Polyion liquid carrier as well as preparation method and application thereof

Abstract

The invention provides a polyion liquid carrier as well as a preparation method and application thereof. The polyion liquid carrier is obtained by copolymerizing monomers including divinyl benzene and functional monomers; the functional monomer is ionic liquid containing cations and trifluoroacetic acid anions, and the cations comprise imidazole cations and / or pyridine cations; the imidazole cation has a structure shown in a formula I: # imgabs 0 #, and the pyridine cation has a structure shown in a formula II: # imgabs 1 #. The polyionic liquid carrier is suitable for a metallocene catalyst, and the loaded metallocene catalyst has high olefin polymerization activity.

Description

Technical Field

[0001] The present invention belongs to the field of catalysts, and specifically relates to a metallocene catalyst system and a preparation method and application thereof, and in particular to a polyionic liquid carrier, a polyionic liquid carrier-type metallocene catalyst system and a preparation method and application thereof. Background Art

[0002] In order to make metallocene catalysts suitable for industrial slurry polymerization or gas phase polymerization, it is very important to load metallocene to prepare supported metallocene catalysts. At present, the carriers used to load metallocene catalysts usually have inorganic carriers and polymer carriers. There are many reports of inorganic carriers as metallocene catalyst carriers, such as US4,808,561, US5,026,797, US5,763,543, US5,661,098, US6,455,647, CN1174549, CN1356343 report the use of inorganic materials such as silicon dioxide, magnesium chloride, aluminum oxide, etc. as carriers to prepare supported metallocene catalysts. Because the introduction of inorganic carriers will affect the performance of polyolefins after polymerization, such as causing higher ash content in polymers and causing fish eyes in thin films. In addition, the presence of "acidic" groups on the surface of inorganic carriers used for metallocene catalysts can cause catalyst deactivation, and complex surface treatment of inorganic carriers is required before loading metallocene catalysts. 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 gel carrier for metallocene or post-metallocene catalyst loading, which was further used to catalyze ethylene polymerization. However, its ethylene polymerization activity was low, the preparation process was complicated, and the inorganic silica gel carrier easily led to a high ash content in the polymer.

[0003] In recent years, organic polymer carriers containing porous structures have unique properties and good copolymerization properties. They can regulate the molecular weight of polymers through the nano-confinement effect during olefin polymerization through the polymer pore structure. In addition, the prepared polymer products have low inorganic ash content, which is increasingly attracting attention from the industry and academia. US5,587,439 discloses an ethylene / methacrylate copolymer loaded with metallocene. After the carrier reacts with cyclopentadienyl sodium, it can be used to load CpZrCl3 or ZrCl4(THF)2, and MAO is used as a co-catalyst to catalyze the polymerization of ethylene in a toluene solution. CN1624005 performs chloromethyl functionalization on linear polystyrene and crosslinks it through a DA reaction. The main disadvantage of this method is that the functional group structure of the carrier is unclear and the functional groups are unevenly distributed in the carrier. CN1396186 uses crosslinked polystyrene copolymerized with polypropylene alcohol as a polymer carrier. Currently, only solid carriers are reported. On the one hand, such solid carriers are not conducive to the loading of catalysts. On the other hand, solid carriers are not easy to break during the catalytic polymerization of ethylene, which is not conducive to the release of active centers. EP528092 discloses a preparation method of Me2Si(Ind)2ZrCl2-MAO loaded with polypropylene particles, and the polymer-loaded metallocene catalyst prepared by the method has good stability, and the corresponding polyolefin product has good morphology. CN101440137A discloses a copolymer of polystyrene, divinylbenzene and acrylonitrile loaded with metallocene, and the prepared copolymer carrier is a monodisperse porous polymer. However, the pore volume and average pore size of the copolymer carrier prepared by these two methods are small, which is not conducive to the loading of the metallocene catalyst, resulting in low catalyst activity. "Ionic Liquid-Modified Porous Organic Polymers as Efficient Metallocene Catalyst Supports" in "Catalysts" reports that the porous organic polymer divinylbenzene skeleton is modified with 1-n-butyl-3 vinyl imidazole chloride to prepare an ionic liquid-modified porous organic polymer for loading metallocene catalysts, which is used to catalyze ethylene polymerization and has good activity. Summary of the invention

[0004] In order to solve the above problems, the purpose of the present invention is to provide a polyionic liquid carrier and a preparation method and application thereof. The polyionic liquid carrier is suitable for metallocene catalysts, and the prepared metallocene catalyst has high olefin polymerization activity.

[0005] In order to achieve the above object, the present invention provides a polyionic liquid carrier, which is obtained by copolymerizing monomers including divinylbenzene and functional monomers; the functional monomers are ionic liquids containing cations and trifluoroacetic acid anions, and the cations include imidazolium cations and / or pyridinium cations (preferably pyridinium cations);

[0006] The imidazolium cation has a structure shown in Formula I:

[0007]

[0008] In Formula I, X is C1-C 12 Alkylene and its derivatives, R is selected from C1-C 15 Alkyl and its derivatives, phenyl and its derivatives;

[0009] The pyridinium cation has a structure shown in Formula II:

[0010]

[0011] In Formula II, Y is C1-C 12 Alkylene and its derivatives, R' is selected from C1-C 15 Alkyl and its derivatives, phenyl and its 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 monomer is selected from

[0015]

[0016] One or a combination of two or more.

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

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

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

[0020] The present invention also provides a method for preparing the polyionic liquid carrier, which comprises the following steps: using monomers including the divinylbenzene, the functional monomer and the additional monomer as raw materials, copolymerizing to obtain the polyionic liquid carrier; the additional monomer accounts for 0-60% of the total weight of the monomer.

[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 method comprises the following steps: adding divinylbenzene, functional monomers, additional monomers to a dispersion solvent, and then adding a template and an initiator, 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 a C1-C4 alcohol and ethylene glycol, and 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 alcohol includes one or a combination of two or more of methanol, ethanol, propanol, isopropanol, 1-butanol and isobutanol.

[0024] According to a specific embodiment of the present invention, preferably, the template 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 is 6000-12000.

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

[0027] According to a specific embodiment of the present invention, preferably, the initiator comprises azobisisobutyronitrile and / or dibenzoyl 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 monomers.

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

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

[0031] (I) Preparation of polymerizable ionic liquids

[0032] (1) Preparation of Vinylphenyl Magnesium Chloride Grignard Reagent

[0033] Prepare a mixed solution of toluene, tetrahydrofuran and chlorostyrene, wherein the chlorostyrene is 2-chlorostyrene, 3-chlorostyrene or 4-chlorostyrene. Under nitrogen protection, take a small amount of the mixed solution to wet magnesium powder, the magnesium powder accounts for 20-30% of the mass of chlorostyrene, add 1,2-dibromoethane initiator to the magnesium powder, accounting for 2-6% of the mass of chlorostyrene in the mixed solution, initiate the reaction, further slowly add the mixed solution, react at room temperature for 2-8 hours, and prepare a vinylphenyl magnesium chloride Grignard reagent (structure as shown in formula III, hereinafter referred to as Grignard reagent),

[0034]

[0035] (2) Preparation of intermediates

[0036] Using cuprous chloride as a catalyst, slowly drop the above-mentioned vinylphenyl magnesium chloride Grignard reagent into a dihalogenated alkane at 0-10° C., the molar ratio of the dihalogenated alkane to the vinylphenyl magnesium chloride Grignard reagent is about 5:1-3:1, after reacting for 2-5 hours, adjusting the pH of the system to 5-6 with dilute sulfuric acid, separating and removing the aqueous phase, and distilling under reduced pressure to obtain an intermediate (the structure is shown in Formula IV); the dihalogenated alkane includes but is not limited to dichloromethane, 1,2-dichloroethane, 1,3- 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-dibromodoundecane, 1,12-dibromododecane;

[0037]

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

[0039] Add R'-substituted pyridine or R-substituted imidazole to an inert solvent (such as toluene, hexane), slowly add the intermediate (compound shown in Formula IV), wherein the molar ratio of R'-substituted pyridine or R-substituted imidazole to the intermediate is 1.5:1-1:1, and react at 80-120°C for 20-24 hours. Remove the solvent by vacuum distillation, and wash with anhydrous ether to obtain a polymerizable ionic liquid N + Cl - Dissolve N in a small amount of deionized water. + Cl -, under ice bath stirring condition, slowly dropwise add trifluoroacetic acid with a molar ratio of 1.1:1-1.5:1. After the dropwise addition is completed, nitrogen protection is applied, and the ice bath reaction is continued for 0.5-2h, and then the ice bath is removed to allow the reaction system to warm to room temperature, and the reaction is continued with stirring for 2-4h. After the reaction is completed, the mixture is decompressed and rotary evaporated to remove water, and finally vacuum dried at 80°C for 24h to obtain trifluoroacetic acid ionic liquid N + CF3COO - , N + is an imidazolium cation or a pyridinium cation;

[0040] (II) Preparation of polyionic liquid carriers

[0041] At room temperature, divinylbenzene, a basic monomer except for the polymerization inhibitor, and an ionic liquid functional monomer are sequentially added to a dispersing solvent, wherein the dispersing solvent is a C1-C4 lower alcohol or a mixed solvent system of a C1-C4 alcohol and ethylene glycol, wherein the mass ratio of the C1-C4 alcohol to the ethylene glycol in the mixed solvent system is 5-10:1, and the C1-C4 alcohol is methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, etc.; a template agent (such as polyvinyl alcohol or polypropylene oxide-ethylene oxide copolymer) is added at room temperature, wherein the weight average molecular weight of the template agent is controlled between 6000 and 10000, and the amount added is 1-5% of the total mass of the reaction monomers; a free radical initiator is added for reaction, and any common free radical initiator can be used, including azobisisobutyronitrile (AIBN) or dibenzoyl 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 reaction monomers. After the reaction is completed, the unreacted monomers, template agents and other impurities are washed away with C1-C4 lower alcohol to obtain a polyionic liquid carrier (denoted as IPOP).

[0042] The present invention also provides a polyionic liquid carrier type metallocene catalyst system, which comprises the polyionic liquid carrier, a cocatalyst and a metallocene compound; wherein the cocatalyst can be used to activate the polyionic liquid carrier.

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

[0044] According to a specific embodiment of the present invention, preferably, the usage ratio of Al in the co-catalyst to the polyionic liquid carrier is 1 mmol Al / g carrier to 12 mmol Al / g carrier, more preferably 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 the metal atom in the metallocene compound to the polyionic liquid carrier is 5 micromoles metallocene / gram carrier to 100 micromoles metallocene / gram carrier, more preferably 10 micromoles metallocene / gram carrier to 50 micromoles 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 general formula of the metallocene compound is Cp x MA y B z , wherein 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 a halogen atom, a hydrogen atom, an alkyl group, x, y, z are 0-3 respectively, and x, y, 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 a C1-C8 alkyl group or chlorine; 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 -Si(CH3)2-, -C(CH3)2-, -CH2-, -CH2-CH2- and the like.

[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 cyclopentadienyl, indenyl and its derivatives or fluorenyl and its derivatives substituted by C1-C6 straight alkyl groups.

[0053] According to a specific embodiment of the present invention, preferably, the metallocene compound includes one or a combination of two or more of di(cyclopentadienyl)metal dihalide, di(cyclopentadienyl)metal monoalkyl monohalide, di(cyclopentadienyl)metal dialkyl compound, and di(indenyl)metal dihalide.

[0054] According to a specific embodiment of the present invention, preferably, the metallocene compound includes bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)hafnium dimethyl, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)hafnium dichloride, bis(n-butylcyclopentadienyl)zirconium dimethyl, bis(n-butylcyclopentadienyl) Dimethyl hafnium, bis(dimethylcyclopentadienyl) dimethyl zirconium, bis(tetramethylcyclopentadienyl) dimethyl hafnium, diindenyl zirconium dichloride, methylene-bridged diindenyl zirconium dichloride, di(4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylene-bridged di(indenyl) zirconium dichloride, diindenyl hafnium dichloride, methylene-bridged diindenyl hafnium dichloride, di(4,5,6,7-tetrachloro-1-indenyl) hafnium dichloride, Ethylene bridged-bis(indenyl)dichlorohafnium, ethylene bridged-bis(indenyl)dichlorotitanium, bis(4,5,6,7-tetra-hydro-1-indenyl)dichlorotitanium, bis(n-butylcyclopentadienyl)dichlorotitanium, bis(cyclopentadienyl)dichlorotitanium, dimethylsilyl bridged-bis(2-methyl-4-phenylindenyl)dichlorozirconium, dimethylsilyl bridged-bis(2-methyl-4-phenylindenyl)dichlorohafnium, dimethylsilyl bridged-bis(2-methyl-4-phenylindenyl)dichlorotitanium One or a combination of two or more of dimethylsilyl-bis(2-methyl-4-phenylindenyl) zirconium dimethyl, dimethylsilyl-bridged bis(2-methylindenyl) zirconium dichloride, dimethylsilyl-bridged bis(2-methylindenyl) hafnium dichloride, dimethylsilyl-bridged bis(2-methyl-benzoindenyl) zirconium dichloride, dimethylsilyl-bridged bis(2-methyl-benzoindenyl) zirconium dimethyl, and dimethylsilyl-bridged bis(2-methylindenyl) zirconium dimethyl.

[0055] The present invention also provides a method for preparing the above-mentioned polyionic liquid carrier type metallocene catalyst system, which comprises the following steps: under anhydrous and oxygen-free conditions, mixing the polyionic liquid carrier, co-catalyst and solvent, adding a metallocene compound, and reacting at 0-40° C. for 60-180 minutes to obtain the polyionic liquid carrier type metallocene catalyst system.

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

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

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

[0059] The cocatalyst alkylaluminoxane of the present invention is first loaded onto the polyionic liquid through non-covalent bonds to obtain a cocatalyst activated polyionic liquid carrier, and then a metallocene compound is added to obtain a polyionic liquid loaded metallocene catalyst. For example, methylaluminoxane MAO is used to activate the polyionic liquid, and Al-CH3 in MAO reacts with imidazolium cations or pyridinium cations in the polyionic liquid carrier to remove CH4 and load it onto the porous polyionic liquid carrier skeleton. Meanwhile, the trifluoroacetate anion has an electron-donating effect and reacts with Al in MAO to modify MAO to form IPOP-CF3COO---Al-MAO activated carrier. When the metallocene compound is added for reaction, the MAO on the activated carrier methylates the metallocene compound to form [Cp2MMe] + [IPOP-CF3COO---Al-MAO] - Ion pair, it is generally believed that M is the effective active center (M = Zr, Ti, Hf, etc., Cp is cyclopentadienyl, etc., IPOP is the prepared polyionic liquid carrier, and the molecular structure is a simplified molecular structure for illustration only).

[0060] The present invention also provides application of the polyionic liquid-carrier type 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 and propylene copolymerization, ethylene and α-olefin copolymerization or propylene and α-olefin copolymerization.

[0062] According to a specific embodiment of the present invention, preferably, the α-olefin includes one or a combination of two or more 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 An alkane, more preferably hexane.

[0067] According to a specific embodiment of the present invention, preferably, a small amount of alkyl aluminum compounds, such as triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-hexyl aluminum, etc., can also be added into the polymerization reaction as an impurity remover for the polymerization reaction system.

[0068] The present invention forms a stable ion pair [Cp2MMe] by designing and optimizing the ionic liquid skeleton structure and anion, regulating the pore structure of the polyionic liquid carrier and the chemical environment of the metal active center. + [IPOP-CF3COO---Al-MAO] - Through the synergistic effect of trifluoroacetate anion and co-catalyst, the metallocene active center M is increased. + The concentration of 1-butyl-3-vinyl imidazolium chloride can obtain a higher catalytic activity, so that the prepared metallocene catalyst has a higher olefin polymerization activity than the organic carrier modified with 1-n-butyl-3-vinyl imidazolium chloride. The polyionic liquid of the present invention has the excellent properties of both ionic liquid and polymer. When the polyionic liquid carrier type metallocene catalyst catalyzes olefin polymerization, it has the characteristics of both homogeneous catalysis and heterogeneous catalysis. DETAILED DESCRIPTION

[0069] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be understood as limiting the scope of the present invention. In the following examples, specific conditions and experimental methods are not specified, and conventional conditions are usually used.

[0070] The monomer divinylbenzene (DVB) used in the preparation process of the support of the following metallocene catalyst system can be a commercially available monomer with a DVB monomer content of 55% or 80%. It needs to be pretreated before use to remove the polymerization inhibitor before use. There are many methods for removing the polymerization inhibitor in the prior art, such as washing with sodium hydroxide solution and distilled water. In the following examples, divinylbenzene needs to be used with a 10% sodium hydroxide solution to remove the polymerization inhibitor before use, and then washed three times with deionized water before use.

[0071] The Al and metal active center atoms such as zirconium and hafnium in the polyionic liquid-supported metallocene catalyst were analyzed and tested using the VISTA-MPX inductively coupled plasma emission spectrometry of Varian Corporation of the United States: the sample was first burned into ash in a muffle furnace, then perchloric acid and aqua regia were added, heated and digested, dissolved with 2% HCl solution, and the volume was fixed. Then the characteristic peak intensity of Al and metal active center atoms in the metallocene catalyst was determined, and their content was calculated according to the standard curve.

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

[0073] The specific surface area was tested by Nova 2000e using the BET nitrogen adsorption method. The specific surface area of ​​the polyionic liquid carrier prepared in the following examples is greater than 100 m 2 / g, 100~600m 2 / g, pore volume greater than 0.2cm 3 / g.

[0074] Chemical structure of the polymerizable ionic liquid prepared in Preparation Example 1-8:

[0075]

[0076]

[0077] Preparation Example 1-8 Preparation of polymerizable ionic liquid

[0078] Preparation Example 1

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

[0080] Prepare a mixed solution of 50g 4-chlorostyrene (Aladdin reagent, >97%), 75g anhydrous tetrahydrofuran, and 75g anhydrous toluene; under nitrogen protection, add 10g of metal magnesium powder to a 500mL reaction container, take a small amount of the above mixed solution, wet the magnesium powder, slowly add 1g of 1,2-dibromoethane (Aladdin reagent, 99%) dropwise under stirring to initiate the reaction, the magnesium powder bubbles and turns dark green, slowly add the p-chlorostyrene mixed solution dropwise to the reaction container, control the reaction temperature at 25°C, and complete the addition in about 2 hours to obtain 4-vinylphenylmagnesium chloride Grignard reagent;

[0081] In another 500mL reaction container, add 91g of dichloromethane (Aladdin reagent, ≥99.8%) and 1g of cuprous chloride catalyst, slowly add 4-vinylphenylmagnesium chloride Grignard reagent dropwise at 10°C for about 3 hours, add 150mL of deionized water after the reaction, adjust the pH to 5-6 with dilute sulfuric acid, separate the liquids and distill under reduced pressure to obtain 48g of 4-vinylbenzyl chloride;

[0082] In a 500mL reaction container, 33g 1-methylimidazole (Aladdin reagent, 99%), 200mL toluene, and 48g 4-vinylbenzyl chloride were added in sequence, and the reaction was carried out at 80°C for 24 hours. After the solvent was removed by distillation under reduced pressure, anhydrous ether was added to precipitate a solid, and the solid was washed with anhydrous ether, dried and added to a 500mL reaction container, and a small amount of deionized water was added to dissolve the solid. Under ice bath stirring conditions, 37g trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was completed, nitrogen protection was applied, and the ice bath reaction was continued for 2 hours, and then the ice bath was removed to warm the reaction system to room temperature. The reaction was continued to stir for 3 hours. After the reaction was completed, the mixture was rotary evaporated under reduced pressure to remove water, and vacuum dried at 80°C for 24 hours to obtain 62.4g trifluoroacetic acid ionic liquid IL-1, which was verified by nuclear magnetic resonance to have a correct structure.

[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 mixed solution of 50g 2-chlorostyrene (Aladdin reagent, >97%), 75g anhydrous tetrahydrofuran, and 75g anhydrous toluene; under nitrogen protection, add 15g metal magnesium powder to a 500mL reaction container, take a small amount of the mixed solution, wet the magnesium powder, slowly add 3g 1,2-dibromoethane (Aladdin reagent, 99%) dropwise under stirring to initiate the reaction, the magnesium powder bubbles and turns dark green, slowly add the 2-chlorostyrene mixed solution dropwise to the reaction container, control the reaction temperature at 25°C, and complete the addition in about 6 hours to obtain 2-vinylphenylmagnesium chloride Grignard reagent;

[0087] In another 500mL reaction container, add 229g 1,3-dichlorobutane (Aladdin reagent, ≥98%), 1g cuprous chloride catalyst, slowly add 2-vinylphenylmagnesium chloride Grignard reagent at 0°C, and add for about 3 hours. After the reaction, add 150mL deionized water, adjust the pH to 5-6 with dilute sulfuric acid, separate the liquids, and distill under reduced pressure to obtain 62g of the intermediate;

[0088] In a 500mL reaction container, 64g 3-butylpyridine (Aladdin reagent, 98%), 200mL toluene, and 62g intermediate were added in sequence, and the reaction was carried out at 100°C for 24 hours. After the solvent was removed by distillation under reduced pressure, anhydrous ether was added to precipitate a solid, and the solid was washed with anhydrous ether, dried and added to a 500mL reaction container, and a small amount of deionized water was added to dissolve the solid. Under ice bath stirring conditions, 39g trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was completed, nitrogen protection was applied, and the ice bath reaction was continued for 2 hours, and then the ice bath was removed to warm the reaction system to room temperature. The reaction was continued to stir for 4 hours. After the reaction was completed, the mixture was rotary evaporated under reduced pressure to remove water, and vacuum dried at 80°C for 24 hours to obtain 99.6g trifluoroacetic acid ionic liquid IL-2, which was verified by nuclear magnetic resonance to have a correct structure.

[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 50g 3-chlorostyrene (Aladdin reagent, >97%), 75g anhydrous tetrahydrofuran, and 75g anhydrous toluene. Under nitrogen protection, add 12g of metal magnesium powder to a 500mL reaction container, take a small amount of the above mixture, wet the magnesium powder, slowly add 2.2g 1,2-dibromoethane (Aladdin reagent, 99%) to initiate the reaction, the magnesium powder bubbles and turns dark green, slowly add 3-chlorostyrene mixture to the reaction container, control the reaction temperature at 25°C, and complete the addition in about 4 hours to obtain 3-vinylphenyl magnesium chloride Grignard reagent;

[0092] In another 500mL reaction container, add 355g 1,12-dibromododecane (Aladdin reagent, ≥98%), 1g cuprous chloride catalyst, slowly add 3-vinylphenylmagnesium chloride Grignard reagent at 0°C, and the addition is completed in about 3 hours. After the reaction is completed, add 150mL deionized water, adjust the pH to 5-6 with dilute sulfuric acid, separate the liquids, and distill under reduced pressure to obtain 98g of the intermediate;

[0093] In a 500mL reaction container, 71g 4-benzylpyridine (Aladdin reagent, 98%), 200mL toluene, and 98g intermediate were added in sequence, and the reaction was carried out at 100°C for 20 hours. After the solvent was removed by distillation under reduced pressure, anhydrous ether was added to precipitate a solid, and the solid was washed with anhydrous ether, dried and added to a 500mL reaction container, and a small amount of deionized water was added to dissolve the solid. Under ice bath stirring conditions, 49.2g trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was completed, nitrogen protection was applied, and the ice bath reaction was continued for 2 hours, and then the ice bath was removed to warm the reaction system to room temperature. The reaction was continued to stir for 4 hours. After the reaction was completed, the mixture was rotary evaporated under reduced pressure to remove water, and vacuum dried at 80°C for 24 hours to obtain 119.4g trifluoroacetic acid ionic liquid IL-3, which was verified by nuclear magnetic resonance to have a correct structure.

[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 50g 3-chlorostyrene (Aladdin reagent, >97%), 75g anhydrous tetrahydrofuran, and 75g anhydrous toluene. Under nitrogen protection, add 13g of metal magnesium powder to a 500mL reaction container, take a small amount of the above mixture, wet the magnesium powder, slowly stir and drop 1.8g 1,2-dibromoethane (Aladdin reagent, 99%) to initiate the reaction, the magnesium powder bubbles and turns dark green, slowly drop 3-chlorostyrene mixture into the reaction container, control the reaction temperature at 25°C, and drop in about 4 hours to obtain 3-vinylphenyl magnesium chloride Grignard reagent;

[0097] In another 500mL reaction container, add 223g 1,6-dichlorohexane (Aladdin reagent, ≥98%), 1g cuprous chloride catalyst, slowly add 3-vinylphenylmagnesium chloride Grignard reagent at 0°C, and add for about 3 hours. After the reaction, add 150mL deionized water, adjust the pH to 5-6 with dilute sulfuric acid, separate the liquids, and distill under reduced pressure to obtain 72g of the intermediate;

[0098] In a 500mL reaction container, 52g of 1-butylimidazole (Aladdin reagent, 98%), 200mL of toluene, and 72g of the intermediate were added in sequence, and the reaction was carried out at 100°C for 20 hours. After the solvent was removed by distillation under reduced pressure, anhydrous ether was added to precipitate a solid, and the solid was washed with anhydrous ether, dried and added to a 500mL reaction container, and a small amount of deionized water was added to dissolve the solid. Under ice bath stirring conditions, 37.9g ​​of trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was completed, nitrogen protection was applied, and the ice bath reaction was continued for 2 hours, and then the ice bath was removed to warm the reaction system to room temperature. The reaction was continued to stir for 4 hours. After the reaction was completed, the mixture was rotary evaporated under reduced pressure to remove water, and vacuum dried at 80°C for 24 hours to obtain 76.0g of trifluoroacetic acid ionic liquid IL-4, which was verified by nuclear magnetic resonance to have a correct structure.

[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 50g 3-chlorostyrene (Aladdin reagent, >97%), 75g anhydrous tetrahydrofuran, and 75g anhydrous toluene. Under nitrogen protection, add 13g of metal magnesium powder to a 500mL reaction container, take a small amount of the above mixture, wet the magnesium powder, slowly add 2.6g 1,2-dibromoethane (Aladdin reagent, 99%) to initiate the reaction under stirring, the magnesium powder bubbles and turns dark green, slowly add the 3-chlorostyrene mixture to the reaction container, control the reaction temperature at 25°C, and complete the addition in about 3 hours to obtain 3-vinylphenylmagnesium chloride Grignard reagent;

[0102] In another 500mL reaction container, add 279g 1,7-dibromoheptane (Aladdin reagent, ≥98%), 1g cuprous chloride catalyst, slowly add 3-vinylphenylmagnesium chloride Grignard reagent at 0°C, and add for about 3 hours. After the reaction, add 150mL deionized water, adjust the pH to 5-6 with dilute sulfuric acid, separate the liquids, and distill under reduced pressure to obtain 83g of the intermediate;

[0103] In a 500mL reaction container, 96g 4-ethylpyridine (Aladdin reagent, 98%), 200mL toluene, and 83g intermediate were added in sequence, and the reaction was carried out at 100°C for 24 hours. After the solvent was removed by distillation under reduced pressure, anhydrous ether was added to precipitate a solid, and the solid was washed with anhydrous ether, dried and added to a 500mL reaction container, and a small amount of deionized water was added to dissolve the solid. Under ice bath stirring conditions, 37.3g trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was completed, nitrogen protection was applied, and the ice bath reaction was continued for 2 hours, and then the ice bath was removed to warm the reaction system to room temperature. The reaction was continued to stir for 4 hours. After the reaction was completed, the mixture was rotary evaporated under reduced pressure to remove water, and vacuum dried at 80°C for 24 hours to obtain 103.3g trifluoroacetic acid ionic liquid IL-5, which was verified by nuclear magnetic resonance to have a correct structure.

[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 50g 3-chlorostyrene (Aladdin reagent, >97%), 75g anhydrous tetrahydrofuran, and 75g anhydrous toluene. Under nitrogen protection, add 13g of metal magnesium powder to a 500mL reaction container, take a small amount of the above mixture, wet the magnesium powder, slowly add 2.6g 1,2-dibromoethane (Aladdin reagent, 99%) to initiate the reaction under stirring, the magnesium powder bubbles and turns dark green, slowly add the 3-chlorostyrene mixture to the reaction container, control the reaction temperature at 25°C, and complete the addition in about 3 hours to obtain 3-vinylphenylmagnesium chloride Grignard reagent;

[0107] In another 500mL reaction container, add 137g 1,4-dichlorobutane (Aladdin reagent, ≥98%), 1g cuprous chloride catalyst, slowly add 3-vinylphenylmagnesium chloride Grignard reagent at 0°C, and add for about 3 hours. After the reaction, add 150mL deionized water, adjust the pH to 5-6 with dilute sulfuric acid, separate the liquids, and distill under reduced pressure to obtain 68g of the intermediate;

[0108] In a 500mL reaction container, 88g of 2-benzylpyridine (Aladdin reagent, 98%), 200mL of toluene, and 68g of the intermediate were added in sequence, and the reaction was carried out at 100°C for 24 hours. After the solvent was removed by distillation under reduced pressure, anhydrous ether was added to precipitate a solid, and the solid was washed with anhydrous ether, dried and added to a 500mL reaction container, and a small amount of deionized water was added to dissolve the solid. Under ice bath stirring conditions, 39.1g of trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was completed, nitrogen protection was applied, and the ice bath reaction was continued for 2 hours, and then the ice bath was removed to warm the reaction system to room temperature. The reaction was continued to stir for 4 hours. After the reaction was completed, the mixture was rotary evaporated under reduced pressure to remove water, and vacuum dried at 80°C for 24 hours to obtain 95.8g of trifluoroacetic acid ionic liquid IL-6, which was verified by nuclear magnetic resonance to have a correct structure.

[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 50g 4-chlorostyrene (Aladdin reagent, >97%), 75g anhydrous tetrahydrofuran, and 75g anhydrous toluene. Under nitrogen protection, add 13g of metal magnesium powder to a 500mL reaction container, take a small amount of the above mixture, wet the magnesium powder, slowly add 2.6g 1,2-dibromoethane (Aladdin reagent, 99%) to initiate the reaction, the magnesium powder bubbles and turns dark green, slowly add 4-chlorostyrene mixture to the reaction container, control the reaction temperature at 25°C, and complete the addition in about 3 hours to obtain 3-vinylphenylmagnesium chloride Grignard reagent;

[0112] In another 500mL reaction container, add 122g 1,3-dichloropropane (Aladdin reagent, ≥98%), 1g cuprous chloride catalyst, slowly add 4-vinylphenylmagnesium chloride Grignard reagent at 0°C, and add it in about 3 hours. After the reaction, add 150mL deionized water, adjust the pH to 5-6 with dilute sulfuric acid, separate the liquids, and distill under reduced pressure to obtain 57g of the intermediate.

[0113] In a 500mL reaction container, 35g 3-methylpyridine (Aladdin reagent, 99%), 200mL toluene, and 57g intermediate were added in sequence, and the reaction was carried out at 120°C for 24 hours. After the solvent was removed by distillation under reduced pressure, anhydrous ether was added to precipitate a solid, and the solid was washed with anhydrous ether, dried and added to a 500mL reaction container, and a small amount of deionized water was added to dissolve the solid. Under ice bath stirring conditions, 37.5g trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was completed, nitrogen protection was applied, and the ice bath reaction was continued for 2 hours, and then the ice bath was removed to warm the reaction system to room temperature. The reaction was continued to stir for 4 hours. After the reaction was completed, the mixture was rotary evaporated under reduced pressure to remove water, and vacuum dried at 80°C for 24 hours to obtain 79.9g trifluoroacetic acid ionic liquid IL-7, which was verified by nuclear magnetic resonance to have a correct structure.

[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 50g 4-chlorostyrene (Aladdin reagent, >97%), 75g anhydrous tetrahydrofuran, and 75g anhydrous toluene. Under nitrogen protection, add 13g of metal magnesium powder to a 500mL reaction container, take a small amount of the above mixture, wet the magnesium powder, slowly add 2.6g 1,2-dibromoethane (Aladdin reagent, 99%) to initiate the reaction, the magnesium powder bubbles and turns dark green, slowly add 4-chlorostyrene mixture to the reaction container, control the reaction temperature at 25°C, and complete the addition in about 3 hours to obtain 4-vinylphenyl magnesium chloride Grignard reagent;

[0117] In another 500mL reaction container, add 203g 1,5-dichloropentane (Aladdin reagent, ≥98%), 1g cuprous chloride catalyst, slowly add 4-vinylphenylmagnesium chloride Grignard reagent at 0°C, and add for about 3 hours. After the reaction, add 150mL deionized water, adjust the pH to 5-6 with dilute sulfuric acid, separate the liquids, and distill under reduced pressure to obtain 68g of the intermediate;

[0118] In a 500mL reaction container, 73g of 1-phenylethylimidazole (Aladdin reagent, >98%), 200mL of toluene, and 68g of the intermediate were added in sequence, and the reaction was carried out at 120°C for 20 hours. After the solvent was removed by distillation under reduced pressure, anhydrous ether was added to precipitate a solid, and the solid was washed with anhydrous ether, dried and added to a 500mL reaction container, and a small amount of deionized water was added to dissolve the solid. Under ice bath stirring conditions, 39.1g of trifluoroacetic acid (Aladdin reagent, ≥99%) was slowly added dropwise. After the addition was completed, nitrogen protection was applied, and the ice bath reaction was continued for 2 hours, and then the ice bath was removed to allow the reaction system to warm to room temperature. The reaction was continued with stirring for 4 hours. After the reaction was completed, the mixture was rotary evaporated under reduced pressure to remove water, and vacuum dried at 80°C for 24 hours to obtain 78.3g of trifluoroacetic acid ionic liquid IL-8, which was verified by nuclear magnetic resonance to have a correct structure.

[0119] Example 1-10 Preparation of polyionic liquid carrier

[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 container as a dispersant, and 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 4.8 g of ionic liquid IL-1 were added to the system in sequence, stirred at room temperature for 10 minutes, and then 2% of the total weight of the monomer as the template polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added, and stirred at 50°C for 30 minutes until the template was completely dissolved, and 5% of the total weight of the monomer as the initiator AIBN was added, the temperature was raised to 70°C for reaction for 3 hours, and then the temperature was raised to 80°C for reaction for 6 hours. After the reaction, the temperature was lowered to 50°C, filtered, washed three times with methanol, filtered 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 container as a dispersant, and 4.8 g of divinylbenzene (Aladdin reagent, 55%) and 1.8 g of ionic liquid IL-4 were added to the system in sequence, stirred at room temperature for 10 minutes, and then 2% of the total weight of the monomer as the template polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added, and stirred at 50° C. for 30 minutes until the template was completely dissolved, and 2% of the total weight of the monomer as the initiator AIBN was added, the temperature was raised to 70° C. for reaction for 3 hours, and then the temperature was raised to 80° C. for reaction for 6 hours. After the reaction was completed, the temperature was lowered to 50° C., filtered, washed three times with methanol, filtered 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 container as a dispersant, and 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 2.1 g of ionic liquid IL-2 were added to the system in sequence, stirred at room temperature for 10 minutes, and then 2% of the total weight of the monomer as the template polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added, and stirred at 50° C. for 30 minutes until the template was completely dissolved, and 2% of the total weight of the monomer as the initiator AIBN was added, the temperature was raised to 70° C. for reaction for 2 hours, and then the temperature was raised to 80° C. for reaction for 5 hours. After the reaction was completed, the temperature was lowered to 50° C., filtered, washed with ethanol three times, filtered 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 container as a dispersant, and 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 6.9 g of ionic liquid IL-3 were added to the system in sequence, stirred at room temperature for 10 minutes, and then 2% of the total weight of the monomer as the template polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added, and stirred at 50° C. for 30 minutes until the template was completely dissolved, and 2% of the total weight of the monomer as the initiator AIBN was added, the temperature was raised to 70° C. for reaction for 2 hours, and then the temperature was raised to 80° C. for reaction for 5 hours. After the reaction was completed, the temperature was lowered to 50° C., filtered, washed three times with isobutanol, filtered 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 container as a dispersant, and 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 3.8 g of ionic liquid IL-8 were added to the system in sequence, stirred at room temperature for 10 minutes, and then 5% of the total weight of the monomer template polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added, and stirred at 50° C. for 30 minutes until the template was completely dissolved, and 2% of the total weight of the monomer initiator AIBN was added, the temperature was raised to 70° C. for reaction for 3 hours, and then the temperature was raised to 80° C. for reaction for 5 hours. After the reaction, the temperature was lowered to 50° C., filtered, washed with ethanol three times, filtered 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 container as dispersants, and 4.8 g of divinylbenzene (Aladdin reagent, 55%) and 6.8 g of ionic liquid IL-6 were added to the system in sequence, stirred at room temperature for 10 minutes, and then 3% of the total weight of the monomer as the template polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added, and stirred at 50° C. for 30 minutes until the template was completely dissolved, and 5% of the total weight of the monomer as the initiator AIBN was added, the temperature was raised to 70° C. for reaction for 3 hours, and then the temperature was raised to 80° C. for reaction for 8 hours. After the reaction was completed, the temperature was lowered to 50° C., filtered, washed with ethanol three times, filtered 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 container as a dispersant, and 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 2.1 g of ionic liquid IL-5 were added to the system in sequence, stirred at room temperature for 10 minutes, and then 2% of the total weight of the monomer as the template polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added, and stirred at 50° C. for 30 minutes until the template was completely dissolved, and 2% of the total weight of the monomer as the initiator AIBN was added, the temperature was raised to 70° C. for reaction for 3 hours, and then the temperature was raised to 80° C. for reaction for 5 hours. After the reaction was completed, the temperature was lowered to 50° C., filtered, washed with ethanol three times, filtered 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 container as a dispersant, and 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 3.2 g of ionic liquid IL-5 and 1.7 g of hydroxyethyl methacrylate were added to the system in sequence. The mixture was stirred at room temperature for 10 minutes, and then 2% of the total weight of the monomer as the template 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 was completely dissolved. 2% of the total weight of the monomer as the initiator AIBN was added, the mixture was heated to 70° C. for reaction for 3 hours, and then heated to 80° C. for reaction for 5 hours. After the reaction, the mixture was cooled to 50° C., filtered, washed with ethanol three times, filtered 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 container as a dispersant, and 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 3.5 g of ionic liquid IL-7 were added to the system in sequence, stirred at room temperature for 10 minutes, and then 2% of the total weight of the monomer as the template polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added, and stirred at 50° C. for 30 minutes until the template was completely dissolved, and 2% of the total weight of the monomer as the initiator AIBN was added, the temperature was raised to 70° C. for reaction for 3 hours, and then the temperature was raised to 80° C. for reaction for 5 hours. After the reaction was completed, the temperature was lowered to 50° C., filtered, washed with ethanol three times, filtered 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 container as a dispersant, and 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 to the system in sequence, and stirred at room temperature for 10 minutes, and then 2% of the total weight of the monomer template polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added, and stirred at 50° C. for 30 minutes until the template was completely dissolved, and 2% of the total weight of the monomer initiator AIBN was added, and the temperature was raised to 70° C. for reaction for 3 hours, and then raised to 80° C. for reaction for 5 hours. After the reaction, the temperature was lowered to 50° C., filtered, washed with ethanol three times, filtered and dried to obtain 7.9 g of polyionic liquid IPOP-10.

[0150] Comparative Example 1

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

[0152] In a 250mL round-bottom glass reactor, 130mL of ethanol and 15mL of deionized water were added, followed by 4.8g of 80% divinylbenzene and 2.4g of hydroxyethyl methacrylate (Aladdin reagent, 90%), stirred at room temperature for 10 minutes, and 2% of the total weight of the monomer of polypropylene oxide-polyethylene oxide copolymer F127 (BASF, molecular weight 12000) was added, stirred at 55°C for 30 minutes, and after F127 was completely dissolved, 2% of the monomer weight of initiator AIBN was added, the temperature was raised to 70°C for reaction for 3 hours, and then raised to 80°C for reaction for 5 hours, washed with a mixture of ethanol and water, filtered and dried to obtain 4.6g (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 container as a dispersant, and 4.8 g of divinylbenzene (Aladdin reagent, 80%) and 3.5 g of 1-vinyl-3-butylimidazole chloride (Zhengzhou Alpha Chemical Co., Ltd., 98%) were added to the system in sequence, and stirred at room temperature for 10 minutes, and then 2% of the total weight of the monomer template polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added, and stirred at 50° C. for 30 minutes until the template was completely dissolved, and 2% of the total weight of the monomer initiator AIBN was added, and the temperature was raised to 70° C. for reaction for 3 hours, and then raised to 80° C. for reaction for 5 hours. After the reaction, the temperature was lowered to 50° C., filtered, washed with ethanol three times, filtered and dried to obtain 6.8 g of 1-vinyl-3-butylimidazole 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 results of the carrier

[0158] Carrier <![CDATA[Specific surface area m 2 / g]]> <![CDATA[Pore volume cm 3 / g]]> D(50)μm Particle size distribution 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 the present invention has a high specific surface area, which can reach 500m 2 / g or more, pore volume greater than 0.2cm 3 The polyionic liquid carrier of the present invention has good fluidity, no obvious agglomeration, is not easy to absorb moisture, has no obvious agglomeration, and has a narrow particle size distribution, which is generally less than 2.

[0160] Example 11-20 Preparation of Metallocene Catalyst

[0161] Embodiment 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 vacuum dried at 120°C for 10 hours. The treated carrier was added to a 250mL nitrogen-substituted multi-port reactor, and 25mL of 10% (mass percentage) MAO (produced by PetroChina Lanzhou Chemical Research Center, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution was added, and stirred at room temperature for 1 hour. Then 0.19g (n-BuCp) 2ZrCl2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL toluene were added, and stirred at 25°C for 3 hours. The reaction was terminated, and the solvent was removed by vacuum distillation and dried to obtain catalyst Cat-1, in which the Al content was 4.7 mmol / g and the Zr content was 47.2 micromol / g.

[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 vacuum dried at 120°C for 10 hours. The treated carrier was added to a 250mL nitrogen-substituted multi-port reactor, and 25mL of 10% (mass percent) MAO (produced by Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution was added, and stirred at room temperature for 1 hour. Then 0.19g (n-BuCp) 2ZrCl 2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL toluene were added, and stirred at 40°C for 3 hours. The reaction was terminated, and the solvent was removed by vacuum distillation and dried to obtain the catalyst Cat-2, in which the Al content was 5.0 mmol / g and the Zr content was 44.7 micromol / g.

[0167] Embodiment 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 vacuum dried at 120°C for 10 hours. The treated carrier was added to a 250mL nitrogen-substituted multi-port reactor, and 30mL of 10% (mass percentage) MAO (produced by Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution was added, and stirred at room temperature for 1 hour. Then 0.23g (n-BuCp) 2ZrCl2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL toluene were added, and stirred at 0°C for 3 hours. The reaction was terminated, and the solvent was removed by vacuum distillation and dried to obtain the catalyst Cat-3, in which the Al content was 5.3 mmol / g and the Zr content was 46.2 micromol / g.

[0170] Embodiment 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 vacuum dried at 120°C for 10 hours. The treated carrier was added to a 250mL nitrogen-substituted multi-port reactor, and 25mL of 10% (mass percent) 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 was added, and stirred at room temperature for 1 hour. Then 0.14g (1-Me-3-n-BuCp) 2ZrCl 2 bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride metallocene compound was added, 10mL toluene was stirred at 25°C for 3 hours, the reaction was completed, and the solvent was removed by underpressure distillation and dried to obtain catalyst Cat-4, in which the Al content was 5.7 mmol / g and the Zr content was 37.5 micromol / g.

[0173] Embodiment 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 vacuum dried at 120°C for 10 hours. The treated carrier was added to a 250mL nitrogen-substituted multi-port reactor, and 25mL of 10% (mass percent) MAO (produced by PetroChina Lanzhou Chemical Research Center, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution was added, and stirred at room temperature for 1 hour. Then 0.19g (n-BuCp) 2ZrCl 2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL toluene were added, and stirred at 25°C for 3 hours. The reaction was terminated, and the solvent was removed by underpressure distillation and dried to obtain a catalyst Cat-5, in which the Al content was 5.3 mmol / g and the Zr content was 43.4 micromol / 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 vacuum dried at 120°C for 10 hours. The treated carrier was added to a 250mL nitrogen-substituted multi-port reactor, and 25mL of 10% (mass percentage) MAO (produced by PetroChina Lanzhou Chemical Research Center, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution was added, and stirred at room temperature for 1 hour. Then 0.19g (n-BuCp) 2HfCl2 (bis-n-butylcyclopentadienyl hafnium dichloride) metallocene compound and 10mL toluene were added, and stirred at 30°C for 3 hours. The reaction was terminated, and the solvent was removed by vacuum distillation and dried to obtain a catalyst Cat-6, in which the Al content of the catalyst was 6.0 mmol / g and the Hf content was 38.7 micromol / g.

[0179] Embodiment 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 vacuum dried at 120°C for 10 hours. The treated carrier was added to a 250mL nitrogen-substituted multi-port reactor, and 25mL of 10% (mass percentage) MAO (produced by PetroChina Lanzhou Chemical Research Center, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution was added, 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-benzoindenyl) zirconium dichloride] metallocene compound and 10mL toluene were added, and stirred at 25°C for 3 hours. The reaction was terminated, and the solvent was removed by vacuum distillation and dried to obtain the catalyst Cat-7, in which the Al content was 4.7 mmol / g and the Zr content was 51.2 micromol / g.

[0182] Embodiment 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 vacuum dried at 120°C for 10 hours. The treated carrier was added to a 250mL nitrogen-substituted multi-port reactor, and 25mL of 10% (mass percent) MAO (produced by Lanzhou Chemical Research Center of PetroChina, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution was added, and stirred at room temperature for 1 hour. Then 0.19g of En(Ind)2ZrCl2 ethylene-bridged bis-indenyl zirconium dichloride metallocene compound and 10mL toluene were added, and stirred at 25°C for 3 hours. The reaction was terminated, and the solvent was removed by underpressure distillation and dried to obtain a catalyst Cat-8, in which the Al content was 4.7 mmol / g and the Zr content was 39.8 micromol / g.

[0185] Embodiment 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 vacuum dried at 120°C for 10 hours. The treated carrier was added to a 250mL nitrogen-substituted multi-port reactor, and 25mL of 10% (mass percentage) MAO (produced by PetroChina Lanzhou Chemical Research Center, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution was added, and stirred at room temperature for 1 hour. Then 0.19g (n-BuCp) 2ZrCl 2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL toluene were added, and stirred at 25°C for 3 hours. The reaction was terminated, and the solvent was removed by vacuum distillation and dried to obtain the catalyst Cat-9, in which the Al content was 4.7 mmol / g and the Zr content was 41.9 micromol / g.

[0188] Embodiment 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 vacuum dried at 120°C for 10 hours. The treated carrier was added to a 250mL nitrogen-substituted multi-port reactor, and 25mL of 10% (mass percentage) MAO (produced by PetroChina Lanzhou Chemical Research Center, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution was added, and stirred at room temperature for 1 hour. Then 0.19g (n-BuCp) 2ZrCl 2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL toluene were added, and stirred at 25°C for 3 hours. The reaction was terminated, and the solvent was removed by vacuum distillation and dried to obtain the catalyst Cat-10, in which the Al content was 5.0 mmol / g and the Zr content was 48.3 micromol / g.

[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 vacuum dried at 120°C for 10 hours. The treated carrier was added to a 250mL nitrogen-substituted multi-port reactor, and 25mL of 10% (mass percentage) MAO (produced by PetroChina Lanzhou Chemical Research Center, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution was added, and stirred at room temperature for 1 hour. Then 0.19g (n-BuCp) 2ZrCl 2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL toluene were added, and stirred at 25°C for 3 hours. The reaction was terminated, and the solvent was removed by vacuum distillation and dried to obtain the catalyst Cat-11, in which the Al content was 4.3 mmol / g and the Zr content was 42.7 micromol / 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 vacuum dried at 120°C for 10 hours. The treated carrier was added to a 250mL nitrogen-substituted multi-port reactor, and 25mL of 10% (mass percentage) MAO (produced by PetroChina Lanzhou Chemical Research Center, with a trimethylaluminum TMA content of less than 0.2%, the same below) toluene solution was added, and stirred at room temperature for 1 hour. Then 0.19g (n-BuCp) 2ZrCl 2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10mL toluene were added, and stirred at 25°C for 3 hours. The reaction was terminated, and the solvent was removed by vacuum distillation and dried to obtain the catalyst Cat-12, in which the Al content was 4.6 mmol / g and the Zr content was 43.7 micromol / g.

[0197] Comparative Example 5

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

[0199] 5 g of Grace 955 silica gel was dried at 600°C for 8 hours to remove surface moisture and a large amount of hydroxyl groups, and then cooled to room temperature under nitrogen protection. The treated silica gel carrier was then added to a 250 mL nitrogen-substituted reactor, and 28 mL of 10% MAO (mass percentage, produced by PetroChina Lanzhou Chemical Research Center) toluene solution was added, stirred at 20°C for 1 hour, and then 0.2 g (n-BuCp) 2ZrCl2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound and 10 mL of toluene were added, stirred at 25°C for 3 hours, the reaction was terminated, the solvent was removed by reduced pressure distillation and dried to obtain catalyst Cat-13, the Al content in the catalyst was 5.1 mmol / g, and the Zr content was 43.7 μmol / g.

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

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

[0202] Ethylene homopolymerization: Add 2L of anhydrous hexane to a 5L polymerization reactor after nitrogen replacement and drying, add 5mL of triethylaluminum TEAL (10% hexane solution), add 0.2g of the above catalyst, replace the reactor with ethylene three times and maintain the pressure in the reactor at 1MPa, polymerize at 80°C for 1 hour, terminate the reaction, cool to room temperature, filter to remove the hexane and dry to obtain a polyethylene product.

[0203] Copolymerization of ethylene and α-olefin: 2L of anhydrous hexane was added to a 5L polymerization reactor after nitrogen replacement and drying, and 5mL of triethylaluminum TEAL (10% hexane solution), 30mL of 1-hexene, and 0.2g of the above catalyst were added in sequence. The reactor was replaced with ethylene three times and the pressure in the reactor was maintained at 1MPa. The polymerization was carried out at 80°C for 1 hour, the reaction was terminated, and the reaction was cooled to room temperature. The hexane was filtered out and dried to obtain the ethylene and hexene copolymer product.

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

[0205] Table 2 Olefin polymerization results

[0206] Test Case catalyst Ethylene homopolymerization activity g / (gcat·h) Ethylene-hexene copolymerization activity g / (gcat·h) 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] From the results of ethylene homopolymerization and copolymerization of ethylene and 1-hexene, it can be seen that the metallocene catalyst supported by the polyionic liquid containing trifluoroacetic acid ionic liquid of the present invention has a higher polymerization activity, which is higher than the porous organic polymer support functionalized with hydroxyethyl methacrylate and the porous organic polymer supported metallocene catalyst modified with 1-vinyl-3-butylimidazole chloride, and the polymerization activity is significantly higher than the inorganic silica gel support supported metallocene catalyst.

[0208] Test Example 14 Propylene Polymerization

[0209] 1.0 kg of dry propylene was added to a 10 L high-pressure polymerization reactor after nitrogen substitution and drying, and 20 mL of triethylaluminum (10% hexane solution) was added. After stirring for 10 minutes, 0.1 g of catalyst Cat-7 was added, and polymerization was carried out at 70°C for 1 hour. The reaction was terminated, 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 Copolymerization of ethylene and octene

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

Claims

1. A polyionic liquid carrier, which is obtained by copolymerizing monomers including divinylbenzene and functional monomers; The functional monomer is an ionic liquid comprising a cation and a trifluoroacetic acid anion, wherein the cation comprises an imidazolium cation and / or a pyridinium cation; The imidazolium cation has a structure shown in Formula I: In Formula I, X is C1-C 12 Alkylene and its derivatives, R is selected from C1-C 15 Alkyl and its derivatives, phenyl and its derivatives; The pyridinium cation has a structure shown in Formula II: In Formula II, Y is C1-C 12 Alkylene and its derivatives, R' is selected from C1-C 15 Alkyl and its derivatives, phenyl and its derivatives.

2. The polyionic liquid carrier according to claim 1, wherein In formula I, X is a C3-C6 alkylene group and its derivatives, and R is selected from CH3, C2H5, C3H7, C4H9, CH2C6H5, CH2CH2C6H5, CH2CH2CH2C6H5; Preferably, in formula II, Y is C3-C6 alkylene and its derivatives, and R' is selected from CH3, C2H5, C3H7, C4H9, CH2C6H5, CH2CH2C6H5, CH2CH2CH2C6H5.

3. The polyionic liquid carrier according to claim 1, wherein The functional monomer is selected from One or a combination of two or more.

4. The polyionic liquid carrier according to claim 1, wherein Taking the mass of the polyionic liquid carrier as 100%, the mass fraction of the functional monomer is 10%-50%, preferably 20%-40%; Preferably, the polyionic liquid carrier further comprises less than 60 wt % of additional monomers, based on the mass of the polyionic liquid carrier being 100 wt %; Preferably, the additional monomer includes one or a combination of two or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxypropyl acrylate.

5. A method for preparing a polyionic liquid carrier according to any one of claims 1 to 4, comprising the following steps: The polyionic liquid carrier is prepared by copolymerizing monomers including the divinylbenzene, the functional monomer and the additional monomer as raw materials; Preferably, the polyionic liquid carrier is prepared by dispersion polymerization, suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization; the dispersion polymerization method comprises the following steps: adding divinylbenzene, functional monomers, additional monomers into a dispersion solvent, then adding a template and an initiator, reacting at 50-80°C for 3-12 hours to obtain the polyionic liquid carrier.

6. The preparation method according to claim 5, wherein: The dispersing solvent is a C1-C4 alcohol or a mixture of a C1-C4 alcohol and ethylene glycol, and the mass ratio of the C1-C4 alcohol to ethylene glycol is 5-10:1; Preferably, the C1-C4 alcohol includes one or a combination of two or more of methanol, ethanol, propanol, isopropanol, 1-butanol, and isobutanol; Preferably, the template comprises polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer; Preferably, the weight average molecular weight of the template is 6000-12000; Preferably, the amount of the template added is 1-5% of the total mass of the monomer; Preferably, the initiator comprises azobisisobutyronitrile and / or dibenzoyl peroxide; Preferably, the amount of the initiator added is 1-5% of the total mass of the monomers; Preferably, the divinylbenzene is pretreated divinylbenzene, and the pretreatment is to remove the polymerization inhibitor.

7. A polyionic liquid carrier type metallocene catalyst system, comprising a polyionic liquid carrier, a co-catalyst, and a metallocene compound, wherein the polyionic liquid carrier is the polyionic liquid carrier according to any one of claims 1 to 4.

8. The polyionic liquid-supported metallocene catalyst system according to claim 7, wherein: The molar ratio of Al in the co-catalyst to the metal atom in the metallocene compound is 75-500, preferably 100-300; Preferably, the ratio of Al in the co-catalyst to the polyionic liquid carrier is 1 mmol Al / g carrier to 12 mmol Al / g carrier, more preferably 3 mmol Al / g carrier to 8 mmol Al / g carrier; Preferably, the ratio of the metal atom in the metallocene compound to the polyionic liquid carrier is 5 micromoles of metallocene / gram of carrier to 100 micromoles of metallocene / gram of carrier, more preferably 10 micromoles of metallocene / gram of carrier to 50 micromoles of metallocene / gram of carrier.

9. The polyionic liquid-supported metallocene catalyst system according to claim 7, wherein: The cocatalyst comprises an alkylaluminoxane; Preferably, the alkylaluminoxane comprises methylaluminoxane and / or alkyl-modified methylaluminoxane; Preferably, the alkylaluminoxane comprises methylaluminoxane.

10. The polyionic liquid-supported metallocene catalyst system according to claim 7, wherein: The general formula of the metallocene compound is Cp x MA y B z , wherein 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 a halogen atom, a hydrogen atom, an alkyl group, x, y, z are 0-3, and x, y, z cannot be 0 at the same time; Preferably, x+y+z=4, y+z≤3; Preferably, A and B are each independently selected from C1-C8 alkyl or chlorine; Preferably, when x=2, Cp is bridged by polymethylene or dialkylsilane; Preferably, M is zirconium, hafnium or titanium, 1≤x≤3, and Cp is selected from cyclopentadienyl, indenyl and its derivatives or fluorenyl and its derivatives substituted by C1-C6 straight alkyl groups; Preferably, the metallocene compound comprises one or a combination of two or more of bis(cyclopentadienyl)metal dihalide, bis(cyclopentadienyl)metal monoalkyl monohalide, bis(cyclopentadienyl)metal dialkyl compound, and bis(indenyl)metal dihalide; Preferably, the metallocene compound includes bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)hafnium dimethyl, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)hafnium dichloride, bis(n-butylcyclopentadienyl)zirconium dimethyl, bis(n-butylcyclopentadienyl)hafnium dimethyl, bis(dimethyl dimethyl zirconium, bis(tetramethylcyclopentadienyl)dimethyl hafnium, diindenyl zirconium dichloride, methylene-bridged diindenyl zirconium dichloride, bis(4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylene-bridged di(indenyl) zirconium dichloride, diindenyl hafnium dichloride, methylene-bridged diindenyl hafnium dichloride, bis(4,5,6,7-tetrachloro-1-indenyl) hafnium dichloride, ethylene-bridged di(indenyl) zirconium dichloride (Indenyl) 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( One or a combination of two or more of dimethylsilyl-bridged bis(2-methylindenyl) zirconium dimethyl, dimethylsilyl-bridged bis(2-methylindenyl) zirconium dichloride, dimethylsilyl-bridged bis(2-methylindenyl) hafnium dichloride, dimethylsilyl-bridged bis(2-methyl-benzoindenyl) zirconium dichloride, dimethylsilyl-bridged bis(2-methyl-benzoindenyl) zirconium dimethyl, and dimethylsilyl-bridged bis(2-methylindenyl) zirconium dimethyl.

11. A method for preparing a polyionic liquid-supported metallocene catalyst system according to any one of claims 7 to 10, comprising the following steps: Under anhydrous and oxygen-free conditions, the polyionic liquid carrier, the co-catalyst and the solvent are mixed, a metallocene compound is added, and the reaction is carried out at 0-40° C. for 60-180 minutes to obtain the polyionic liquid carrier type metallocene catalyst system; Preferably, the solvent includes one or a combination of two or more of aromatic hydrocarbons and their derivatives, ethers, cyclic ethers, esters, and alkanes, and more preferably toluene.

12. Use of the polyionic liquid-supported metallocene catalyst system according to any one of claims 7 to 10 in olefin polymerization; Preferably, the olefin polymerization is ethylene homopolymerization, propylene homopolymerization, ethylene and propylene copolymerization, ethylene and α-olefin copolymerization or propylene and α-olefin copolymerization; Preferably, the α-olefin includes one or a combination of two or more of butene, pentene, hexene, octene, and 4-methyl-1-pentene; Preferably, the olefin polymerization is gas phase polymerization, bulk polymerization or slurry polymerization; Preferably, the polymerization temperature is 30-120°C; the polymerization pressure is 0.5-1.5MPa; Preferably, the solvent for the slurry polymerization is C5-C 10 An alkane, more preferably hexane.

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