CN108997504B - Preparation method of ionic liquid functionalized cellulose carbamate material - Google Patents
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Abstract
The invention discloses a preparation method of an ionic liquid functionalized cellulose carbamate material, which comprises the following steps: 1) dissolving cellulose in ionic liquid, adding halogenated alkyl isocyanate for reaction to obtain a halogenated cellulose carbamate ester solution, and drying to obtain halogenated cellulose carbamate ester; 2) mixing and reacting halogenated cellulose carbamate with tertiary amine or tertiary phosphine to obtain chloride ionic liquid functionalized cellulose carbamate mixed solution; 3) adding C to the mixture1‑C3Obtaining halogen salt ionic liquid functionalized cellulose carbamate; 4) using halogen salt ionic liquid functionalized cellulose carbamate and salt as raw materials to carry out ion exchange, pouring the solution after ion exchange into C1‑C3Filtering, purifying and drying the lower fatty alcohol to obtain the ionic liquid functionalized cellulose carbamate containing different anions. The invention has the characteristics of simple preparation process and adjustable structure of the cellulose carbamate material.
Description
Technical Field
The invention relates to a preparation method of a cellulose carbamate material, in particular to a preparation method of an ionic liquid functionalized cellulose carbamate material.
Background
Ionic liquids possess unique and advantageous properties, such as: the ionic liquid has the advantages of low vapor pressure, non-volatility, non-flammability, large hot melting, good thermal stability, high ionic conductivity, wide electrochemical window and strong dissolving capacity, so that the ionic liquid is widely applied to many fields as a novel green solvent. In addition, the ionic liquid has good controllability, and the ionic liquid with rich structure and various functions can be obtained by selecting proper anions or adjusting structures of cations, so that the ionic liquid is regarded as a green designable solvent. However, in practical application, the ionic liquid has certain disadvantages, such as high price and difficult separation of products when being used as a solvent; when used as a catalyst, the catalyst is relatively difficult to recover. The appearance of the polyion liquid overcomes the limitation of the ionic liquid to a certain extent, and expands the application range of the polyion liquid. The polyionic liquid is a Polymer with cationic and anionic electrolyte groups on a repeating unit, not only has the characteristics of a high molecular material, but also keeps some special properties of the ionic liquid, and has recently become a research hotspot in the fields of heterogeneous catalytic materials (adv. Mater.2014,26, 6810-.
Polyionic liquids can be divided into: polycationic ionic liquid, polyanionic ionic liquid, polyamphoteric ionic liquid and copolymerization ionic liquid. Polyionic liquids can be prepared by two routes: (1) self-polymerization of ionic liquid monomers; (2) the ionic liquid is immobilized on the existing polymer. The method (1) is the most direct and simple method conceptually, and the polyion liquid is prepared by using a polymerizable ionic liquid monomer containing double bonds as a raw material and through a plurality of polymerization methods, so that the homopolymerized ionic liquid and the copolymerized ionic liquid can be obtained, wherein the polymerization methods comprise: free radical polymerization, atom transfer free radical polymerization, reversible addition fragmentation chain transfer, and the like. Green and the like take vinyl imidazole as raw materials to prepare a series of alkyl-substituted polyvinyl imidazole ionic liquids with different lengths through free radical polymerization, and the anion of the obtained polyvinyl imidazole ionic liquid is Br-And BF4 -(Macromol.Chem.Phys.2011,212:2522-2528)。
The approach (2) is to carry out chemical modification on the existing polymer and fix ionic liquid groups on a polymer carrier to obtain the corresponding polyion liquid, and the method can keep the characteristics of the polymer such as the specific macromolecular skeleton, the polymerization degree and the like and can also prepare the polyion liquid which cannot be synthesized by the approach (1). The polymer skeleton can be synthetic polymer, such as: polyethylene, polystyrene, silica, and the like. Morse and others are prepared on silicon dioxide (SiO) by Atom Transfer Radical Polymerization (ATRP)2) Surface grafting polymethacryloxyethyltrimethyltetrafluoroAmmonium borate (P [ MATMA ]][BF4]) The polyion liquid can be applied to supercritical carbon dioxide foaming (2011, 25, 6, 1039-. The invention patent with the application number of 2014103917099 discloses a preparation method and application of a polyvinyl alcohol immobilized ionic liquid 1-octyl-3-methylimidazole hexafluorophosphate adsorbing material, wherein the preparation method is a blending material obtained by directly mixing, heating and stirring polyvinyl alcohol, ionic liquid and sodium alginate, and the adsorbing material has good enrichment and recovery effects on low-concentration rare metals; has better removal effect on heavy metal ions in the wastewater.
Compared with synthetic polymers, natural polymers have unique properties including rich sources, biodegradability, low cost and good biocompatibility, so that polyion liquid prepared by taking natural polymers as carriers is favored by researchers. Cellulose is a natural polymer with the most abundant yield, and the ionic liquid functionalized fiber can be obtained by utilizing hydroxyl on a repeating unit of the cellulose to fixedly carry the ionic liquid on a cellulose framework through ether bonds. The invention patent with publication number CN 103497279A adopts an etherification method to obtain quaternized cellulose, firstly uses sodium hydroxide solution to treat the cellulose to obtain alkaline cellulose to realize hydroxyl activation, then uses 3-chlorine-2-hydroxypropyl trimethyl ammonium chloride as an etherification reagent to perform quaternization modification on the alkaline cellulose to obtain 2-hydroxypropyl trimethyl ammonium chloride functionalized cellulose, and the quaternized cellulose obtained after sulfonic acid treatment can be used for treating heavy metal ion wastewater and organic wastewater. Zhang Li Na and so on utilize low temperature sodium hydroxide/urea system to dissolve cellulose, under homogeneous phase conditions 3-chlorine-2-hydroxypropyl trimethyl ammonium chloride as etherification reagent to modify cellulose, through changing reaction conditions can obtain different degrees of substitution of ionic liquid functional cellulose material, and apply it in gene transfer, protein carrier and drug transfer. (Biomacromolecules 2008,9, 2259-. The method is characterized in that ionic liquid groups are linked to cellulose, and only chain ionic liquid functionalized cellulose can be obtained due to the limitation of an etherification reagent, and the structure is single. The invention patent with publication number CN 102580689A uses waste newspaper as raw material, after deinking, sodium hydroxide solution with mass concentration of 20% is stirred for 1-2 hours at normal temperature, and pH value is adjusted to be more than 13 to obtain turbid liquid, epichlorohydrin with mass 5-15 times of the waste newspaper is added into the turbid liquid, stirring is carried out for 6-8 hours at 60-70 ℃, solid-phase glycidyl etherified fiber is obtained by filtering, and finally the solid-phase glycidyl etherified fiber reacts with ethanol solution of triethylamine for 3-4 hours at 80-85 ℃ to obtain ionic liquid functionalized cellulose, and the cellulose functionalized material can be applied to anionic dye wastewater treatment. The steps for preparing the ionic liquid functionalized cellulose are relatively complicated, and only products with single structures can be obtained. The aminated cellulose material is prepared by using chlorinated cellulose as a raw material, and the literature reports that the chlorinated cellulose prepared by the method is used as the raw material by Silva Filho and the like, and is further reacted with ethylenediamine and ethylene sulfide or directly reacted with 2-aminopyridine, and the synthesized cellulose material can be used for adsorbing divalent metal ions in wastewater (carbon Polymer.2013, 921203-1210; Materials research.2013; 16(1): 79-87). Xihaibo et al uses cellulose as raw material, chloridizes the hydroxyl group at the 6 th position to obtain chlorinated cellulose, reacts with tertiary amine or tertiary phosphine under the condition of no solvent or solvent to obtain chloride salt ionic liquid functionalized cellulose material, further obtains ionic liquid functionalized cellulose material of different anions through ion exchange, and can be used in the aspects of catalyst, pH detection material, metal ion detection material, fluorescent material, etc. (patent numbers: 201510237943.0, RSC Advances,2015,5,44598-. However, the preparation of the related ionic liquid functionalized cellulose carbamate material by using the chlorinated cellulose as a raw material is not reported in documents and patents.
Disclosure of Invention
The invention aims to provide a preparation method of an ionic liquid functionalized cellulose carbamate material. The invention has the characteristics of simple preparation process and adjustable structure of the cellulose carbamate material.
The technical scheme of the invention is as follows: a preparation method of an ionic liquid functionalized cellulose carbamate material comprises the following steps:
1) dissolving cellulose in ionic liquid, adding halogenated alkyl isocyanate to react for 2-72 hours at 40-100 ℃ to obtain halogenated amino cellulose formate solution; after the reaction is finished, cooling to room temperature, separating out the product in a precipitation form by using pure water, washing and purifying, and freeze-drying to obtain halogenated cellulose carbamate;
2) mixing the halogenated cellulose carbamate prepared in the step 1) with tertiary amine or tertiary phosphine, and reacting for 2-72 hours at 50-150 ℃ to obtain chloride ionic liquid functionalized cellulose carbamate mixed solution;
3) adding C into the mixed solution prepared in the step 2)1-C3Precipitating, separating, washing and purifying the lower fatty alcohol to obtain halide salt ionic liquid functionalized cellulose carbamate;
4) taking the halide salt ionic liquid functionalized cellulose carbamate and salt prepared in the step 3) as raw materials, carrying out ion exchange by taking water or acetone as a solvent, and pouring the solution after ion exchange into a reactor C1-C3Then filtering, purifying and drying the solid mixture obtained by filtering to obtain the ionic liquid functionalized cellulose carbamate containing different anions.
In the preparation method of the ionic liquid functionalized cellulose carbamate material, in step 1), the cellulose is dissolved in the ionic liquid to prepare a solution with a mass concentration of 1-5%; the ionic liquid comprises one or a mixture of more than two of 1-allyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole chloride salt or 1-ethyl-3-methylimidazole acetate.
In the preparation method of the ionic liquid functionalized cellulose carbamate material, in step 1), the halogenated alkyl isocyanate includes one or a mixture of two or more of chloroethyl isocyanate, chloropropyl isocyanate, chlorobutyl isocyanate, bromoethyl isocyanate, bromopropyl isocyanate, bromobutyl isocyanate, iodoethyl isocyanate, iodopropyl isocyanate, or iodobutyl isocyanate.
In the preparation method of the ionic liquid functionalized cellulose carbamate material, in step 1), the specific chemical structural formula of the halogenated cellulose carbamate is as follows:
wherein 1< n <1500, 0< m <5, and the degree of substitution of the halogenated carbamate is 0.1-2.5.
In the preparation method of the ionic liquid functionalized cellulose carbamate material, in step 2), the molar ratio of the tertiary amine or tertiary phosphine to the halogenated cellulose carbamate ester is 2: 1-50: 1.
in the preparation method of the ionic liquid functionalized cellulose carbamate material, in step 2), the tertiary amine or tertiary phosphine is one or a mixture of two or more of the following structures:
in the preparation method of the ionic liquid functionalized cellulose carbamate material, in step 3), step C is1-C3The volume ratio of the lower aliphatic alcohol to the solution is 0.5-10: 1; said C1-C3The lower aliphatic alcohol is one or mixture of two or more of methanol, ethanol or isopropanol.
In the preparation method of the ionic liquid functionalized cellulose carbamate material, in the step 3), the structural formula of the prepared halide salt ionic liquid functionalized cellulose carbamate is as follows:
wherein takeDegree of substitution of 0.1-2.5, R2Is one of the following structures:
in the preparation method of the ionic liquid functionalized cellulose carbamate material, in step 4), the purification is performed by using C1-C3The lower fatty alcohol is prepared from the following functional cellulose carbamate according to the mass ratio of the lower fatty alcohol to the halogen salt ionic liquid: washing 1-5 times at the ratio of 1:1-100:1, and vacuum drying.
In the preparation method of the ionic liquid functionalized cellulose carbamate material, in step 4), halide salt ionic liquid functionalized cellulose carbamate and salt are used as raw materials, and ion exchange is performed by using water or acetone as a solvent, wherein the salt used in the preparation method comprises: NaBr, KBr, NaI, KI, CH3COONa、CH3COOK、HCOONa、HCOOK、CF3COONa、CF3COOK、F3CSO3Na、F3CSO3K、NaBF4、KBF4、NaPF6、KPF6、(F3CSO2)2NLi、FeCl3、FeBr3、ZnCl2、ZnBr2、InCl3、SbCl3One or a mixture of two or more of PdCl2, PtCl2, potassium salicylate, sodium salicylate and compounds with the following structural characteristics:
in the preparation method of the ionic liquid functionalized cellulose carbamate material, the molar ratio of the salt in the raw material to the halide salt ionic liquid functionalized cellulose carbamate is 1-5: 1.
in the preparation method of the ionic liquid functionalized cellulose carbamate material, in the step 4), the structural formula of the prepared ionic liquid functionalized cellulose carbamate containing different anions is as follows:
wherein
Is one or a mixture of two or more than two of the following structures:
wherein
Is one or a mixture of two or more than two of the following structures: cl-、Br-、I-、CH3COO-、HCOO-、CF3CSO3 -、BF4 -、PF6 -、(F3SO2)2N-、FeCl4 -、Fe2Cl7 -、FeBr3Cl-、Fe2Br6Cl-、Fe3Br9Cl-、ZnCl3 -、Zn2Cl5 -、Zn3Cl7 -、InCll4 -、In2Cl7 -、In3Cll0 -、SbCl4 -、Sb2Cl7 -、Sb3Cll0 -、
Based on the ionic liquid structure, the obtained ionic liquid functionalized cellulose material can be applied to different fields, such as catalytic materials, pH detection materials, metal ion detection materials, fluorescent materials and the like. We catalyze CO by using halogen salt ionic liquid functionalized cellulose as catalyst2The cycloaddition reaction with epoxy compound is a model application to illustrate the application potential of the ionic liquid functionalized cellulose prepared by the invention, and particularly, see example 10. The experimental result shows that under the same reaction condition, different halogen salt ionic liquid functionalized celluloses show different catalytic effects, and the catalytic effects are as shown in the specification I->Br->Cl-In turn, increases, which correlates with the nucleophilicity and leaving ability of the halide ion. The yield of cyclic carbonates decreases with decreasing catalyst usage under the same conditions (table 2, nos. 4-8); increasing the reaction temperature of the system increased the yield of cyclic carbonate (table 2, nos. 3, 8).
The invention has the advantages of
1. The preparation method disclosed by the invention is simple in preparation steps, convenient to process, easy to realize large-scale production and good in industrial popularization prospect.
2. The invention can obtain chain or ring structure ionic liquid functionalized cellulose by introducing different tertiary amine or tertiary phosphine.
3. The invention can obtain ionic liquid functionalized cellulose carbamate materials with different anions through room temperature ion exchange.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of methylimidazole chloride cellulose carbamate obtained under the condition of Table 1 No. 3 in example 1.
FIG. 2 is a nuclear magnetic carbon spectrum of methylimidazole chloride cellulose carbamate obtained under the condition of Table 1 No. 3 in example 1.
FIG. 3 is a carbamate infrared spectrum of methylimidazole chloride cellulose obtained under the condition of Table 1 No. 3 in example 2.
FIG. 4 is a thermogravimetric analysis chart of the methylimidazole chloride cellulose carbamate obtained under the condition of Table 1 No. 3 in example 2.
FIG. 5 is a DSC chart of carbamate of methylimidazole chloride cellulose obtained under the condition of Table 1 No. 3 in example 2.
FIG. 6 is a nuclear magnetic carbon spectrum of methylimidazole chloride cellulose carbamate obtained under the condition of Table 1 No. 3 in example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Examples of the invention
Example 1:
10 g of dried 1-allyl-3-methylimidazolium chloride (AmimCl) was added to a 100ml two-necked flask, 0.5g of microcrystalline cellulose was added thereto, and the mixture was mechanically stirred at 80 ℃ for 2 hours to obtain a homogeneous transparent cellulose solution. Adding a certain amount of 2-chloroethyl isocyanate under mechanical stirring at 80 ℃, and continuously reacting for a certain time. After the reaction is finished, cooling to room temperature, precipitating the product by pure water, grinding the precipitate, stirring for a period of time, filtering, and washing with water for three times. After suction filtration, a small amount of water is added to the solid matter, and the mixture is frozen and dried for 48 hours.
The degree of substitution was controlled by varying the reaction temperature and reaction time, and the results are shown in table 1:
TABLE 1 cellulose chloroacetcarbamates prepared under different conditionsa
aThe experimental conditions are as follows: the cellulose concentration was 5 wt%.bThe molar ratio of 2-chloroethyl isocyanate to hydroxyl groups.c"+" indicates dissolution and "-" indicates no dissolution.
Example 2:
10 g of dried 1-allyl-3-methylimidazolium chloride (AmimCl) was added to a 100ml two-necked flask, 0.5g of microcrystalline cellulose was then added thereto, and the mixture was mechanically stirred at 80 ℃ for 2 hours to obtain a homogeneous transparent cellulose solution. 2.375 ml of 3-chloropropyl isocyanate (molar ratio to hydroxyl: 2.5:1) was added at 80 ℃ with mechanical stirring and reacted for 24 hours. After the reaction is finished, cooling to room temperature, precipitating the product by pure water, grinding the precipitate, stirring for a period of time, filtering, and washing with water for three times. After suction filtration, a small amount of water is added to the solid matter, and the mixture is frozen and dried for 48 hours.
Example 3
Adding 1 g of chloroacetic amino cellulose ester into a 100ml two-neck flask, adding 20 ml of DMSO (dimethyl sulfoxide) for dissolving, then adding 5 ml of N-methylimidazole, heating to 100 ℃, mechanically stirring and refluxing for 48 hours, separating out a precipitate by using 3 times of volume of anhydrous methanol after the reaction is finished, washing the filtered precipitate product three times by using 20 times of anhydrous methanol, and carrying out vacuum drying at 60 ℃ for 24 times to obtain 1.6 g of a product.
Example 4
2 g of chloroacetic amino cellulose ester and 50 ml of pyridine are added into a 100ml two-neck flask, the mixture is placed in a 100 ℃ oil bath kettle and mechanically stirred and refluxed for 4 hours, 10 times of volume of absolute ethyl alcohol is used for precipitation after the reaction is finished, the product obtained after filtration is washed for 5 times by 50 times of absolute ethyl alcohol, and the product is dried in vacuum for 24 hours at 60 ℃ to obtain 2.6 g of product.
Example 5
2 g of chloroacetic amino cellulose ester and 60 ml of triethylamine are added into a 100ml two-neck flask, the mixture is placed into a 50 ℃ oil bath kettle and mechanically stirred and refluxed for 12 hours, after the reaction is finished, isopropanol with the same volume is used for separating out and precipitating, products obtained through filtration are washed for 1 time by using 100 times of isopropanol, and the products are dried for 24 hours in vacuum at 60 ℃ to obtain 2.2 g of products.
Example 6
Weighing 1 g of methylimidazole chloride cellulose carbamate, dissolving in 20 ml of water, adding 40 g of sodium iodide, stirring at room temperature for 24 hours, pouring into 5 times of absolute ethyl alcohol to separate out a precipitate, washing the precipitate with the absolute ethyl alcohol for three times, and drying in vacuum at 60 ℃ for 24 hours to obtain 2.3 g of a product.
Example 7
Weighing 1 g of methylimidazole chloride cellulose carbamate, dissolving in 20 ml of water, adding 19 g of sodium bromide, stirring at room temperature for 24 hours, pouring into 5 times of anhydrous methanol to separate out a precipitate, washing the precipitate with anhydrous methanol for 5 times, and drying under vacuum at 60 ℃ for 24 hours to obtain 0.83 g of a product.
Example 8
Weighing 1 g of methylimidazole chloride cellulose carbamate, dispersing in 20 ml of acetone, adding 5g of zinc chloride, stirring at room temperature for 24 hours, pouring into 5 times of absolute ethyl alcohol to separate out a precipitate, washing the precipitate with the absolute ethyl alcohol for three times, and drying in vacuum at 60 ℃ for 24 hours to obtain 1.23 g of a product.
Example 9
Weighing 1 g of methylimidazole chloride cellulose carbamate and dissolving the methyl imidazole chloride cellulose carbamate in 20 ml of water, adding 12 g of direct ash D, stirring the mixture at room temperature for 24 hours, pouring the mixture into 5 times of absolute ethyl alcohol to separate out a precipitate, washing the precipitate with the absolute ethyl alcohol for three times, and drying the precipitate in vacuum at 60 ℃ for 24 hours to obtain 2.85 g of a product.
Example 10
Applying methylimidazole halide salt cellulose as a catalyst in a cyclization reaction of carbon dioxide in an epoxy compound:
adding phenyl glycidyl ether (20mmol) and a catalyst methyl imidazolium cellulose carbamate (1mmol) into a 100mL high-pressure reaction kettle, introducing carbon dioxide to stabilize to 2MPa, placing the mixture in an oil bath kettle at 120 ℃ for reaction for 6 hours, cooling the mixture by using an ice water bath after the reaction is finished, slowly releasing redundant carbon dioxide, washing the bottom of the kettle and precipitating by using ethyl acetate, collecting an organic phase, removing the ethyl acetate by rotary evaporation, and separating by using column chromatography to obtain a target product, wherein the results are shown in Table 2:
TABLE 2 Methylimidazolium halide cellulose carbamate catalyzed carbon dioxide to cyclic carbonate
Claims (10)
1. A preparation method of an ionic liquid functionalized cellulose carbamate material is characterized by comprising the following steps:
1) dissolving cellulose in ionic liquid, adding halogenated alkyl isocyanate to react for 2-72 hours at 40-100 ℃ to obtain halogenated amino cellulose formate solution; after the reaction is finished, cooling to room temperature, separating out the product in a precipitation form by using pure water, washing and purifying, and freeze-drying to obtain halogenated cellulose carbamate;
2) mixing the halogenated cellulose carbamate prepared in the step 1) with tertiary amine or tertiary phosphine, and reacting for 2-72 hours at 50-150 ℃ to obtain chloride ionic liquid functionalized cellulose carbamate mixed solution;
3) adding C into the mixed solution prepared in the step 2)1-C3Precipitating, separating, washing and purifying the lower fatty alcohol to obtain a halide salt ionic liquid functionalized cellulose carbamate material;
4) taking the halide salt ionic liquid functionalized cellulose carbamate and salt prepared in the step 3) as raw materials, carrying out ion exchange by taking water or acetone as a solvent, and pouring the solution after ion exchange into a reactor C1-C3Then filtering the lower aliphatic alcohol, purifying and drying a solid mixture obtained by filtering to obtain ionic liquid functionalized cellulose carbamate containing different anions;
in the step 1), the cellulose is dissolved in ionic liquid to prepare a solution with the mass concentration of 1-5%; the ionic liquid comprises one or a mixture of more than two of 1-allyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole chloride salt or 1-ethyl-3-methylimidazole acetate;
in the step 2), the molar ratio of the tertiary amine or tertiary phosphine to the halogenated cellulose carbamate is 2: 1-50: 1.
2. the method for preparing an ionic liquid functionalized cellulose carbamate material according to claim 1, wherein: in the step 1), the halogenated alkyl isocyanate comprises one or a mixture of more than two of chloroethyl isocyanate, chloropropyl isocyanate, chlorobutyl isocyanate, bromoethyl isocyanate, bromopropyl isocyanate, bromobutyl isocyanate, iodoethyl isocyanate, iodopropyl isocyanate or iodobutyl isocyanate.
3. The method for preparing an ionic liquid functionalized cellulose carbamate material according to claim 1, wherein: in the step 1), the specific chemical structural formula of the halogenated cellulose carbamate is as follows:
wherein 1< n <1500, 0< m <5, and the degree of substitution of the halogenated carbamate is 0.1-2.5.
4. The method for preparing an ionic liquid functionalized cellulose carbamate material according to claim 1, wherein: in the step 2), the tertiary amine or tertiary phosphine is one or a mixture of two or more of the following structures:
5. the method for preparing an ionic liquid functionalized cellulose carbamate material according to claim 1, wherein: in step 3), the C1-C3The volume ratio of the lower aliphatic alcohol to the solution is 0.5:1-10: 1; said C1-C3The lower aliphatic alcohol is methanol, ethanol orOne or a mixture of two or more of isopropyl alcohol.
6. The method for preparing an ionic liquid functionalized cellulose carbamate material according to claim 1, wherein: in the step 3), the structural formula of the prepared halide salt ionic liquid functionalized cellulose carbamate is as follows:
wherein the degree of substitution is from 0.1 to 2.5, R2Is one of the following structures:
7. the method for preparing an ionic liquid functionalized cellulose carbamate material according to claim 1, wherein: in step 4), the purification is carried out by using C1-C3The mass ratio of the lower aliphatic alcohol to the halogen salt ionic liquid functionalized cellulose carbamate is 1:1-100:1 amount is washed 1-5 times and then dried in vacuum.
8. The method for preparing an ionic liquid functionalized cellulose carbamate material according to claim 1, wherein: in the step 4), the halide salt ionic liquid functionalized cellulose carbamate and salt are used as raw materials, and ion exchange is carried out by using water or acetone as a solvent, wherein the used salt comprises: NaBr, KBr, NaI, KI, CH3COONa、CH3COOK、HCOONa、HCOOK、CF3COONa、CF3COOK、F3CSO3Na、F3CSO3K、NaBF4、KBF4、NaPF6、KPF6、(F3CSO2)2NLi、FeCl3、FeBr3、ZnCl2、ZnBr2、InCl3、SbCl3、PdCl2、PtCl2Potassium salicylate, sodium salicylate and compounds having the following structural features:
9. the method for preparing an ionic liquid functionalized cellulose carbamate material according to claim 8, wherein: the molar ratio of the salt to the halide ionic liquid functionalized cellulose carbamate in the raw materials is 1-5: 1.
10. the method for preparing an ionic liquid functionalized cellulose carbamate material according to claim 1, wherein: in the step 4), the structural formula of the prepared ionic liquid functionalized cellulose material containing different anions is as follows:
wherein
Is one or a mixture of two or more than two of the following structures:
wherein
Is one or a mixture of two or more than two of the following structures: cl-、Br-、I-、CH3COO-、HCOO-、CF3CSO3 -、BF4 -、PF6 -、(F3SO2)2N-、FeCl4 -、Fe2Cl7 -、FeBr3Cl-、Fe2Br6Cl-、Fe3Br9Cl-、ZnCl3 -、Zn2Cl5 -、Zn3Cl7 -、InCll4 -、In2Cl7 -、In3Cll0 -、SbCl4 -、Sb2Cl7 -、Sb3Cll0 -、
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