminum chloride composite ionic liquid.The catalyst in the present application has high activity and high selectivity in the process of ethylene polymerization, and can obtain an ultra-high molecular weight polyethylene product, and meanwhile, the performance of the ultra-high molecular weight polyethylene is excellent.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalyst technology, in particular to an environmentally friendly catalyst and its application in preparing ultra-high molecular weight polyolefin film material. BACKGROUND

[0002] Ultra-high molecular weight polyethylene (UHMWPE) is a kind of polyethylene material with extremely high molecular weight, its molecular weight is usually above 3 million. Due to its unique physical properties, such as extremely high molecular weight, excellent wear resistance, impact resistance and chemical stability, UHMWPE has become an indispensable important material in the field of engineering plastics. UHMWPE film material has been widely used in many fields such as aerospace, medical equipment, personal protective equipment, etc. due to its excellent performance.

[0003] With the continuous progress of science and technology, the performance requirements of UHMWPE film material are becoming higher and higher, which requires us not only to improve its production efficiency, but also to further improve the quality of the final product. At present, the production efficiency and product quality of UHMWPE depend largely on the performance of the catalyst used. Therefore, the development of new high-efficiency catalysts is of great significance for further improving the performance of UHMWPE film material. SUMMARY

[0004] In the present application, unless otherwise specified, the pressure referred to is gauge pressure, and the room temperature referred to is 20-35℃.

[0005] The first aspect of the present application provides an environmentally friendly catalyst, which comprises a carrier and an active component loaded on the carrier; wherein the active component comprises a metal complex and an aluminum chloride composite ionic liquid.

[0006] The catalyst in the present application can realize high-activity polymerization of ethylene, thereby obtaining ultra-high molecular weight polyethylene, and the ultra-high molecular weight polyethylene prepared has excellent performance.

[0007] As a preferred technical solution of the present application, the carrier is selected from molecular sieves.

[0008] As a preferred technical solution of the present application, the molecular sieve is selected from TS-1 titanium silicate molecular sieve, ZSM-11 molecular sieve and NaY type molecular sieve.

[0009] As a more preferred technical solution of the present application, the molecular sieve is TS-1 titanium silicate molecular sieve, preferably the molar ratio of silicon to titanium of the TS-1 titanium silicate molecular sieve is 30-70, and preferably the average particle size of the TS-1 titanium silicate molecular sieve is 0.2-10 microns.

[0010] In the present application, it is found that using molecular sieve as carrier, especially TS-1 titanium silicalite as carrier, not only has excellent catalytic activity, but also the ultra-high molecular weight polyethylene prepared by using the catalyst has excellent particle size uniformity.

[0011] The TS-1 titanium silicalite in the present application can be commercially available, for example, purchased from Raodong (Liaoning) New Material Co., Ltd.

[0012] As a preferred technical solution of the present application, the metal in the metal complex includes Mg and Ni.

[0013] As a more preferred technical solution of the present application, the metal in the metal complex further includes an alkali metal.

[0014] The alkali metal element in the metal complex of the present application can further increase the activity of the catalyst and the polyethylene prepared by using the catalyst in the polymerization has a higher molecular weight.

[0015] As a more preferred technical solution of the present application, the alkali metal is selected from at least one of Li, K and Na, and is preferably Na.

[0016] As a preferred technical solution of the present application, the ligand in the metal complex is selected from 5,10,15,20-tetrakis(4-hydroxyphenyl) porphyrin and trimesic acid.

[0017] In the present application, using 5,10,15,20-tetrakis(4-hydroxyphenyl) porphyrin and trimesic acid as the double ligand finally prepared the catalyst has better catalytic activity, it is speculated that because the metal atom can make the atomic coordination distribution more uniform by the above double ligand.

[0018] As a more preferred technical solution of the present application, the molar ratio of 5,10,15,20-tetrakis(4-hydroxyphenyl) porphyrin to trimesic acid is 1: (0.1-0.5), for example, 1:0.1, 1:0.2, 1:0.3, 1:0.4 or 1:0.5, and preferably 1: (0.2-0.3).

[0019] The amount of ligand in the catalyst in the present application is calculated based on the amount of addition.

[0020] As a preferred technical solution of the present application, the aluminum chloride complex ionic liquid is selected from aluminum chloride-quaternary ammonium ionic liquid.

[0021] As a more preferred technical solution of the present application, the aluminum chloride-quaternary ammonium ionic liquid is selected from at least one of aluminum chloride-trioctylmethylammonium bis(trifluoromethanesulfonyl) imide salt, aluminum chloride-trimethylamine hydrochloride and aluminum chloride-trioctylmethylammonium tetrafluoroborate.

[0022] Currently, in order to increase the antistatic property of the ultra-high molecular weight, an antistatic agent is usually added in the preparation process to reduce the resistivity of the ultra-high molecular weight polyethylene. However, the addition of the antistatic agent will reduce the mechanical properties, corrosion resistance, wear resistance and swelling resistance and other properties of the ultra-high molecular weight polyethylene. The ultra-high molecular weight polyethylene and the film product prepared by using the catalyst of the present application can increase the antistatic property of the ultra-high molecular weight polyethylene and the film product to a certain extent, and reduce the use of the antistatic agent in the subsequent preparation process of the ultra-high molecular weight polyethylene.

[0023] As a preferred technical solution of the present application, the preparation method of the environmentally friendly catalyst comprises:

[0024] S1 Preparation of metal complex: first mixing the metal source with the first organic solvent, then adding the ligand for complexation reaction, then adding sodium hydride for first reaction, and finally first post-treatment to obtain the metal complex;

[0025] S2 Preparation of aluminum chloride composite ionic liquid: adding the quaternary ammonium ionic liquid and aluminum chloride into n-hexane for reflux reaction, and then removing n-hexane to obtain the aluminum chloride composite ionic liquid;

[0026] S3 Loading of active component: adding the metal complex and the carrier into the third organic solvent for third mixing, then filtering and solid-phase drying in sequence to obtain a catalyst intermediate; dispersing the catalyst intermediate in a mixed system of the aluminum chloride composite ionic liquid and water, then performing room temperature impregnation, and then drying to obtain the environmentally friendly catalyst.

[0027] As a preferred technical solution of the present application, in step S1, the metal source is selected from magnesium salt and nickel salt.

[0028] As a preferred technical solution of the present application, in step S1, the molar ratio of the magnesium salt to the nickel salt is (0.2-1):1, for example, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1 or 1:1, preferably (0.4-0.5):1, wherein the magnesium salt is calculated based on the magnesium element and the nickel salt is calculated based on the nickel element.

[0029] The magnesium salt in the present application can be any magnesium salt in the art, and the magnesium salt can be at least one selected from the group consisting of magnesium nitrate, magnesium acetate, magnesium carbonate and magnesium sulfate; the magnesium salt in the present application can exist in a hydrated form, for example, magnesium nitrate hexahydrate.

[0030] The nickel salt in the present application can be any nickel salt in the art, and the nickel salt can be at least one selected from the group consisting of nickel nitrate, nickel acetate, nickel sulfate and nickel chloride; the nickel salt in the present application can exist in a hydrated form, for example, nickel nitrate hexahydrate.

[0031] As a preferred technical solution of the present application, in step S1, the first organic solvent is at least one selected from the group consisting of N,N-dimethylformamide, N,N-dimethylformamide and dimethyl sulfoxide and tetrahydrofuran; the first organic solvent in the present application is exemplarily illustrated by N,N-dimethylformamide, but not limited to the present application.

[0032] As a preferred technical solution of the present application, in step S1, the mass ratio of the metal source to the first organic solvent is (0.8-1.5):100.

[0033] In the present application, the mixing conditions of the first mixture are not particularly limited, as long as the ligand can be uniformly mixed with the first organic solvent, for example, mixing at 40-50℃ for 10-30 minutes.

[0034] As a preferred technical solution of the present application, in step S1, the metal source is calculated by metal, and the molar ratio of the ligand to the metal source is 1:(0.8-1.2).

[0035] As a preferred technical solution of the present application, in step S1, the complexing reaction conditions include: under a nitrogen atmosphere, the complexing temperature is 65-75℃, and the complexing time is 4-8 hours.

[0036] As a preferred technical solution of the present application, in step S1, the first reaction conditions include: the reaction temperature is 0~-10℃, and the reaction time is 1-2 hours.

[0037] As a preferred technical solution of the present application, in step S1, the molar ratio of sodium hydride to the ligand is (1.5-3):1.

[0038] In the present application, the first post-treatment can be carried out by using conventional technical means in the art, for example, after the complexing reaction is completed, the reaction liquid is cooled to room temperature, and then filtered, the obtained solid is washed with n-hexane, and then vacuum dried to constant weight to obtain the metal complex.

[0039] As a preferred technical solution of the present application, in step S2, the molar ratio of the quaternary ammonium ionic liquid to aluminum chloride is 1:(1.5-2).

[0040] As a preferred technical solution of the present application, in step S2, the mass ratio of n-hexane to quaternary ammonium ionic liquid is 10: (1-2).

[0041] As a preferred technical solution of the present application, in step S2, the reflux reaction conditions include: temperature of 70-80℃, time of 2-4 hours.

[0042] The method for removing n-hexane in step S2 of the present application can be a conventional method in the art, for example, using a rotary evaporation method.

[0043] As a preferred technical solution of the present application, in step S3, the mass ratio of the metal complex to the carrier is (25-40): 100.

[0044] As a preferred technical solution of the present application, in step S3, the mass ratio of the carrier to the third organic solvent is 1: (20-30).

[0045] As a preferred technical solution of the present application, in step S3, the third organic solvent is selected from at least one of tetrahydrofuran, toluene and benzene, preferably tetrahydrofuran.

[0046] As a preferred technical solution of the present application, in step S3, the third mixing conditions include: room temperature, time of 4-8 hours.

[0047] The solid-phase drying and drying in step S3 of the present application can be a conventional drying method in the art, for example, drying at 100-120℃ for 6-12 hours.

[0048] As a preferred technical solution of the present application, in step S3, the mass ratio of the aluminum chloride composite ionic liquid to the carrier is (20-25): 100.

[0049] As a preferred technical solution of the present application, in step S3, the mass ratio of the aluminum chloride composite ionic liquid to water is 1: (10-15).

[0050] As a preferred technical solution of the present application, in step S3, the dispersion can be a conventional dispersion method in the art, for example, ultrasonic dispersion.

[0051] As a preferred technical solution of the present application, in step S3, the room temperature immersion time is 12-18 hours.

[0052] The second aspect of the present application provides an environmentally friendly catalyst for preparing an ultra-high molecular weight polyolefin film material, wherein the environmentally friendly catalyst comprises the environmentally friendly catalyst of the first aspect of the present application.

[0053] In the present application, the ultra-high molecular weight polyolefin film material in the present application can be prepared according to the conventional preparation method in the art.

[0054] Compared with the prior art, the present application has at least the following beneficial effects:

[0055] 1. The catalyst of the present application can improve the molecular weight of UHMWPE, optimize the molecular structure, and enhance the physical properties of the film material, such as better improving the impact resistance of the film;

[0056] 2. The catalyst in the present application is environmentally friendly, can reduce environmental pollution and reduce resource consumption, and can be used without using a cocatalyst. DETAILED DESCRIPTION

[0057] The present application will be described in detail below by examples, and the following examples are only exemplary descriptions of specific technical solutions of the present application, and do not limit the scope of the present application, that is, it should be understood that non-essential simple modifications, adjustments and combinations made by those skilled in the art according to the inventive concept of the present application are within the scope of the present application.

[0058] Example 1

[0059] Preparation of S1 metal complex:

[0060] Nickel nitrate hexahydrate, magnesium nitrate hexahydrate and N,N-dimethylformamide with a mass ratio of 29:11.2:4000 were mixed at 45℃ for 23 minutes, then the ligand (5,10,15,20-tetra(4-hydroxyphenyl) porphyrin and trimesic acid with a molar ratio of 1:0.23) was added, after the addition of the ligand, the air in the system was replaced with nitrogen, and the temperature was raised to 70℃, and the complexation reaction was carried out at 70℃ for 6 hours, after the completion of the complexation reaction, the reaction system was placed in an ice water bath at-10℃, sodium hydride was added and reacted for 1 hour, then filtered under room temperature, the obtained solid was washed with n-hexane for 5 times, then vacuum dried to constant weight to obtain the metal complex;

[0061] wherein the nickel nitrate hexahydrate is calculated as nickel element, the magnesium nitrate hexahydrate is calculated as magnesium element, and the molar amount of the ligand is 1:1 compared with the total molar amount of the nickel nitrate hexahydrate and the magnesium nitrate hexahydrate;

[0062] The total molar amount of the nickel nitrate hexahydrate and the magnesium nitrate hexahydrate is 1:2.5 compared with the molar amount of sodium hydride.

[0063] Preparation of S2 aluminum chloride composite ionic liquid:

[0064] Tricaprylmethylammonium bis(trifluoromethanesulfonyl) imide salt and aluminum chloride with a molar ratio of 1:1.8 were added to n-hexane and refluxed at 75℃ for 3 hours, then n-hexane was removed by rotary evaporation to obtain the aluminum chloride composite ionic liquid.

[0065] The mass ratio of n-hexane to tricaprylylmethylammonium bis(trifluoromethanesulfonyl)imide salt is 10:1.4.

[0066] Loading of S3 active component:

[0067] The metal complex, TS-1 titanium silicate molecular sieve (silicon-titanium molar ratio of 60, average particle size of 5 microns, purchased from Raodong (Liaoning) New Material Co., Ltd.) was added to tetrahydrofuran and mixed at room temperature for 6 hours, and then filtered, solid-phase dried at 110°C for 8 hours to obtain a catalyst intermediate;

[0068] The aluminum chloride composite ionic liquid was mixed with water to obtain a mixed system, which was ultrasonically dispersed and then impregnated at room temperature for 14 hours, and then dried at 110°C for 12 hours to obtain a catalyst;

[0069] The mass ratio of the metal complex to TS-1 titanium silicate molecular sieve is 34:100;

[0070] The mass ratio of TS-1 titanium silicate molecular sieve to tetrahydrofuran is 1:25;

[0071] The mass ratio of aluminum chloride composite ionic liquid to TS-1 titanium silicate molecular sieve is 22:100;

[0072] The mass ratio of aluminum chloride composite ionic liquid to water is 1:12.5.

[0073] Example 2

[0074] Preparation of S1 metal complex:

[0075] Nickel nitrate hexahydrate, magnesium nitrate hexahydrate and N,N-dimethylformamide in a mass ratio of 29:12:4000 were mixed at 45°C for 30 minutes, and then the ligand (5,10,15,20-tetra(4-hydroxyphenyl)porphyrin and trimesic acid in a molar ratio of 1:0.28) was added. After the addition of the ligand, the system was replaced with nitrogen to remove air, and the temperature was raised to 70°C. The complexation reaction was carried out at 70°C for 6 hours. After the completion of the complexation reaction, the reaction system was placed in an ice water bath at -10°C, and sodium hydride was added and reacted for 1 hour. Then, the obtained solid was washed with n-hexane for 5 times, and then vacuum dried to constant weight to obtain the metal complex.

[0076] The mass ratio of nickel nitrate hexahydrate to magnesium nitrate hexahydrate was 1:1, and the molar ratio of the ligand to the total moles of nickel nitrate hexahydrate and magnesium nitrate hexahydrate was 1:1.

[0077] The molar ratio of the total moles of nickel nitrate hexahydrate and magnesium nitrate hexahydrate to sodium hydride was 1:2.2.

[0078] Preparation of S2 aluminum chloride composite ionic liquid:

[0079] Tri-n-octylmethylammonium bis(trifluoromethanesulfonyl)imide salt with a molar ratio of 1:1.5 and aluminum chloride were added into n-hexane and reacted at 80°C for 2 hours, and then n-hexane was removed by rotary evaporation to obtain the aluminum chloride composite ionic liquid;

[0080] The mass ratio of n-hexane to tri-n-octylmethylammonium bis(trifluoromethanesulfonyl)imide salt was 10:2.

[0081] S3 loading of active components:

[0082] The metal complex and TS-1 titanium silicate molecular sieve (silicon-titanium molar ratio of 60, average particle size of 5 microns, purchased from Raodong (Liaoning) New Materials Co., Ltd.) were added to tetrahydrofuran and mixed at room temperature for 8 hours, and then filtered, solid-phase dried at 110°C for 8 hours to obtain a catalyst intermediate;

[0083] The aluminum chloride composite ionic liquid was mixed with water to obtain a mixed system, which was ultrasonically dispersed and then impregnated at room temperature for 18 hours, and then dried at 110°C for 12 hours to obtain a catalyst.

[0084] The mass ratio of the metal complex to TS-1 titanium silicate molecular sieve was 34:100.

[0085] The mass ratio of TS-1 titanium silicate molecular sieve to tetrahydrofuran was 1:30.

[0086] The mass ratio of aluminum chloride composite ionic liquid to TS-1 titanium silicate molecular sieve was 25:100.

[0087] The mass ratio of aluminum chloride composite ionic liquid to water was 1:10.

[0088] Example 3

[0089] According to the method of Example 1, except that:

[0090] TS-1 titanium silicate molecular sieve was replaced by ZSM-11 molecular sieve (silicon-aluminum molar ratio of 85, average particle size of 1.5 microns, Raodong (Liaoning) New Materials Co., Ltd.), and finally a catalyst was obtained.

[0091] Example 4

[0092] According to the method of Example 1, except that:

[0093] S1 preparation of metal complex:

[0094] Nickel nitrate hexahydrate, magnesium nitrate hexahydrate and N,N-dimethylformamide in a mass ratio of 29:11.2:4000 were mixed at 45°C for 23 minutes, and then the ligand (5,10,15,20-tetra(4-hydroxyphenyl)porphyrin and trimesic acid in a molar ratio of 1:0.23) was added. After the addition of the ligand, the air in the system was replaced with nitrogen, and the temperature was raised to 70°C. The complexation reaction was carried out at 70°C for 6 hours. After the completion of the complexation reaction, the reaction system was placed in an ice water bath at -10°C, and sodium hydride was added. The reaction was carried out for 1 hour at room temperature. The obtained solid was washed with n-hexane for 5 times, and then vacuum dried to constant weight to obtain the metal complex. The nickel nitrate hexahydrate was calculated based on the nickel element, the magnesium nitrate hexahydrate was calculated based on the magnesium element, and the molar ratio of the ligand to the total moles of nickel nitrate hexahydrate and magnesium nitrate hexahydrate was 1:1.

[0095] The final catalyst was obtained.

[0096] Example 5

[0097] According to the method of Example 1, except that:

[0098] The tricaprylylmethylammonium bis(trifluoromethanesulfonyl)imide salt was replaced with trimethylamine hydrochloride, and the final catalyst was obtained.

[0099] Example 6

[0100] According to the method of Example 1, except that:

[0101] The ligand was 5,10,15,20-tetra(4-hydroxyphenyl)porphyrin, and the final catalyst was obtained.

[0102] Comparative Example 1

[0103] Nickel nitrate hexahydrate, magnesium nitrate hexahydrate and N,N-dimethylformamide in a mass ratio of 29:11.2:4000 were mixed at 45°C for 23 minutes, and then the ligand (5,10,15,20-tetra(4-hydroxyphenyl)porphyrin and trimesic acid in a molar ratio of 1:0.23) was added. After the addition of the ligand, the air in the system was replaced with nitrogen, and the temperature was raised to 70°C. The complexation reaction was carried out at 70°C for 6 hours. After the completion of the complexation reaction, the reaction system was placed in an ice water bath at -10°C, and sodium hydride was added. The reaction was carried out for 1 hour at room temperature. The obtained solid was washed with n-hexane for 5 times, and then vacuum dried to constant weight to obtain the metal complex.

[0104] The nickel nitrate hexahydrate was calculated based on the nickel element, the magnesium nitrate hexahydrate was calculated based on the magnesium element, and the molar ratio of the ligand to the total moles of nickel nitrate hexahydrate and magnesium nitrate hexahydrate was 1:1.

[0105] The molar ratio of the total moles of nickel nitrate hexahydrate and magnesium nitrate hexahydrate to sodium hydride was 1:2.5.

[0106] Loading of S3 active component:

[0107] The metal complex, TS-1 titanium silicalite (molar ratio of silicon to titanium is 60, average particle size is 5 microns, purchased from Raodong (Liaoning) New Material Co., Ltd.) was added to tetrahydrofuran and mixed at room temperature for 6 hours, and then filtered, and solid-phase dried at 110°C for 8 hours to obtain the catalyst.

[0108] Application Example

[0109] Application Example 1-6

[0110] Polyethylene was prepared using the catalysts in Examples 1-6, respectively.

[0111] Polymerization process: after nitrogen replacement, dehydrated n-heptane 2L and catalyst 13 mg were sequentially added into a 5L stainless steel autoclave, and then ethylene was introduced until the pressure was 0.8 MPa, and the polymerization reaction was carried out at 55°C for 3 hours under the pressure of 0.8 MPa to obtain polymer powder (ultrahigh molecular weight polyethylene).

[0112] Preparation of ultrahigh molecular weight polyethylene particles: the polymer powder was added into the hopper of the twin-screw extruder, and was melted, mixed and plasticized in the twin-screw extruder, wherein the temperatures of the six zones of the twin-screw extruder were 175°C, 245°C, 260°C, 270°C, 260°C and 235°C, respectively, and the feeding speed was set to 150 pph, and finally the ultrahigh molecular weight polyethylene particles were obtained.

[0113] Preparation of standard sample: the single-screw extruder was started, and the temperatures of the four zones of the single-screw extruder were set to 100°C, 180°C, 210°C and 220°C, respectively, and the temperature of the head extrusion sheet die was 210°C, and after the temperature was constant, it was kept constant for 20 minutes; then the ultrahigh molecular weight polyethylene particles were added into the hopper of the single-screw extruder, and the rotating speed was set to 3 rpm, and the single-screw extruder was used to extrude the melt, and the melt was extruded into a rough sheet film through a film forming die, and the rough sheet film was made into a standard sample with a size of 100mm*100mm.

[0114] Preparation of high molecular weight polyethylene film material: the standard sample was placed on the sample holder of the film biaxial stretching tester, the edges of the sample were fixed flat by the stretching clamp, and then the film entered the preheating zone under the action of the guide rail, was preheated at 136°C for 1 minute, and was stretched on the film biaxial stretching tester with the transverse stretching ratio and the longitudinal stretching ratio set to 2, the transverse stretching speed set to 23.83 MPa, and the longitudinal stretching speed set to 43.54 MPa, after the stretching was completed, the film was cooled by cold air, and returned to the sample inlet zone under the action of the guide rail, the clamp was loosened, and the sample (ultrahigh molecular weight polyethylene film material) was taken out.

[0115] Comparative Application Example 1

[0116] Polymerization process: in 5L stainless steel autoclave, after nitrogen replacement, dehydrated n-heptane 2L, catalyst 10mg in comparative example 1 and hexane solution of aluminum chloride composite ionic liquid (example 1) (the mass of triethylaluminum is 3mg, the concentration is 1mol / L) were added in turn, then ethylene was introduced to 0.8MPa, at 55℃, the pressure was kept at 0.8MPa for 3 hours, the polymerization powder (ultrahigh molecular weight polyethylene) was obtained, then the preparation of ultrahigh molecular weight polyethylene particles, the preparation of standard sample and high molecular weight polyethylene film material were prepared in turn according to the method of application example.

[0117] Comparative application example 2

[0118] Polymerization process: in 5L stainless steel autoclave, after nitrogen replacement, dehydrated n-heptane 2L, catalyst 10mg in comparative example 1 and hexane solution of aluminum chloride composite ionic liquid (example 1) (the mass of triethylaluminum is 3mg, the concentration is 1mol / L) were added in turn, then ethylene was introduced to 0.8MPa, at 55℃, the pressure was kept at 0.8MPa for 3 hours, the polymerization powder (ultrahigh molecular weight polyethylene) was obtained, then the preparation of ultrahigh molecular weight polyethylene particles, the preparation of standard sample and high molecular weight polyethylene film material were prepared in turn according to the method of application example.

[0119] Determination of polymerization results: the weight average molecular weight Mw of the polymerization powder, the polymerization activity and the mass content of the particle size of 100-250 microns in the polymerization powder were determined respectively.

[0120] The Izod impact strength of the standard sample was determined according to GB / T1843-2008.

[0121] The volume resistivity of the ultrahigh molecular weight polyethylene film material was determined by using C46A type digital high resistance meter.

[0122] The test results are shown in table 1.

[0123] Mw / million Polymerization activity 10 4 gPE / gcat Mass content of particles having a particle size of 100 to 250 micrometers in the polymerized powder Izod impact strength (KJ / m 2 )]]> Volume resistivity (Ω / cm)*10 11 ]] Application Example 1 532 2.62 98.8 197 2.73 Application Example 2 529 2.54 97.3 193 3.64 Application Example 3 513 2.03 85.6 177 4.73 Application Example 4 465 2.08 93.4 169 5.6 Application Example 5 523 2.48 96.3 191 118.6 Application Example 6 454 2.03 93.6 179 8.04 Comparative Application Example 1 444 1.8 70 146 2932.7 Comparative Application Example 2 428 1.75 66.1 140 748.1

[0124] From the results in table 1, it can be seen that the catalyst in the application has high activity and high selectivity in the process of ethylene polymerization, and can obtain ultrahigh molecular weight polyethylene product, and excellent performance of ultrahigh molecular weight polyethylene.

Claims

1. An environmentally friendly catalyst, characterized by, The catalyst comprises a carrier and an active component supported on the carrier; wherein the active component comprises a metal complex and an aluminum chloride composite ionic liquid; The carrier is selected from a molecular sieve, and the molecular sieve is TS-1 titanium silicalite; The metal in the metal complex comprises Mg and Ni, and the metal in the metal complex further comprises an alkali metal; The ligand in the metal complex is selected from 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin and trimesic acid; The aluminum chloride composite ionic liquid is selected from aluminum chloride-trioctylmethylammonium bis(trifluoromethanesulfonyl)imide salt.

2. The catalyst according to claim 1, characterized in that, The preparation method of the catalyst comprises: S1. Preparation of a metal complex: a metal source is mixed with a first organic solvent, then a ligand is added for complexation, then sodium hydride is added for a first reaction, and finally a first post-treatment is performed to obtain the metal complex; S2. Preparation of an aluminum chloride composite ionic liquid: a quaternary ammonium ionic liquid and aluminum chloride are added to n-hexane for a reflux reaction, and then n-hexane is removed to obtain the aluminum chloride composite ionic liquid; S3. Loading of the active component: the metal complex and the carrier are added to a third organic solvent for a third mixing, and then filtration and solid-phase drying are sequentially performed to obtain a catalyst intermediate; the catalyst intermediate is dispersed in a mixed system of the aluminum chloride composite ionic liquid and water, and then room-temperature impregnation is performed, followed by drying to obtain the environmentally friendly catalyst.

3. The catalyst of claim 2, wherein In step S1: The metal source is selected from a magnesium salt and a nickel salt; The molar ratio of the ligand to the metal source is 1:(0.8-1.2) based on the metal content of the metal source; The complexation is performed under a nitrogen atmosphere, the complexation temperature is 65-75°C, and the complexation time is 4-8 hours; The first reaction is performed at a reaction temperature of 0~-10°C for a reaction time of 1-2 hours; The molar ratio of sodium hydride to the ligand is (1.5-3):

1.

4. The catalyst of claim 2, wherein In step S2: The molar ratio of the quaternary ammonium ionic liquid to aluminum chloride is 1:(1.5-2); The mass ratio of n-hexane to the quaternary ammonium ionic liquid is 10:(1-2); The reflux reaction is performed at a temperature of 70-80°C for a time of 2-4 hours.

5. The catalyst of claim 2, wherein In step S3: The mass ratio of the metal complex to the carrier is (25-40):100; The mass ratio of the carrier to the third organic solvent is 1:(20-30); The mass ratio of the aluminum chloride composite ionic liquid to water is 1:(10-15).

6. An environmentally friendly catalyst for use in the preparation of ultra-high molecular weight polyolefin film material, characterized by, The environmentally friendly catalyst comprises the environmentally friendly catalyst according to any one of claims 1-5.