Polyionic liquid carrier, preparation method and application thereof

Abstract

This invention provides a polyionic liquid support, its preparation method, and its application. The polyionic liquid support is obtained by copolymerization of monomers comprising divinylbenzene and functional monomers; the functional monomers are ionic liquids containing cations and trifluoroacetic acid anions, the cations including imidazole cations and / or pyridine cations; the imidazole cations have the structure shown in Formula I; the pyridine cations have the structure shown in Formula II; this polyionic liquid support is suitable for metallocene catalysts, and the supported metallocene catalysts exhibit high olefin polymerization activity.

Description

Technical Field

[0001] This invention belongs to the field of catalysts, specifically relating to a metallocene catalyst system, its preparation method and application, and particularly to a polyionic liquid support, a polyionic liquid support type metallocene catalyst system, its preparation method and application. Background Technology

[0002] To make metallocene catalysts suitable for industrial slurry polymerization or gas-phase polymerization, the preparation of supported metallocene catalysts is crucial. Currently, supports for supported metallocene catalysts are typically inorganic or polymeric. There are numerous reports on the use of inorganic supports as metallocene catalyst supports, such as US4,808,561, US5,026,797, US5,763,543, US5,661,098, US6,455,647, CN1174549, and CN1356343, which report the preparation of supported metallocene catalysts using inorganic materials such as silica, magnesium chloride, and alumina. However, the introduction of inorganic supports into the polymerization process can affect the properties of polyolefins, such as leading to higher polymer ash content and fisheye defects in the film. Furthermore, the presence of acidic groups on the surface of inorganic supports used for metallocene catalysts can cause catalyst deactivation, necessitating complex surface treatment of the inorganic supports before loading the metallocene catalyst. For example, the article "Metallocenes and post-metallocenes immobilized on ionic liquid-modified silica as catalysts for polymerization of ethylene" published in Applied Catalysis A: General reported an ionic liquid-modified silica support for supporting metallocene or post-metallocene catalysts, which was then used to catalyze ethylene polymerization. However, its ethylene polymerization activity was low, the preparation process was complex, and the inorganic silica support easily led to the problem of high polymer ash content.

[0003] In recent years, porous organic polymer supports have attracted increasing attention from industry and academia due to their unique properties, excellent copolymerization performance, and ability to regulate polymer molecular weight through nano-confinement effects during olefin polymerization. Furthermore, the polymer products prepared from these supports have low inorganic ash content. US5,587,439 discloses a metallocene-supported ethylene / methacrylate copolymer. After reaction with sodium cyclopentadienyl, the support can be used to support CpZrCl3 or ZrCl4(THF)2, using MAO as a co-catalyst for the catalytic polymerization of ethylene in toluene solution. CN1624005 describes the chloromethyl functionalization of linear polystyrene followed by crosslinking via a DA reaction. The main drawback of this method is the unclear functional group structure of the support and the uneven distribution of functional groups within the support. CN1396186 uses crosslinked polystyrene copolyacrylol as a polymer support. Currently reported supports are only solid, which is detrimental to catalyst loading and makes the supports less prone to breakage during ethylene polymerization, hindering the release of active sites. EP528092 discloses a method for preparing Me2Si(Ind)2ZrCl2-MAO supported on polypropylene particles. The polymer-supported metallocene catalyst prepared by this method exhibits good stability, and the corresponding polyolefin product has a good morphology. CN101440137A discloses a method for supporting metallocene with a copolymer of polystyrene, divinylbenzene, and acrylonitrile, preparing a monodisperse porous polymer support. However, the copolymer supports prepared by these two methods have small pore volumes and average pore sizes, which are unfavorable for supporting metallocene catalysts, resulting in low catalyst activity. The article "Ionic Liquid-Modified Porous OrganicPolymers as Efficient Metallocene Catalyst Supports" in *Catalysts* reports the use of 1-n-butyl-3-vinylimidazolium chloride to modify the porous organic polymer divinylbenzene framework, preparing an ionic liquid-modified porous organic polymer for supporting metallocene catalysts. This polymer exhibits good activity in catalyzing ethylene polymerization. Summary of the Invention

[0004] To address the aforementioned problems, the present invention aims to provide a polyionic liquid support, its preparation method, and its application. This polyionic liquid support is suitable for metallocene catalysts, and the prepared metallocene catalyst exhibits high olefin polymerization activity.

[0005] To achieve the above objectives, the present invention provides a polyionic liquid carrier, which is obtained by copolymerization of a monomer comprising divinylbenzene and a functional monomer; wherein the functional monomer is an ionic liquid containing a cation and a trifluoroacetic acid anion, and the cation includes an imidazole cation and / or a pyridine cation (preferably a pyridine cation);

[0006] The imidazole cation has the structure shown in Formula I:

[0007]

[0008] In Equation I, X is C1-C 12 alkylene groups and their derivatives, where R is selected from C1-C1. 15 Alkyl groups and their derivatives, phenyl groups and their derivatives;

[0009] The pyridine cation has the structure shown in Formula II:

[0010]

[0011] In Equation II, Y is C1-C 12 alkylene groups and their derivatives, where R' is selected from C1-C6. 15 Alkyl groups and their derivatives, phenyl groups and their derivatives.

[0012] According to a specific embodiment of the present invention, preferably, in Formula I, X is a C3-C6 alkylene group and its derivatives, and R is selected from CH3, C2H5, C3H7, C4H9, CH2C6H5, CH2CH2C6H5, and CH2CH2CH2C6H5.

[0013] According to a specific embodiment of the present invention, preferably, in formula II, Y is a C3-C6 alkylene group and its derivatives, and R' is selected from CH3, C2H5, C3H7, C4H9, CH2C6H5, CH2CH2C6H5, and CH2CH2CH2C6H5.

[0014] According to a specific embodiment of the present invention, preferably, the functional unit is selected from...

[0015]

[0016] One or more combinations of the above.

[0017] According to a specific embodiment of the present invention, preferably, the mass fraction of the functional monomer is 10%-50%, more preferably 20%-40%, calculated based on the mass of the polyionic liquid carrier as 100%; the content of the functional monomer in the polyionic liquid carrier is determined by the amount of divinylbenzene and the ionic liquid added.

[0018] According to a specific embodiment of the present invention, preferably, the polyionic liquid carrier further comprises less than 60 wt% of additional monomers, calculated based on 100% by mass.

[0019] According to a specific embodiment of the present invention, preferably, the additional monomer includes one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxypropyl acrylate.

[0020] The present invention also provides a method for preparing the above-mentioned polyionic liquid carrier, which includes the following steps: using monomers including the divinylbenzene, the functional monomer and the additional monomer as raw materials, the polyionic liquid carrier is obtained by copolymerization; the additional monomer accounts for 0-60% of the total mass of the monomers.

[0021] According to a specific embodiment of the present invention, preferably, the polyionic liquid carrier is prepared by dispersion polymerization, suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization, and has a microporous and mesoporous structure; the dispersion polymerization includes the following steps: adding divinylbenzene, functional monomers and additional monomers to a dispersion solvent, then adding a template agent and an initiator, and reacting at 50-80°C for 3-12 hours to obtain the polyionic liquid carrier.

[0022] According to a specific embodiment of the present invention, preferably, the dispersing solvent is a C1-C4 alcohol or a mixture of C1-C4 alcohol and ethylene glycol, wherein the mass ratio of the C1-C4 alcohol to ethylene glycol is 5-10:1.

[0023] According to a specific embodiment of the present invention, preferably, the C1-C4 alcohols include one or more combinations of methanol, ethanol, propanol, isopropanol, 1-butanol, and isobutanol.

[0024] According to a specific embodiment of the present invention, preferably, the template agent comprises polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer.

[0025] According to a specific embodiment of the present invention, preferably, the weight-average molecular weight of the template agent is 6000-12000.

[0026] According to a specific embodiment of the present invention, preferably, the amount of the template agent added is 1-5% of the total mass of the monomer.

[0027] According to a specific embodiment of the present invention, preferably, the initiator includes azobisisobutyronitrile and / or benzoyl peroxide.

[0028] According to a specific embodiment of the present invention, preferably, the amount of the initiator added is 1-5% of the total mass of the monomer.

[0029] According to a specific embodiment of the present invention, preferably, the divinylbenzene is a pretreated divinylbenzene, wherein the pretreatment is to remove the polymerization inhibitor.

[0030] According to a specific embodiment of the present invention, the above preparation method includes the following specific steps:

[0031] (I) Preparation of Polymerizable Ionic Liquids

[0032] (1) Preparation of vinylphenyl magnesium chloride Grignard reagent

[0033] A mixture of toluene, tetrahydrofuran, and chlorostyrene is prepared, wherein the chlorostyrene is 2-chlorostyrene, 3-chlorostyrene, or 4-chlorostyrene. Under nitrogen protection, a small amount of the mixture is used to wet magnesium powder, which accounts for 20-30% of the mass of the chlorostyrene. A 1,2-dibromoethane initiator, accounting for 2-6% of the mass of the chlorostyrene in the mixture, is added dropwise to the magnesium powder to initiate the reaction. Further, the mixture is slowly added dropwise, and the reaction is carried out at room temperature for 2-8 hours to prepare a vinylphenyl magnesium chloride Grignard reagent (structure shown in Formula III, hereinafter referred to as the Grignard reagent).

[0034]

[0035] (2) Preparation of intermediates

[0036] Using cuprous chloride as a catalyst, the above-mentioned vinylphenyl magnesium chloride Grignard reagent was slowly added dropwise to a dihaloalkane at 0-10°C. The molar ratio of the dihaloalkane to the vinylphenyl magnesium chloride Grignard reagent was approximately 5:1-3:1. After reacting for 2-5 hours, the pH of the system was adjusted to 5-6 with dilute sulfuric acid. The aqueous phase was removed by separation, and the intermediate (structure shown in Formula IV) was obtained by vacuum distillation. The dihaloalkane included, but was not limited to, dichloromethane, 1,2-dichloroethane, and 1,3-dichloroethane. Dichloropropane, 1,2-dichloropropane, 1,3-dichlorobutane, 1,4-dichlorobutane, 1,4-dibromobutane, 1,2-dibromobutane, 2,4-dibromopentane, 1,5-dichloropentane, 1,4-dibromopentane, 1,6-dichlorohexane, 2,5-dibromohexane, 1,7-dichloroheptane, 1,8-dichlorooctane, 1,9-dichlorononane, 1,10-dichlorononane, 1,11-dibromoundecane, 1,12-dibromododecane;

[0037]

[0038] (3) Preparation of trifluoroacetic acid ionic liquid

[0039] R'-substituted pyridine or R-substituted imidazole is added to an inert solvent (such as toluene or hexane), and an intermediate (the compound shown in Formula IV) is slowly added, wherein the molar ratio of R'-substituted pyridine or R-substituted imidazole to the intermediate is 1.5:1 to 1:1. The reaction is carried out at 80-120°C for 20-24 hours. The solvent is removed by vacuum distillation, and the product is washed with anhydrous diethyl ether to obtain the polymerizable ionic liquid N. + Cl - Dissolve N in a small amount of deionized water. + Cl -Trifluoroacetic acid (TCA) at a molar ratio of 1.1:1 to 1.5:1 was slowly added dropwise under ice bath stirring conditions. After the addition was complete, nitrogen protection was maintained, and the reaction was continued in the ice bath for 0.5–2 hours. Then, the ice bath was removed, and the reaction system was heated to room temperature and stirred for another 2–4 hours. After the reaction was completed, the mixture was evaporated under reduced pressure to remove moisture. Finally, it was vacuum dried at 80 °C for 24 hours to obtain the trifluoroacetic acid ionic liquid N0. + CF3COO - N + It is an imidazole cation or a pyridine cation;

[0040] (II) Preparation of Polyionic Liquid Carrier

[0041] At room temperature, the basic monomer divinylbenzene (with the polymerization inhibitor removed) and the ionic liquid functional monomer are sequentially added to a dispersion solvent. The dispersion solvent is a C1-C4 lower alcohol or a mixed solvent system of C1-C4 alcohol and ethylene glycol, wherein the mass ratio of C1-C4 alcohol to ethylene glycol in the mixed solvent system is 5-10:1. The C1-C4 alcohol is methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, etc. A template agent (e.g., polyvinyl alcohol or polypropylene oxide-ethylene oxide copolymer) is added at room temperature. The weight average molecular weight of the template agent is controlled between 6000-10000, and the amount added is 1-5% of the total mass of the reactants. A free radical initiator is added to carry out the reaction. Common free radical initiators are acceptable, including azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO). The temperature is raised to 50-80°C, and the reaction is carried out for 3-12 hours. The amount of free radical initiator added is 1-5% of the total mass of the reacting monomers. After the reaction is completed, unreacted monomers, template agents and other impurities are removed by washing with C1-C4 lower alcohols to obtain the polyionic liquid carrier (denoted as IPOP).

[0042] The present invention also provides a polyionic liquid-supported metallocene catalyst system, which comprises the polyionic liquid support, a co-catalyst, and a metallocene compound; wherein the co-catalyst is used to activate the polyionic liquid support.

[0043] According to a specific embodiment of the present invention, preferably, the molar ratio of Al in the co-catalyst to the metal atoms in the metallocene compound is 75-500, more preferably 100-300.

[0044] According to a specific embodiment of the present invention, preferably, the ratio of Al in the co-catalyst to the polyionic liquid carrier is from 1 mmol Al / g carrier to 12 mmol Al / g carrier, more preferably from 3 mmol Al / g carrier to 8 mmol Al / g carrier.

[0045] According to a specific embodiment of the present invention, preferably, the ratio of metal atoms in the metallocene compound to the polyionic liquid carrier is 5 micromoles of metallocene / gram carrier to 100 micromoles of metallocene / gram carrier, more preferably 10 micromoles of metallocene / gram carrier to 50 micromoles of metallocene / gram carrier.

[0046] According to a specific embodiment of the present invention, preferably, the co-catalyst comprises alkylaluminoxane.

[0047] According to a specific embodiment of the present invention, preferably, the alkylaluminoxane includes, but is not limited to, methylaluminoxane (MAO) and / or alkyl-modified methylaluminoxane (MMAO), more preferably methylaluminoxane.

[0048] According to a specific embodiment of the present invention, preferably, the metallocene compound has the general formula Cp. x MA y B z In this context, Cp is selected from cyclopentadienyl and its derivatives, indenyl and its derivatives, fluorenyl and its derivatives, M is a transition metal atom, A and B are each independently selected from halogen atoms, hydrogen atoms, and alkyl groups, and x, y, and z are 0-3 respectively, and x, y, and z cannot be 0 at the same time.

[0049] According to a specific embodiment of the present invention, preferably, x+y+z=4, y+z≤3.

[0050] According to a specific embodiment of the present invention, preferably, A and B are each independently selected from C1-C8 alkyl or chlorine groups; the alkyl group is, for example, methyl, ethyl, n-propyl, n-butyl, isobutyl or n-pentyl.

[0051] According to a specific embodiment of the present invention, preferably, when x = 2, Cp is bridged by polymethylene or dialkylsilane, such as by bridging with -Si(CH3)2-, -C(CH3)2-, -CH2-, -CH2-CH2-, etc.

[0052] According to a specific embodiment of the present invention, preferably, M is zirconium, hafnium or titanium, 1≤x≤3, and Cp is selected from C1-C6 directly alkyl-substituted cyclopentadienyl, indenyl and their derivatives or fluorenyl and their derivatives.

[0053] According to a specific embodiment of the present invention, preferably, the metallocene compound includes one or more of the following: di(cyclopentadienyl) metal dihalides, di(cyclopentadienyl) metal monoalkyl monohalides, di(cyclopentadienyl) metal dialkyl compounds, and di(indenyl) metal dihalides.

[0054] According to a specific embodiment of the present invention, preferably, the metallocene compound includes di(cyclopentadienyl)zirconia dichloride, di(cyclopentadienyl)hafnium dichloride, di(cyclopentadienyl)dimethylzirconia, di(cyclopentadienyl)dimethylhafnium, di(n-butylcyclopentadienyl)zirconia dichloride, di(n-butylcyclopentadienyl)hafnium dichloride, di(n-butylcyclopentadienyl)dimethylzirconia, and di(n-butylcyclopentadienyl)zirconia. Dimethylhafnium, bis(dimethylcyclopentadienyl)dimethylzirconium, bis(tetramethylcyclopentadienyl)dimethylhafnium, diindylzirconium dichloride, methylene-bridged diindylzirconium dichloride, bis(4,5,6,7-tetrahydro-1-indyl)zirconium dichloride, ethylidene-bridged di(indyl)zirconium dichloride, diindylhafnium dichloride, methylene-bridged diindylhafnium dichloride, bis(4,5,6,7-tetrachloro-1-indyl)hafnium dichloride Ethylene-bridged bis(indenyl)hafnium chloride, ethylene-bridged bis(indenyl)titanium chloride, bis(4,5,6,7-tetra-hydro-1-indenyl)titanium chloride, bis(n-butylcyclopentadienyl)titanium chloride, bis(cyclopentadienyl)titanium chloride, dimethylsilicon-bridged bis(2-methyl-4-phenylindenyl)zirconium chloride, dimethylsilicon-bridged bis(2-methyl-4-phenylindenyl)hafnium chloride, dimethylsilicon-bridged One or more of the following: dibis(2-methyl-4-phenylindenyl)dimethylzirconium, dimethylsilyl-bridged dibis(2-methylindenyl)zirconium dichloride, dimethylsilyl-bridged dibis(2-methylindenyl)hafnium dichloride, dimethylsilyl-bridged dibis(2-methyl-benzo[indenyl]zirconium dichloride, dimethylsilyl-bridged dibis(2-methyl-benzo[indenyl]zirconium dichloride, and dimethylsilyl-bridged dibis(2-methylindenyl)zirconium.

[0055] The present invention also provides a method for preparing the above-mentioned polyionic liquid-supported metallocene catalyst system, which includes the following steps: under anhydrous and oxygen-free conditions, the polyionic liquid support, co-catalyst and solvent are mixed, a metallocene compound is added, and the mixture is reacted at 0-40°C for 60-180 minutes to obtain the polyionic liquid-supported metallocene catalyst system.

[0056] According to a specific embodiment of the present invention, preferably, the solvent includes one or more of aromatic hydrocarbons and their derivatives, ethers, cyclic ethers, esters, and alkanes, more preferably toluene.

[0057] According to a specific embodiment of the present invention, the above preparation method includes the following specific steps:

[0058] The polyionic liquid support is vacuum dried to remove residual solvent, moisture, and air. Under anhydrous and oxygen-free conditions, the polyionic liquid support is added to the solvent, followed by the addition of MAO or MMAO co-catalysts (the amount of co-catalyst can be 1 mmol / g support to 10 mmol / g support, for example, 5 mmol / g support to 8 mmol / g support). The mixture is stirred at room temperature for 30-120 minutes, and then the metallocene compound Cp is added. x MA y B z Add the catalyst to the above reaction solution, react at 0-40℃ for 60-180 minutes, and wash with solvents such as toluene or hexane to obtain a polyionic liquid-supported metallocene catalyst system.

[0059] The cocatalyst of this invention, alkylaluminoxane, is first loaded onto a polyionic liquid via non-covalent bonds to obtain a cocatalyst-activated polyionic liquid support. Then, a metallocene compound is added to obtain a metallocene catalyst supported on the polyionic liquid. For example, when methylaluminoxane (MAO) is used to activate the polyionic liquid, the Al-CH3 in MAO reacts with the imidazole or pyridine cations of the polyionic liquid support, removing CH4 and loading onto the porous polyionic liquid support framework. Simultaneously, the trifluoroacetic acid anion has an electron-donating effect, reacting with the Al in MAO to modify it, forming an IPOP-CF3COO---Al-MAO activated support. When a metallocene compound is added, the MAO on the activated support methylates the metallocene compound, forming [Cp2MMe]. + [IPOP-CF3COO---Al-MAO] - Ion pairs, generally considered to have M as the effective active center (M = Zr, Ti, Hf, etc., Cp is cyclopentadienyl, etc., IPOP is the prepared polyionic liquid carrier, the molecular structure is a simplified molecular structure and is only used for illustration).

[0060] This invention also provides the application of the above-mentioned polyionic liquid-supported metallocene catalyst system in olefin polymerization.

[0061] According to a specific embodiment of the present invention, preferably, the olefin polymerization is ethylene homopolymerization, propylene homopolymerization, ethylene-propylene copolymerization, ethylene-α-olefin copolymerization, or propylene-α-olefin copolymerization.

[0062] According to a specific embodiment of the present invention, preferably, the α-olefin includes one or more combinations of butene, pentene, hexene, octene, and 4-methyl-1-pentene.

[0063] According to a specific embodiment of the present invention, preferably, the olefin polymerization is gas-phase polymerization, bulk polymerization or slurry polymerization.

[0064] According to a specific embodiment of the present invention, preferably, the polymerization reaction temperature is 30-120°C.

[0065] According to a specific embodiment of the present invention, preferably, the polymerization reaction pressure is 0.5-1.5 MPa.

[0066] According to a specific embodiment of the present invention, preferably, the solvent for the slurry polymerization is C5-C. 10 The alkane, more preferably hexane.

[0067] According to a specific embodiment of the present invention, preferably, a small amount of alkyl aluminum compound, such as triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-hexylaluminum, etc., may be added to the polymerization reaction as a purification agent for the polymerization reaction system.

[0068] This invention achieves stable ion pairs [Cp2MMe] by designing and optimizing the ionic liquid framework structure and anions, and by controlling the pore structure of the polyionic liquid carrier and the chemical environment of the metal active center. + [IPOP-CF3COO---Al-MAO] - The synergistic effect of trifluoroacetate anion and co-catalyst enhances the activity of the metallocene active center M. + By adjusting the concentration, higher catalytic activity is obtained, resulting in a metallocene catalyst with higher olefin polymerization activity compared to the organic support modified with 1-n-butyl-3-vinylimidazolium chloride. The polyionic liquid of this invention combines the excellent properties of both ionic liquids and polymers. The polyionic liquid-supported metallocene catalyst exhibits both homogeneous and heterogeneous catalytic characteristics when catalyzing olefin polymerization. Detailed Implementation

[0069] To provide a clearer understanding of the technical features, objectives, and beneficial effects of this invention, the technical solution of this invention is described in detail below, but this should not be construed as limiting the scope of implementation of this invention. Specific conditions and experimental methods are not specified in the following embodiments; conventional conditions are generally followed.

[0070] The monomer divinylbenzene (DVB) used in the preparation of the support for the following metallocene catalyst systems can be a commercially available monomer with a content of 55% or 80% DVB. Pretreatment is required before use to remove the polymerization inhibitor. Many methods for removing the polymerization inhibitor exist in the prior art, such as washing with sodium hydroxide solution and distilled water. In the following examples, the divinylbenzene is used to remove the polymerization inhibitor with a 10% sodium hydroxide solution and washed three times with deionized water before use.

[0071] Al and metal active center atoms such as zirconium and hafnium in polyionic liquid-supported metallocene catalysts were analyzed using Varian's VISTA-MPX inductively coupled plasma atomic emission spectrometry (ICP-AES). The samples were first calcined in a muffle furnace to obtain ash, then perchloric acid and aqua regia were added, followed by heating and digestion. The ash was then dissolved in 2% HCl solution and brought to a final volume. The characteristic peak intensities of Al and metal active center atoms in the metallocene catalyst were then measured, and their content was calculated based on a standard curve.

[0072] The particle size of the prepared polyionic liquid carrier was tested using a Malvern laser particle size analyzer Mastersizer 2000. After the carrier was dried, it could be tested directly without ultrasonic dispersion. After stabilization, a monodisperse particle size distribution curve could be obtained. The average particle size was 20-60 μm. The particle size was a single peak with a narrow distribution. Span = [D(90) - D(10)] / D(50) was less than 2.

[0073] Specific surface area was measured using the BET nitrogen adsorption method on a Nova 2000e. The polyionic liquid carriers prepared in the following examples have specific surface areas greater than 100 μm. 2 / g, in the range of 100–600m 2 Between / g, pore volume greater than 0.2cm 3 / g.

[0074] Chemical structures of polymerizable ionic liquids prepared in Examples 1-8:

[0075]

[0076]

[0077] Preparation Examples 1-8: Preparation of Polymerizable Ionic Liquids

[0078] Preparation Example 1

[0079] This preparation example provides a polymerizable ionic liquid, which is prepared by the following steps:

[0080] Prepare a mixture of 50g 4-chlorostyrene (Aladdin reagent, >97%), 75g anhydrous tetrahydrofuran, and 75g anhydrous toluene. Under nitrogen protection, add 10g magnesium powder to a 500mL reaction vessel. Take a small amount of the above mixture, wet the magnesium powder, and slowly add 1g 1,2-dibromoethane (Aladdin reagent, 99%) to initiate the reaction while stirring. The magnesium powder foams and turns dark green. Slowly add the 4-chlorostyrene mixture to the reaction vessel, controlling the reaction temperature at 25℃. The addition is completed in about 2 hours, yielding 4-vinylphenyl magnesium chloride Grignard reagent.

[0081] In another 500 mL reaction vessel, 91 g of dichloromethane (Aladdin reagent, ≥99.8%) and 1 g of cuprous chloride catalyst were added. 4-vinylphenyl magnesium chloride Grignard reagent was slowly added dropwise at 10 °C. The addition was completed in about 3 hours. After the reaction was completed, 150 mL of deionized water was added dropwise, and the pH was adjusted to 5-6 with dilute sulfuric acid. After separation, 48 g of 4-vinylbenzyl chloride was obtained by vacuum distillation.

[0082] In a 500 mL reaction vessel, 33 g of 1-methylimidazole (Aladdin reagent, 99%), 200 mL of toluene, and 48 g of 4-vinylbenzyl chloride were added sequentially. The reaction was carried out at 80 °C for 24 hours. After removing the solvent by vacuum distillation, anhydrous diethyl ether was added, and a solid precipitated. The solid was washed with anhydrous diethyl ether, dried, and added back to the 500 mL reaction vessel. A small amount of deionized water was added to dissolve the solid. Under ice bath stirring, 37 g of trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was complete, nitrogen protection was applied, and the reaction was continued in an ice bath for 2 hours. Then, the ice bath was removed, and the reaction system was heated to room temperature and stirred for another 3 hours. After the reaction was completed, the mixture was evaporated under reduced pressure by rotary evaporation to remove moisture. The mixture was then dried under vacuum at 80 °C for 24 hours to obtain 62.4 g of trifluoroacetic acid ionic liquid IL-1. The structure was verified by NMR.

[0083] 1 H NMR(400MHz,CD3OD)δ9.21(s,1H),8.31-8.37(d,1H),8.09-8.13(d,1H),7.31-7.45(m, 2H),6.88-7.05(m,2H),4.53-4.77(d,2H),5.14-5.22(t,1H),4.08(s,2H),3.63(s,3H).

[0084] Preparation Example 2

[0085] This preparation example provides a polymerizable ionic liquid, which is prepared by the following steps:

[0086] Prepare a mixture of 50g 2-chlorostyrene (Aladdin reagent, >97%), 75g anhydrous tetrahydrofuran, and 75g anhydrous toluene. Under nitrogen protection, add 15g magnesium powder to a 500mL reaction vessel. Take a small amount of the above mixture, wet the magnesium powder, and slowly add 3g 1,2-dibromoethane (Aladdin reagent, 99%) to initiate the reaction while stirring. The magnesium powder foams and turns dark green. Slowly add the 2-chlorostyrene mixture to the reaction vessel, controlling the reaction temperature at 25℃. The addition is completed in about 6 hours, yielding 2-vinylphenyl magnesium chloride Grignard reagent.

[0087] In another 500 mL reaction vessel, 229 g of 1,3-dichlorobutane (Aladdin reagent, ≥98%) and 1 g of cuprous chloride catalyst were added. 2-vinylphenyl magnesium chloride Grignard reagent was slowly added dropwise at 0 °C, with the addition completed in approximately 3 hours. After the reaction was complete, 150 mL of deionized water was added, and the pH was adjusted to 5-6 with dilute sulfuric acid. After separation, the mixture was distilled under reduced pressure to obtain 62 g of the intermediate.

[0088] In a 500 mL reaction vessel, 64 g of 3-butylpyridine (Aladdin reagent, 98%), 200 mL of toluene, and 62 g of intermediate were added sequentially. The reaction was carried out at 100 °C for 24 hours. After removing the solvent by vacuum distillation, anhydrous diethyl ether was added, and a solid precipitated. The solid was washed with anhydrous diethyl ether, dried, and added back to the 500 mL reaction vessel. A small amount of deionized water was added to dissolve the solid. Under ice bath stirring, 39 g of trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was complete, nitrogen protection was applied, and the reaction was continued in an ice bath for 2 hours. Then, the ice bath was removed, and the reaction system was heated to room temperature and stirred for another 4 hours. After the reaction was completed, the mixture was evaporated under reduced pressure by rotary evaporation to remove moisture. The mixture was then dried under vacuum at 80 °C for 24 hours to obtain 99.6 g of trifluoroacetic acid ionic liquid IL-2. The structure was verified by NMR.

[0089] Preparation Example 3

[0090] This preparation example provides a polymerizable ionic liquid, which is prepared by the following steps:

[0091] Prepare a mixture of 50 g 3-chlorostyrene (Aladdin reagent, >97%), 75 g anhydrous tetrahydrofuran, and 75 g anhydrous toluene. Under nitrogen protection, add 12 g of magnesium powder to a 500 mL reaction vessel. Take a small amount of the above mixture, wet the magnesium powder, and slowly add 2.2 g of 1,2-dibromoethane (Aladdin reagent, 99%) with stirring to initiate the reaction. The magnesium powder foams and turns dark green. Slowly add the 3-chlorostyrene mixture to the reaction vessel, controlling the reaction temperature at 25 °C. The addition is completed in about 4 hours, yielding 3-vinylphenyl magnesium chloride Grignard reagent.

[0092] In another 500 mL reaction vessel, 355 g of 1,12-dibromododecane (Aladdin reagent, ≥98%) and 1 g of cuprous chloride catalyst were added. 3-vinylphenyl magnesium chloride Grignard reagent was slowly added dropwise at 0 °C, with the addition completed in approximately 3 hours. After the reaction was complete, 150 mL of deionized water was added, and the pH was adjusted to 5-6 with dilute sulfuric acid. After separation, the mixture was distilled under reduced pressure to obtain 98 g of the intermediate.

[0093] In a 500 mL reaction vessel, 71 g of 4-benzylpyridine (Aladdin reagent, 98%), 200 mL of toluene, and 98 g of intermediate were added sequentially. The reaction was carried out at 100 °C for 20 hours. After removing the solvent by vacuum distillation, anhydrous diethyl ether was added, and a solid precipitated. The solid was washed with anhydrous diethyl ether, dried, and added back to the 500 mL reaction vessel. A small amount of deionized water was added to dissolve the solid. Under ice bath stirring, 49.2 g of trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was complete, nitrogen protection was applied, and the reaction was continued in an ice bath for 2 hours. Then, the ice bath was removed, and the reaction system was heated to room temperature and stirred for another 4 hours. After the reaction was completed, the mixture was evaporated under reduced pressure by rotary evaporation to remove moisture, and then dried under vacuum at 80 °C for 24 hours to obtain 119.4 g of trifluoroacetic acid ionic liquid IL-3. The structure was verified by NMR.

[0094] Preparation Example 4

[0095] This preparation example provides a polymerizable ionic liquid, which is prepared by the following steps:

[0096] Prepare a mixture of 50 g 3-chlorostyrene (Aladdin reagent, >97%), 75 g anhydrous tetrahydrofuran, and 75 g anhydrous toluene. Under nitrogen protection, add 13 g of magnesium powder to a 500 mL reaction vessel. Take a small amount of the above mixture, wet the magnesium powder, and slowly add 1.8 g of 1,2-dibromoethane (Aladdin reagent, 99%) with stirring to initiate the reaction. The magnesium powder foams and turns dark green. Slowly add the 3-chlorostyrene mixture to the reaction vessel, controlling the reaction temperature at 25 °C. The addition is completed in about 4 hours, yielding 3-vinylphenyl magnesium chloride Grignard reagent.

[0097] In another 500 mL reaction vessel, 223 g of 1,6-dichlorohexane (Aladdin reagent, ≥98%) and 1 g of cuprous chloride catalyst were added. 3-vinylphenyl magnesium chloride Grignard reagent was slowly added dropwise at 0 °C, with the addition completed in approximately 3 hours. After the reaction was complete, 150 mL of deionized water was added, and the pH was adjusted to 5-6 with dilute sulfuric acid. After separation, the mixture was distilled under reduced pressure to obtain 72 g of the intermediate.

[0098] In a 500 mL reaction vessel, 52 g of 1-butylimidazole (Aladdin reagent, 98%), 200 mL of toluene, and 72 g of intermediate were added sequentially. The reaction was carried out at 100 °C for 20 hours. After removing the solvent by vacuum distillation, anhydrous diethyl ether was added, and a solid precipitated. The solid was washed with anhydrous diethyl ether, dried, and added back to the 500 mL reaction vessel. A small amount of deionized water was added to dissolve the solid. Under ice bath stirring, 37.9 g of trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was complete, nitrogen protection was applied, and the reaction was continued in an ice bath for 2 hours. Then, the ice bath was removed, and the reaction system was heated to room temperature and stirred for another 4 hours. After the reaction was completed, the mixture was evaporated under reduced pressure by rotary evaporation to remove moisture. The mixture was then dried under vacuum at 80 °C for 24 hours to obtain 76.0 g of trifluoroacetic acid ionic liquid IL-4. The structure was verified by NMR.

[0099] Preparation Example 5

[0100] This preparation example provides a polymerizable ionic liquid, which is prepared by the following steps:

[0101] Prepare a mixture of 50 g 3-chlorostyrene (Aladdin reagent, >97%), 75 g anhydrous tetrahydrofuran, and 75 g anhydrous toluene. Under nitrogen protection, add 13 g of magnesium powder to a 500 mL reaction vessel. Take a small amount of the above mixture, wet the magnesium powder, and slowly add 2.6 g of 1,2-dibromoethane (Aladdin reagent, 99%) with stirring to initiate the reaction. The magnesium powder foams and turns dark green. Slowly add the 3-chlorostyrene mixture to the reaction vessel, controlling the reaction temperature at 25 °C. The addition is completed in about 3 hours, yielding 3-vinylphenyl magnesium chloride Grignard reagent.

[0102] In another 500 mL reaction vessel, 279 g of 1,7-dibromoheptane (Aladdin reagent, ≥98%) and 1 g of cuprous chloride catalyst were added. 3-vinylphenyl magnesium chloride Grignard reagent was slowly added dropwise at 0 °C, with the addition completed in approximately 3 hours. After the reaction was complete, 150 mL of deionized water was added, and the pH was adjusted to 5-6 with dilute sulfuric acid. After separation and vacuum distillation, 83 g of the intermediate was obtained.

[0103] In a 500 mL reaction vessel, 96 g of 4-ethylpyridine (Aladdin reagent, 98%), 200 mL of toluene, and 83 g of intermediate were added sequentially. The reaction was carried out at 100 °C for 24 hours. After removing the solvent by vacuum distillation, anhydrous diethyl ether was added, and a solid precipitated. The solid was washed with anhydrous diethyl ether, dried, and added back to the 500 mL reaction vessel. A small amount of deionized water was added to dissolve the solid. Under ice bath stirring, 37.3 g of trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was complete, nitrogen protection was applied, and the reaction was continued in an ice bath for 2 hours. Then, the ice bath was removed, and the reaction system was heated to room temperature and stirred for another 4 hours. After the reaction was completed, the mixture was evaporated under reduced pressure by rotary evaporation to remove moisture. The mixture was then dried under vacuum at 80 °C for 24 hours to obtain 103.3 g of trifluoroacetic acid ionic liquid IL-5. The structure was verified by NMR.

[0104] Preparation Example 6

[0105] This preparation example provides a polymerizable ionic liquid, which is prepared by the following steps:

[0106] Prepare a mixture of 50 g 3-chlorostyrene (Aladdin reagent, >97%), 75 g anhydrous tetrahydrofuran, and 75 g anhydrous toluene. Under nitrogen protection, add 13 g of magnesium powder to a 500 mL reaction vessel. Take a small amount of the above mixture, wet the magnesium powder, and slowly add 2.6 g of 1,2-dibromoethane (Aladdin reagent, 99%) with stirring to initiate the reaction. The magnesium powder foams and turns dark green. Slowly add the 3-chlorostyrene mixture to the reaction vessel, controlling the reaction temperature at 25 °C. The addition is completed in about 3 hours, yielding 3-vinylphenyl magnesium chloride Grignard reagent.

[0107] In another 500 mL reaction vessel, 137 g of 1,4-dichlorobutane (Aladdin reagent, ≥98%) and 1 g of cuprous chloride catalyst were added. 3-vinylphenyl magnesium chloride Grignard reagent was slowly added dropwise at 0 °C, with the addition completed in approximately 3 hours. After the reaction was complete, 150 mL of deionized water was added, and the pH was adjusted to 5-6 with dilute sulfuric acid. After separation, the mixture was distilled under reduced pressure to obtain 68 g of the intermediate.

[0108] In a 500 mL reaction vessel, 88 g of 2-benzylpyridine (Aladdin reagent, 98%), 200 mL of toluene, and 68 g of intermediate were added sequentially. The reaction was carried out at 100 °C for 24 hours. After removing the solvent by vacuum distillation, anhydrous diethyl ether was added, and a solid precipitated. The solid was washed with anhydrous diethyl ether, dried, and added back to the 500 mL reaction vessel. A small amount of deionized water was added to dissolve the solid. Under ice bath stirring, 39.1 g of trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was complete, nitrogen protection was applied, and the reaction was continued in an ice bath for 2 hours. Then, the ice bath was removed, and the reaction system was heated to room temperature and stirred for another 4 hours. After the reaction was completed, the mixture was evaporated under reduced pressure by rotary evaporation to remove moisture. The mixture was then dried under vacuum at 80 °C for 24 hours to obtain 95.8 g of trifluoroacetic acid ionic liquid IL-6. The structure was verified by NMR.

[0109] Preparation Example 7

[0110] This preparation example provides a polymerizable ionic liquid, which is prepared by the following steps:

[0111] Prepare a mixture of 50 g 4-chlorostyrene (Aladdin reagent, >97%), 75 g anhydrous tetrahydrofuran, and 75 g anhydrous toluene. Under nitrogen protection, add 13 g magnesium powder to a 500 mL reaction vessel. Take a small amount of the above mixture, wet the magnesium powder, and slowly add 2.6 g 1,2-dibromoethane (Aladdin reagent, 99%) dropwise with stirring to initiate the reaction. The magnesium powder foams and turns dark green. Slowly add the 4-chlorostyrene mixture to the reaction vessel, controlling the reaction temperature at 25 °C. The addition is completed in about 3 hours, yielding 3-vinylphenyl magnesium chloride Grignard reagent.

[0112] In another 500 mL reaction vessel, 122 g of 1,3-dichloropropane (Aladdin reagent, ≥98%) and 1 g of cuprous chloride catalyst were added. 4-Vinylphenyl magnesium chloride Grignard reagent was slowly added dropwise at 0 °C, with the addition completed in approximately 3 hours. After the reaction was complete, 150 mL of deionized water was added, and the pH was adjusted to 5-6 with dilute sulfuric acid. After separation and vacuum distillation, 57 g of the intermediate was obtained.

[0113] In a 500 mL reaction vessel, 35 g of 3-methylpyridine (Aladdin reagent, 99%), 200 mL of toluene, and 57 g of intermediate were added sequentially. The reaction was carried out at 120 °C for 24 hours. After removing the solvent by vacuum distillation, anhydrous diethyl ether was added, and a solid precipitated. The solid was washed with anhydrous diethyl ether, dried, and added back to the 500 mL reaction vessel. A small amount of deionized water was added to dissolve the solid. Under ice bath stirring, 37.5 g of trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was complete, nitrogen protection was applied, and the reaction was continued in an ice bath for 2 hours. Then, the ice bath was removed, and the reaction system was heated to room temperature and stirred for another 4 hours. After the reaction was completed, the mixture was evaporated under reduced pressure by rotary evaporation to remove moisture. The mixture was then dried under vacuum at 80 °C for 24 hours to obtain 79.9 g of trifluoroacetic acid ionic liquid IL-7. The structure was verified by NMR.

[0114] Preparation Example 8

[0115] This preparation example provides a polymerizable ionic liquid, which is prepared by the following steps:

[0116] Prepare a mixture of 50 g 4-chlorostyrene (Aladdin reagent, >97%), 75 g anhydrous tetrahydrofuran, and 75 g anhydrous toluene. Under nitrogen protection, add 13 g magnesium powder to a 500 mL reaction vessel. Take a small amount of the above mixture, wet the magnesium powder, and slowly add 2.6 g 1,2-dibromoethane (Aladdin reagent, 99%) dropwise with stirring to initiate the reaction. The magnesium powder foams and turns dark green. Slowly add the 4-chlorostyrene mixture dropwise to the reaction vessel, controlling the reaction temperature at 25 °C. The addition is completed in about 3 hours, yielding 4-vinylphenyl magnesium chloride Grignard reagent.

[0117] In another 500 mL reaction vessel, 203 g of 1,5-dichloropentane (Aladdin reagent, ≥98%) and 1 g of cuprous chloride catalyst were added. 4-Vinylphenyl magnesium chloride Grignard reagent was slowly added dropwise at 0 °C, with the addition completed in approximately 3 hours. After the reaction was complete, 150 mL of deionized water was added, and the pH was adjusted to 5-6 with dilute sulfuric acid. After separation and vacuum distillation, 68 g of the intermediate was obtained.

[0118] In a 500 mL reaction vessel, 73 g of 1-phenylethylimidazolium (Aladdin reagent, >98%), 200 mL of toluene, and 68 g of intermediate were added sequentially. The reaction was carried out at 120 °C for 20 hours. After removing the solvent by vacuum distillation, anhydrous diethyl ether was added, and a solid precipitated. The solid was washed with anhydrous diethyl ether, dried, and added back to the 500 mL reaction vessel. A small amount of deionized water was added to dissolve the solid. Under ice bath stirring, 39.1 g of trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was complete, nitrogen protection was applied, and the reaction was continued in an ice bath for 2 hours. Then, the ice bath was removed, and the reaction system was heated to room temperature and stirred for another 4 hours. After the reaction was completed, the mixture was evaporated under reduced pressure by rotary evaporation to remove moisture, and then dried under vacuum at 80 °C for 24 hours to obtain 78.3 g of trifluoroacetic acid ionic liquid IL-8. The structure was verified by NMR.

[0119] Examples 1-10: Preparation of Polyionic Liquid Carriers

[0120] Example 1

[0121] This embodiment provides a polyionic liquid carrier, which is prepared by the following steps:

[0122] 130 mL of methanol was added to a 250 mL reaction vessel as a dispersant. 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 4.8 g of ionic liquid IL-1 were added sequentially to the system. The mixture was stirred at room temperature for 10 minutes. Then, 2% of the total monomer mass of the template agent polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The mixture was stirred at 50 °C for 30 minutes until the template agent was completely dissolved. 5% of the total monomer mass of the initiator AIBN was added. The temperature was raised to 70 °C and reacted for 3 hours, then raised to 80 °C and reacted for 6 hours. After the reaction was completed, the temperature was lowered to 50 °C, filtered, washed three times with methanol, filtered again, and dried to obtain 7.2 g of porous polyionic liquid carrier IPOP-1.

[0123] Example 2

[0124] This embodiment provides a polyionic liquid carrier, which is prepared by the following steps:

[0125] 130 mL of methanol was added to a 250 mL reaction vessel as a dispersant. 4.8 g of divinylbenzene (Aladdin reagent, 55%) and 1.8 g of ionic liquid IL-4 were added sequentially to the system. The mixture was stirred at room temperature for 10 minutes. Then, 2% of the total monomer mass of the template agent polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The mixture was stirred at 50 °C for 30 minutes until the template agent was completely dissolved. 2% of the total monomer mass of the initiator AIBN was added. The temperature was raised to 70 °C and reacted for 3 hours, then raised to 80 °C and reacted for 6 hours. After the reaction was completed, the temperature was lowered to 50 °C, filtered, washed three times with methanol, filtered again, and dried to obtain 3.7 g of porous polyionic liquid carrier IPOP-2.

[0126] Example 3

[0127] This embodiment provides a polyionic liquid carrier, which is prepared by the following steps:

[0128] 130 mL of ethanol was added to a 250 mL reaction vessel as a dispersant. 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 2.1 g of ionic liquid IL-2 were added sequentially to the system. The mixture was stirred at room temperature for 10 minutes. Then, 2% of the total monomer mass of the template agent polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 50 °C for 30 minutes until the template agent was completely dissolved. 2% of the total monomer mass of the initiator AIBN was added. The temperature was raised to 70 °C and reacted for 2 hours, then raised to 80 °C and reacted for 5 hours. After the reaction was completed, the temperature was lowered to 50 °C, filtered, washed three times with ethanol, filtered again, and dried to obtain 5.2 g of porous polyionic liquid carrier IPOP-3.

[0129] Example 4

[0130] This embodiment provides a polyionic liquid carrier, which is prepared by the following steps:

[0131] 130 mL of isobutanol was added to a 250 mL reaction vessel as a dispersant. 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 6.9 g of ionic liquid IL-3 were added sequentially to the system. The mixture was stirred at room temperature for 10 minutes. Then, 2% of the total monomer mass of the template agent polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 50 °C for 30 minutes until the template agent was completely dissolved. 2% of the total monomer mass of the initiator AIBN was added. The temperature was raised to 70 °C and reacted for 2 hours, then raised to 80 °C and reacted for 5 hours. After the reaction was completed, the temperature was lowered to 50 °C, filtered, washed three times with isobutanol, filtered again, and dried to obtain 8.7 g of porous polyionic liquid carrier IPOP-4.

[0132] Example 5

[0133] This embodiment provides a polyionic liquid carrier, which is prepared by the following steps:

[0134] 130 mL of ethanol was added to a 250 mL reaction vessel as a dispersant. 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 3.8 g of ionic liquid IL-8 were added sequentially to the system. The mixture was stirred at room temperature for 10 minutes. Then, 5% of the total monomer mass of the template agent polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 50 °C for 30 minutes until the template agent was completely dissolved. 2% of the total monomer mass of the initiator AIBN was added. The temperature was raised to 70 °C and reacted for 3 hours, then raised to 80 °C and reacted for 5 hours. After the reaction was completed, the temperature was lowered to 50 °C, filtered, washed three times with ethanol, filtered again, and dried to obtain 6.8 g of porous polyionic liquid carrier IPOP-5.

[0135] Example 6

[0136] This embodiment provides a polyionic liquid carrier, which is prepared by the following steps:

[0137] 130 mL of ethanol and 12 mL of ethylene glycol were added to a 250 mL reaction vessel as dispersants. 4.8 g of divinylbenzene (Aladdin reagent, 55%) and 6.8 g of ionic liquid IL-6 were added sequentially to the system. The mixture was stirred at room temperature for 10 minutes. Then, 3% of the total monomer mass of the template agent polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The mixture was stirred at 50 °C for 30 minutes until the template agent was completely dissolved. 5% of the total monomer mass of the initiator AIBN was added. The temperature was raised to 70 °C and reacted for 3 hours, then raised to 80 °C and reacted for 8 hours. After the reaction was completed, the temperature was lowered to 50 °C, filtered, washed three times with ethanol, filtered again, and dried to obtain 8.8 g of porous polyionic liquid carrier IPOP-6.

[0138] Example 7

[0139] This embodiment provides a polyionic liquid carrier, which is prepared by the following steps:

[0140] 130 mL of ethanol was added to a 250 mL reaction vessel as a dispersant. 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 2.1 g of ionic liquid IL-5 were added sequentially to the system. The mixture was stirred at room temperature for 10 minutes. Then, 2% of the total monomer mass of the template agent polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 50 °C for 30 minutes until the template agent was completely dissolved. 2% of the total monomer mass of the initiator AIBN was added. The temperature was raised to 70 °C and reacted for 3 hours, then raised to 80 °C and reacted for 5 hours. After the reaction was completed, the temperature was lowered to 50 °C, filtered, washed three times with ethanol, filtered again, and dried to obtain 5.8 g of porous polyionic liquid carrier IPOP-7.

[0141] Example 8

[0142] This embodiment provides a polyionic liquid carrier, which is prepared by the following steps:

[0143] 130 mL of ethanol was added to a 250 mL reaction vessel as a dispersant. 4.8 g of divinylbenzene (Aladdin reagent, 80%), 3.2 g of ionic liquid IL-5, and 1.7 g of hydroxyethyl methacrylate were added sequentially to the system. The mixture was stirred at room temperature for 10 minutes. Then, 2% of the total monomer mass of the template agent polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 50 °C for 30 minutes until the template agent was completely dissolved. 2% of the total monomer mass of the initiator AIBN was added. The temperature was raised to 70 °C and reacted for 3 hours, then raised to 80 °C and reacted for 5 hours. After the reaction was completed, the temperature was lowered to 50 °C, filtered, washed three times with ethanol, filtered again, and dried to obtain 8.2 g of porous polyionic liquid carrier IPOP-8.

[0144] Example 9

[0145] This embodiment provides a polyionic liquid carrier, which is prepared by the following steps:

[0146] 130 mL of ethanol was added to a 250 mL reaction vessel as a dispersant. 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 3.5 g of ionic liquid IL-7 were added sequentially to the system. The mixture was stirred at room temperature for 10 minutes. Then, 2% of the total monomer mass of the template agent polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 50 °C for 30 minutes until the template agent was completely dissolved. 2% of the total monomer mass of the initiator AIBN was added. The temperature was raised to 70 °C and reacted for 3 hours, then raised to 80 °C and reacted for 5 hours. After the reaction was completed, the temperature was lowered to 50 °C, filtered, washed three times with ethanol, filtered again, and dried to obtain 7.2 g of porous polyionic liquid carrier IPOP-9.

[0147] Example 10

[0148] This embodiment provides a polyionic liquid carrier, which is prepared by the following steps:

[0149] 130 mL of ethanol was added to a 250 mL reaction vessel as a dispersant. 4.8 g of divinylbenzene (Aladdin reagent, 80%), 2.2 g of ionic liquid IL-7, and 2.2 g of hydroxyethyl methacrylate were added sequentially to the system. The mixture was stirred at room temperature for 10 minutes. Then, 2% of the total monomer mass of the template agent polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 50 °C for 30 minutes until the template agent was completely dissolved. 2% of the total monomer mass of the initiator AIBN was added. The temperature was raised to 70 °C and reacted for 3 hours, then raised to 80 °C and reacted for 5 hours. After the reaction was completed, the temperature was lowered to 50 °C, filtered, washed three times with ethanol, filtered again, and dried to obtain 7.9 g of polyionic liquid IPOP-10.

[0150] Comparative Example 1

[0151] This comparative example provides a porous organic support prepared from a monomer containing hydroxyethyl methacrylate (HEMA), which is obtained by the following steps:

[0152] In a 250 mL round-bottom glass reactor, 130 mL of ethanol and 15 mL of deionized water were added, followed by 4.8 g of 80% divinylbenzene and 2.4 g of hydroxyethyl methacrylate (Aladdin reagent, 90%). The mixture was stirred at room temperature for 10 minutes. Then, 2% of the total monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 55 °C for 30 minutes. After F127 was completely dissolved, 2% of the monomer mass of initiator AIBN was added. The temperature was raised to 70 °C and reacted for 3 hours, then raised to 80 °C and reacted for 5 hours. The mixture was washed with a mixture of ethanol and water, filtered, and dried to obtain 4.6 g of (DVB-co-HEMA) porous organic polymer carrier POP-11.

[0153] Comparative Example 2

[0154] This comparative example provides an organic polymer carrier, which is prepared by the following steps:

[0155] 130 mL of ethanol was added to a 250 mL reaction vessel as a dispersant. 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 3.5 g of 1-vinyl-3-butylimidazolium chloride (Zhengzhou Alpha Chemical Co., Ltd., 98%) were added sequentially to the system. The mixture was stirred at room temperature for 10 minutes. Then, 2% of the total monomer mass of the template agent, polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000), was added. The mixture was stirred at 50 °C for 30 minutes until the template agent was completely dissolved. 2% of the total monomer mass of the initiator, AIBN, was added. The temperature was raised to 70 °C and reacted for 3 hours, then raised to 80 °C and reacted for 5 hours. After the reaction was completed, the temperature was lowered to 50 °C, filtered, washed three times with ethanol, filtered again, and dried to obtain 6.8 g of 1-vinyl-3-butylimidazolium chloride-modified porous organic polymer carrier POP-12.

[0156] The specific surface area, pore volume, average particle size, and particle size distribution of the carriers prepared in Examples 1-10 and Comparative Examples 1-2 are shown in Table 1 below.

[0157] Table 1. Specific surface area, pore volume, average particle size, and particle size distribution of the carrier.

[0158] IPOP-1 135.2 0.28 56 1.82 IPOP-2 295.8 0.23 44 1.69 IPOP-3 437.2 0.32 51 1.93 IPOP-4 238.5 0.26 38 1.38 IPOP-5 528.3 0.37 48 1.72 IPOP-6 293.6 0.27 58 1.83 IPOP-7 438.5 0.32 43 1.76 IPOP-8 268.3 0.25 52 1.38 IPOP-9 382.5 0.33 56 1.52 IPOP-10 364.9 0.26 40 1.66 POP-11 417.2 0.33 45 1.88 POP-12 331.5 0.27 38 1.65

[0159] As can be seen from Table 1, the polyionic liquid carrier prepared by this invention has a high specific surface area, reaching 500 m². 2 / g or more, pore volume greater than 0.2cm 3 / g. The polyionic liquid carrier of the present invention has good flowability, no obvious agglomeration, is not easily hygroscopic, and has a narrow particle size distribution, generally less than 2.

[0160] Examples 11-20: Preparation of metallocene catalysts

[0161] Example 11

[0162] This embodiment provides a metallocene catalyst, which is prepared by the following steps:

[0163] 5g of polyionic liquid carrier IPOP-1 was placed in a vacuum drying oven and dried at 120℃ for 10 hours. The treated carrier was added to a 250mL nitrogen-purged multi-port reactor, along with 25mL of a 10% (mass percentage) MAO (produced by the Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution, and stirred at room temperature for 1 hour. Then, 0.19g of (n-BuCp)2ZrCl2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL of toluene were added, and the mixture was stirred at 25℃ for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation and the mixture was dried to obtain catalyst Cat-1, which contained 4.7 mmol / g Al and 47.2 μmol / g Zr.

[0164] Example 12

[0165] This embodiment provides a metallocene catalyst, which is prepared by the following steps:

[0166] 5g of polyionic liquid carrier IPOP-2 was placed in a vacuum drying oven and dried at 120℃ for 10 hours. The treated carrier was added to a 250mL nitrogen-purged multi-port reactor, along with 25mL of a 10% (mass percentage) MAO (produced by the Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution, and stirred at room temperature for 1 hour. Then, 0.19g of (n-BuCp)2ZrCl2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL of toluene were added, and the mixture was stirred at 40℃ for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation and the mixture was dried to obtain catalyst Cat-2, which contained 5.0 mmol / g Al and 44.7 μmol / g Zr.

[0167] Example 13

[0168] This embodiment provides a metallocene catalyst, which is prepared by the following steps:

[0169] 5g of polyionic liquid carrier IPOP-3 was placed in a vacuum drying oven and dried at 120℃ for 10 hours. The treated carrier was added to a 250mL nitrogen-purged multi-port reactor, along with 30mL of a 10% (mass percentage) toluene solution of MAO (produced by the Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below), and stirred at room temperature for 1 hour. Then, 0.23g of (n-BuCp)2ZrCl2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL of toluene were added, and the mixture was stirred at 0℃ for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation and the mixture was dried to obtain catalyst Cat-3, which contained 5.3 mmol / g of Al and 46.2 μmol / g of Zr.

[0170] Example 14

[0171] This embodiment provides a metallocene catalyst, which is prepared by the following steps:

[0172] 5g of polyionic liquid carrier IPOP-3 was placed in a vacuum drying oven and dried at 120℃ for 10 hours. The treated carrier was added to a 250mL nitrogen-purged multi-port reactor, along with 25mL of a 10% (mass percentage) toluene solution of MAO (produced by the Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below), and stirred at room temperature for 1 hour. Then, 0.14g of (1-Me-3-n-BuCp)2ZrCl2 bis(1-methyl-3-n-butylcyclopentadienyl)zirconia dichloride metallocene compound and 10mL of toluene were added, and the mixture was stirred at 25℃ for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation and the mixture was dried to obtain catalyst Cat-4, which had an Al content of 5.7 mmol / g and a Zr content of 37.5 μmol / g.

[0173] Example 15

[0174] This embodiment provides a metallocene catalyst, which is prepared by the following steps:

[0175] 5g of polyionic liquid carrier IPOP-4 was placed in a vacuum drying oven and dried at 120℃ for 10 hours. The treated carrier was added to a 250mL nitrogen-purged multi-port reactor, along with 25mL of a 10% (mass percentage) MAO (produced by the Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution, and stirred at room temperature for 1 hour. Then, 0.19g of (n-BuCp)2ZrCl2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL of toluene were added, and the mixture was stirred at 25℃ for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation and the mixture was dried to obtain catalyst Cat-5, which had an Al content of 5.3 mmol / g and a Zr content of 43.4 μmol / g.

[0176] Example 16

[0177] This embodiment provides a metallocene catalyst, which is prepared by the following steps:

[0178] 5g of polyionic liquid carrier IPOP-5 was placed in a vacuum drying oven and dried at 120℃ for 10 hours. The treated carrier was added to a 250mL nitrogen-purged multi-port reactor, along with 25mL of a 10% (mass percentage) toluene solution of MAO (produced by the Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below), and stirred at room temperature for 1 hour. Then, 0.19g of (n-BuCp)2HfCl2 (bis-n-butylcyclopentadienyl hafnium dichloride) metallocene compound and 10mL of toluene were added, and the mixture was stirred at 30℃ for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation and the mixture was dried to obtain catalyst Cat-6, which had an Al content of 6.0 mmol / g and an Hf content of 38.7 μmol / g.

[0179] Example 17

[0180] This embodiment provides a metallocene catalyst, which is prepared by the following steps:

[0181] 5g of polyionic liquid carrier IPOP-5 was placed in a vacuum drying oven and dried at 120℃ for 10 hours. The treated carrier was added to a 250mL nitrogen-purged multi-port reactor, along with 25mL of a 10% (mass percentage) toluene solution of MAO (produced by the Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below), and stirred at room temperature for 1 hour. Then, 0.19g of rac-Me2Si-(2-Me-benz[e]Ind)Zr2Cl2 [dimethylsilyl-bridged bis(2-methyl-benzo[ind]zirconium dichloride] metallocene compound and 10mL of toluene were added, and the mixture was stirred at 25℃ for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation and the mixture was dried to obtain catalyst Cat-7, which had an Al content of 4.7 mmol / g and a Zr content of 51.2 μmol / g.

[0182] Example 18

[0183] This embodiment provides a metallocene catalyst, which is prepared by the following steps:

[0184] 5g of polyionic liquid carrier IPOP-5 was placed in a vacuum drying oven and dried at 120℃ for 10 hours. The treated carrier was added to a 250mL nitrogen-purged multi-port reactor, along with 25mL of a 10% (mass percentage) toluene solution of MAO (produced by the Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below), and stirred at room temperature for 1 hour. Then, 0.19g of En(Ind)2ZrCl2 ethylene-bridged bis(indene)zirconia dichloride metallocene compound and 10mL of toluene were added, and the mixture was stirred at 25℃ for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation and the mixture was dried to obtain catalyst Cat-8, which had an Al content of 4.7 mmol / g and a Zr content of 39.8 μmol / g.

[0185] Example 19

[0186] This embodiment provides a metallocene catalyst, which is prepared by the following steps:

[0187] 5g of polyionic liquid carrier IPOP-9 was placed in a vacuum drying oven and dried at 120℃ for 10 hours. The treated carrier was added to a 250mL nitrogen-purged multi-port reactor, along with 25mL of a 10% (mass percentage) MAO (produced by the Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution, and stirred at room temperature for 1 hour. Then, 0.19g of (n-BuCp)2ZrCl2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL of toluene were added, and the mixture was stirred at 25℃ for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation and the mixture was dried to obtain catalyst Cat-9, which had an Al content of 4.7 mmol / g and a Zr content of 41.9 μmol / g.

[0188] Example 20

[0189] This embodiment provides a metallocene catalyst, which is prepared by the following steps:

[0190] 5g of polyionic liquid carrier IPOP-10 was placed in a vacuum drying oven and dried under vacuum at 120℃ for 10 hours. The treated carrier was added to a 250mL nitrogen-purged multi-port reactor, along with 25mL of a 10% (mass percentage) toluene solution of MAO (produced by the Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below), and stirred at room temperature for 1 hour. Then, 0.19g of (n-BuCp)2ZrCl2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL of toluene were added, and the mixture was stirred at 25℃ for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation and the mixture was dried to obtain catalyst Cat-10, which contained 5.0 mmol / g of Al and 48.3 μmol / g of Zr.

[0191] Comparative Example 3

[0192] This comparative example provides a metallocene catalyst, which is prepared by the following steps:

[0193] 5g of polyionic liquid carrier POP-11 was placed in a vacuum drying oven and dried under vacuum at 120℃ for 10 hours. The treated carrier was added to a 250mL nitrogen-purged multi-port reactor, along with 25mL of a 10% (mass percentage) MAO (produced by the Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution, and stirred at room temperature for 1 hour. Then, 0.19g of (n-BuCp)2ZrCl2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL of toluene were added, and the mixture was stirred at 25℃ for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation and the mixture was dried to obtain catalyst Cat-11, which had an Al content of 4.3 mmol / g and a Zr content of 42.7 μmol / g.

[0194] Comparative Example 4

[0195] This comparative example provides a metallocene catalyst, which is prepared by the following steps:

[0196] 5g of polyionic liquid carrier POP-12 was placed in a vacuum drying oven and dried at 120℃ for 10 hours. The treated carrier was added to a 250mL nitrogen-purged multi-port reactor, along with 25mL of a 10% (mass percentage) toluene solution of MAO (produced by the Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below), and stirred at room temperature for 1 hour. Then, 0.19g of (n-BuCp)2ZrCl2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL of toluene were added, and the mixture was stirred at 25℃ for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation and the mixture was dried to obtain catalyst Cat-12, which contained 4.6 mmol / g of Al and 43.7 μmol / g of Zr.

[0197] Comparative Example 5

[0198] This comparative example provides a metallocene catalyst, which is prepared by the following steps:

[0199] Five grams of Grace 955 silica gel were dried at 600°C for 8 hours to remove surface moisture and a large number of hydroxyl groups. The gel was then cooled to room temperature under nitrogen protection. The treated silica gel support was then added to a 250 mL nitrogen-purged reactor, along with 28 mL of a 10% MAO (mass percentage, produced by the Lanzhou Chemical Research Center of PetroChina) toluene solution. The mixture was stirred at 20°C for 1 hour. Then, 0.2 g of (n-BuCp)2ZrCl2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10 mL of toluene were added. The mixture was stirred at 25°C for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation and the mixture was dried to obtain the catalyst Cat-13, which contained 5.1 mmol / g of Al and 43.7 μmol / g of Zr.

[0200] Test Example 1-13 Catalyst for Ethylene Polymerization

[0201] In a 5L polymerization reactor, ethylene slurry polymerization and ethylene-α-olefin copolymerization were carried out using the metallocene catalysts prepared in Examples 11-20 and Comparative Examples 3-5.

[0202] Ethylene homopolymerization: 2L of anhydrous hexane was added to a 5L polymerization reactor that had been purged with nitrogen and dried. 5mL of triethylaluminum (TEAL) (10% hexane solution) was added, along with 0.2g of the above catalyst. The reactor was purged with ethylene three times while maintaining the pressure inside the reactor at 1MPa. Polymerization was carried out at 80℃ for 1 hour. The reaction was then terminated, cooled to room temperature, filtered to remove hexane, and dried to obtain the polyethylene product.

[0203] Ethylene-α-olefin copolymerization: 2L of anhydrous hexane was added to a 5L polymerization reactor that had been purged with nitrogen and dried. Then, 5mL of triethylaluminum (TEAL) (10% hexane solution), 30mL of 1-hexene, and 0.2g of the above catalyst were added sequentially. The reactor was purged with ethylene three times while maintaining the pressure inside the reactor at 1MPa. The polymerization was carried out at 80℃ for 1 hour. The reaction was then terminated, cooled to room temperature, filtered to remove hexane, and dried to obtain the ethylene-hexene copolymer product.

[0204] The aggregation results are shown in Table 2.

[0205] Table 2 Results of olefin polymerization

[0206] 1 Cat-1 2844 3560 2 Cat-2 3200 4360 3 Cat-3 3680 4870 4 Cat-4 2210 3120 5 Cat-5 3320 4360 6 Cat-6 3650 4230 7 Cat-7 4270 5150 8 Cat-8 3950 4510 9 Cat-9 4210 4970 10 Cat-10 3850 4720 11 Cat-11 2320 3520 12 Cat-12 2175 2870 13 Cat-13 790 2280

[0207] The results of ethylene homopolymerization and copolymerization of ethylene and 1-hexene show that the metallocene catalyst supported by the polyionic liquid containing trifluoroacetic acid ionic liquid of the present invention has high polymerization activity, which is higher than that of porous organic polymer supports functionalized with hydroxyethyl methacrylate, higher than that of metallocene catalysts supported by porous organic polymers modified with 1-vinyl-3-butylimidazolium chloride, and significantly higher than that of metallocene catalysts supported on inorganic silica gel supports.

[0208] Test Example 14 Propylene Polymerization

[0209] 1.0 kg of dried propylene was added to a 10 L high-pressure polymerization reactor that had been purged with nitrogen and dried. 20 mL of triethylaluminum (10% hexane solution) was added, and the mixture was stirred for 10 minutes. Then, 0.1 g of catalyst Cat-7 was added, and the reaction was terminated at 70 °C for 1 hour. The mixture was cooled to room temperature and dried to obtain 975 g of polypropylene with a polymerization activity of 9750 gPP / gcat·h.

[0210] Test Example 15: Ethylene-Octoene Copolymerization

[0211] 2 L of dry hexane was added to a 5 L nitrogen-purged and dried polymerization reactor. Then, 3 mL of triethylaluminum (10% hexane solution), 30 mL of 1-octene, and 0.2 g of catalyst Cat-10 were added sequentially. The reactor was purged three times with ethylene, and the pressure inside the reactor was maintained at 1.0 MPa. Polymerization was carried out at 80 °C for 1 hour. The reaction was terminated, cooled to room temperature, filtered to remove hexane, and dried to obtain 1056 g of ethylene-octene copolymer with a polymerization activity of 5280 g / (gcat·h).

Claims

1. A polyionic liquid-supported metallocene catalyst system, comprising a polyionic liquid support, a co-catalyst, and a metallocene compound; The polyionic liquid carrier is obtained by copolymerization of monomers including divinylbenzene and functional monomers; the functional monomers are ionic liquids containing cations and trifluoroacetic acid anions, the cations including imidazole cations and / or pyridine cations; The imidazole cation has the structure shown in Formula I: Formula I, In Equation I, X is C1-C 12 alkylene groups, where R is selected from C1-C1. 15 Alkyl and phenyl groups; The pyridine cation has the structure shown in Formula II: Formula II, In Equation II, Y is C1-C 12 alkylene groups, R' is selected from C1-C 15 Alkyl and phenyl groups; The cocatalyst includes alkylaluminoxane; The metallocene compound has the general formula Cp x MA y B z ,in, Cp is selected from cyclopentadienyl, indene, and fluorenyl; M is a transition metal atom; A and B are each independently selected from halogen atoms, hydrogen atoms, and alkyl groups; x, y, and z are 0-3 respectively; x, y, and z cannot be 0 at the same time; x+y+z=4; y+z≤3. The ratio of Al in the cocatalyst to the polyionic liquid carrier is from 1 mmol Al / g carrier to 12 mmol Al / g carrier; the ratio of metal atoms in the metallocene compound to the polyionic liquid carrier is from 5 μmol metallocene / g carrier to 100 μmol metallocene / g carrier.

2. The polyionic liquid-supported metallocene catalyst system according to claim 1, wherein, In Formula I, X is a C3-C6 alkylene group, and R is selected from CH3, C2H5, C3H7, C4H9, CH2C6H5, CH2CH2C6H5, and CH2CH2CH2C6H5; In Formula II, Y is a C3-C6 alkylene group, and R' is selected from CH3, C2H5, C3H7, C4H9, CH2C6H5, CH2CH2C6H5, and CH2CH2CH2C6H5.

3. The polyionic liquid-supported metallocene catalyst system according to claim 1, wherein, The functional monomer is selected from 、 、 、 、 、 、 , One or more combinations of the above.

4. The polyionic liquid-supported metallocene catalyst system according to claim 1, wherein, Based on the mass of the polyionic liquid carrier being 100%, the mass fraction of the functional monomer is 10%-50%. The polyionic liquid carrier also contains less than 60 wt% of additional monomers; The additional monomers include one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxypropyl acrylate.

5. The polyionic liquid-supported metallocene catalyst system according to claim 4, wherein, Based on the mass of the polyionic liquid carrier being 100%, the mass fraction of the functional monomer is 20%-40%.

6. The polyionic liquid-supported metallocene catalyst system according to claim 1, wherein, The preparation method of the polyionic liquid carrier includes the following steps: The polyionic liquid carrier is prepared by copolymerization using monomers including the divinylbenzene, the functional monomer, and the additional monomer as raw materials; The polyionic liquid carrier is prepared by dispersion polymerization, suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization. The dispersion polymerization method includes the following steps: adding divinylbenzene, functional monomers and additional monomers to a dispersion solvent, then adding a template agent and an initiator, and reacting at 50-80°C for 3-12 hours to obtain the polyionic liquid carrier.

7. The polyionic liquid-supported metallocene catalyst system according to claim 6, wherein, The dispersing solvent is a C1-C4 alcohol or a mixture of C1-C4 alcohol and ethylene glycol, wherein the mass ratio of the C1-C4 alcohol to ethylene glycol is 5-10:

1. The C1-C4 alcohols include one or more of methanol, ethanol, propanol, isopropanol, 1-butanol, and isobutanol. The template agent includes polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer; The template agent has a weight-average molecular weight of 6000-12000; The amount of the template agent added is 1-5% of the total mass of the monomers; The initiator includes azobisisobutyronitrile and / or benzoyl peroxide; The amount of the initiator added is 1-5% of the total mass of the monomers; The divinylbenzene is a pretreated divinylbenzene, wherein the pretreatment is to remove the polymerization inhibitor.

8. The polyionic liquid-supported metallocene catalyst system according to claim 1, wherein, The molar ratio of Al in the co-catalyst to the metal atoms in the metallocene compound is 75-500.

9. The polyionic liquid-supported metallocene catalyst system according to claim 8, wherein, The molar ratio of Al in the co-catalyst to the metal atoms in the metallocene compound is 100-300.

10. The polyionic liquid-supported metallocene catalyst system according to claim 1, wherein, The ratio of Al in the co-catalyst to the polyionic liquid carrier is from 3 mmol / g Al / g carrier to 8 mmol / g carrier.

11. The polyionic liquid-supported metallocene catalyst system according to claim 1, wherein, The ratio of metal atoms in the metallocene compound to the polyionic liquid carrier is from 10 micromoles of metallocene / gram carrier to 50 micromoles of metallocene / gram carrier.

12. The polyionic liquid-supported metallocene catalyst system according to claim 1, wherein, The alkylaluminoxanes include methylaluminoxanes and / or alkyl-modified methylaluminoxanes.

13. The polyionic liquid-supported metallocene catalyst system according to claim 1, wherein, A and B are each independently selected from C1-C8 alkyl or chlorine groups; M is zirconium, hafnium, or titanium, 1 ≤ x ≤ 3, and Cp is selected from C1-C6 alkyl-substituted cyclopentadienyl, indenyl, or fluorenyl groups.

14. The polyionic liquid-supported metallocene catalyst system according to claim 1, wherein, When x=2, Cp is bridged by polymethylene or dialkylsilane.

15. The polyionic liquid-supported metallocene catalyst system according to claim 1, wherein, The metallocene compounds include one or more of the following: di(cyclopentadienyl) metal dihalides, di(cyclopentadienyl) metal monoalkyl monohalides, di(cyclopentadienyl) metal dialkyl compounds, and di(indenyl) metal dihalides.

16. The polyionic liquid-supported metallocene catalyst system according to claim 1, wherein, The metallocene compounds include di(cyclopentadienyl)zirconia dichloride, di(cyclopentadienyl)hafnium dichloride, di(cyclopentadienyl)dimethylzirconia, di(cyclopentadienyl)dimethylhafnium, di(n-butylcyclopentadienyl)zirconia dichloride, di(n-butylcyclopentadienyl)hafnium dichloride, di(n-butylcyclopentadienyl)dimethylzirconia, di(n-butylcyclopentadienyl)dimethylhafnium, di(dimethylcyclopentadienyl)zonium, di(n-butylcyclopentadienyl)dimethylhafnium, di(dimethylcyclopentadienyl)zonium, di(n-butylcyclopentadienyl)zon ... Dienyl)dimethylzirconium, bis(tetramethylcyclopentadienyl)dimethylhafnium, diindylzirconium dichloride, methylene-bridged diindylzirconium dichloride, bis(4,5,6,7-tetrahydro-1-indyl)zirconium dichloride, ethylidene-bridged di(indyl)zirconium dichloride, diindylhafnium dichloride, methylene-bridged diindylhafnium dichloride, bis(4,5,6,7-tetrachloro-1-indyl)hafnium dichloride, ethylidene-bridged di(indyl)zirconium dichloride, di(tetramethylcyclopentadienyl)dimethylhafnium dichloride, di ... Hafnium dichloride, ethylene-bridged bis(indenyl)titanium dichloride, bis(4,5,6,7-tetra-hydro-1-indenyl)titanium dichloride, bis(n-butylcyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)titanium dichloride, dimethylsilyl-bridged bis(2-methyl-4-phenylindenyl)zirconium dichloride, dimethylsilyl-bridged bis(2-methyl-4-phenylindenyl)hafnium dichloride, dimethylsilyl-bridged bis(2-methyl-4-phenylindenyl)hafnium dichloride, dimethylsilyl-bridged bis(2-methyl-4-phenylindenyl)hafnium dichloride One or more combinations of the following: (-methyl-4-phenylindenyl)dimethylzirconium, dimethylsilyl-bridged bis(2-methylindenyl)zirconium dichloride, dimethylsilyl-bridged bis(2-methylindenyl)hafnium dichloride, dimethylsilyl-bridged bis(2-methyl-benzo[indenyl])zirconium dichloride, dimethylsilyl-bridged bis(2-methyl-benzo[indenyl])dimethylzirconium, and dimethylsilyl-bridged bis(2-methylindenyl)dimethylzirconium.

17. A method for preparing the polyionic liquid-supported metallocene catalyst system according to any one of claims 1-16, comprising the following steps: Under anhydrous and oxygen-free conditions, the polyionic liquid support, co-catalyst and solvent are mixed, a metallocene compound is added, and the mixture is reacted at 0-40°C for 60-180 minutes to obtain the polyionic liquid support type metallocene catalyst system. The solvent includes one or more of aromatic hydrocarbons, ethers, cyclic ethers, esters, and alkanes.

18. The preparation method according to claim 17, wherein, The solvent is toluene.

19. The application of the polyionic liquid-supported metallocene catalyst system according to any one of claims 1-16 in olefin polymerization; The olefin polymerization is ethylene homopolymerization, propylene homopolymerization, ethylene-propylene copolymerization, ethylene-α-olefin copolymerization, or propylene-α-olefin copolymerization.

20. The application according to claim 19, wherein, The α-olefin includes one or more of butene, pentene, hexene, octene, and 4-methyl-1-pentene.

21. The application according to claim 19, wherein, The olefin polymerization is gas-phase polymerization, bulk polymerization, or slurry polymerization.

22. The application according to claim 19, wherein, The polymerization reaction temperature is 30-120℃; the polymerization reaction pressure is 0.5-1.5 MPa.

23. The application according to claim 21, wherein, The solvent for the slurry polymerization is C5-C. 10 Alkanes.

24. The application according to claim 21, wherein, The solvent used for slurry polymerization is hexane.

Images