CN115838495B - Self-supporting covalent cross-linking functional polyelectrolyte porous membrane and preparation method and application thereof - Google Patents
Self-supporting covalent cross-linking functional polyelectrolyte porous membrane and preparation method and application thereof Download PDFInfo
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Abstract
A self-supporting covalent cross-linking functional polyelectrolyte porous membrane and a preparation method and application thereof belong to the field of functional membrane materials. The invention firstly prepares amino functional polyion liquid, obtains a polymer film by utilizing an industrial mature knife coating technology, then is soaked into a mixed reaction solution formed by a 1, 2-dicarbonyl compound-aldehyde compound and acid, and can prepare the covalent crosslinking functional polyelectrolyte porous membrane with high charge density in one step under the condition of room temperature. The covalent cross-linked polyionic liquid porous membrane has controllable thickness, pore diameter, mechanical property and designable structure and shape. The method can realize the large-scale preparation of the covalent cross-linking functional polyelectrolyte porous membrane under the room temperature condition. The self-supporting covalent cross-linked polyionic liquid porous membrane prepared by the invention has excellent chemical and thermal stability and has wide practical application prospect in the energy fields of sea water desalination, lithium-magnesium separation and the like.
Description
Technical Field
The invention belongs to the field of functional membrane materials, and particularly relates to a self-supporting covalent cross-linking functional polyelectrolyte porous membrane, and a preparation method and application thereof.
Background
Polyelectrolyte Porous Membrane (PPM) has great application prospect in the fields of adsorption separation, lubrication, optics, nano electronic devices, energy storage and the like due to pore effect and charge characteristic. However, it is difficult to prepare a high-quality polyelectrolyte porous membrane by the current industry-established phase separation method due to its water solubility. Thus, for nearly two centuries, researchers have made great efforts to find a reliable film preparation technique that achieves high quality PPM in the industry.
The mass preparation method of the polyelectrolyte porous membrane developed at present mainly comprises a layer-by-layer self-assembly (LBL), an electrostatic crosslinking method and a hydrogen bond supermolecule crosslinking method, and a Part of PPM (PPM) for preparing the LBL has been industrialized. However, the PPM prepared by the methods has poor structural stability, holes are dissociated in a high-salt or thermal environment, the application prospect is greatly limited, and the preparation process of the LBL is extremely time-consuming and labor-consuming. Therefore, a PPM which can be prepared in a large scale and has good heat resistance and solvent resistance is developed, and the PPM has great significance and application value.
The polyionic liquid is a novel functional polyelectrolyte developed in recent years, has the excellent characteristics of the ionic liquid and the solution processability of a polymer, and has good application prospect in the field of membrane science.
Disclosure of Invention
The invention aims to solve the problems of labor consumption, time consumption, salt/thermal instability of a prepared PPM structure and the like of the conventional polyelectrolyte porous membrane synthesis method, and provides a preparation method of a self-supporting covalent crosslinking functional polyelectrolyte porous membrane with low cost, easy obtainment, easy large-scale preparation, designable and adjustable pore diameter, structure and mechanical property and high charge density and structural stability. The functional polyelectrolyte porous membrane can be prepared in one step in an aqueous solution system at normal temperature and normal pressure, and can realize industrial large-scale preparation. Provides a technical support for extracting metal lithium from seawater under the conditions of environmental protection and low energy consumption.
The technical scheme of the invention is as follows:
a method for preparing a self-supporting covalent cross-linking functional polyelectrolyte porous membrane, comprising the following steps:
(1) Preparation of amino-containing ionic liquid monomer: mixing amino-containing halogenated compound, vinyl-containing compound and good solvent in a proportion of 1mol: (0.5-2) mol: (10-1000 ml) mixing, stirring for 2-48 h at 30-90 ℃ under nitrogen or inert gas atmosphere to carry out quaternization reaction, and then recrystallizing in poor solvent to obtain the amino-containing ionic liquid monomer;
(2) Preparation of amino-containing hydrophobic one-component polyionic liquid homopolymer: mixing the amino-containing ionic liquid monomer prepared in the step (1), azodiisobutyronitrile and 75% ethanol aqueous solution according to the mass ratio of 1: (0.01-0.1): (10-100), stirring for 12-72 h at 60-100 ℃ under nitrogen or inert gas atmosphere, removing solvent by rotary evaporation, washing and drying by diethyl ether, adding sodium hydroxide solution to adjust pH to 9-10, dialyzing the obtained solution for 2-5 days, and adding hydrophobic anion lithium salt (wherein the molar ratio of the amino-containing ionic liquid monomer to the hydrophobic anion lithium salt is 1 (1-10)), thus obtaining the amino-containing hydrophobic single-component polyionic liquid homopolymer;
(3) Preparing a mixed reaction solution: adding a 1, 2-dicarbonyl compound and an aldehyde compound into an aqueous solution of 5-50% of acid by mass percent, and heating and dissolving at 25-70 ℃ to obtain a mixed reaction solution;
(4) Preparing a polyion liquid film: mixing the hydrophobic single-component polyionic liquid homopolymer obtained in the step (2) with dimethylformamide or dimethyl sulfoxide according to the proportion of 1g: (1-50) ml, stirring and dissolving at 25-70 ℃ to prepare a polymer solution, scraping the polymer solution on a glass plate by using an industrial film scraping machine, heating at 50-120 ℃ for 2-48 hours, and drying the solvent to obtain the polyion liquid film with the matrix;
(5) Preparation of self-supporting covalent cross-linking functional polyelectrolyte porous membranes: soaking the polyion liquid film prepared in the step (4) into the mixed reaction solution prepared in the step (3), and reacting for 1-48 h at the temperature of 0-80 ℃ to obtain the self-supporting covalent cross-linking functional polyelectrolyte porous film.
Preferably, the amino-containing halogenated compound is:
the vinyl-containing compound is
The good solvent is one or more of methanol, acetone, tetrahydrofuran, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, sulfolane, dioxane, hydroxy propionic acid, ethylamine, ethylenediamine, glycerol, diethylene glycol dimethyl ether, 1, 3-dioxolane, pyridine, formamide, acetonitrile, propanol or isopropanol;
the poor solvent is one or more of ethanol, acetone, diethyl ether, dioxane, diethylene glycol dimethyl ether, 1, 3-dioxolane, pyridine, propanol or isopropanol;
the amino-containing hydrophobic single-component polyionic liquid homopolymer is as follows:
the hydrophobic anion lithium salt is
CF 3 SO 3 Li、(CF 3 SO 2 ) 2 NLi or (CF) 3 CF 2 SO 2 ) 2 NLi；
Wherein R' is R is alkyl with 0-18 carbon atoms; n is an integer of 10 to 1000; m is an integer of 1 to 18; x is Cl, br or I; x' is X, (-) -X> ClO 4 、BF 4 、PF 6 、CF 3 SO 3 、(CF 3 SO 2 ) 2 N or (CF) 3 CF 2 SO 2 ) 2 N; x' is->
CF 3 SO 3 、(CF 3 SO 2 ) 2 N or (CF) 3 CF 2 SO 2 ) 2 N。
Preferably, the 1, 2-dicarbonyl compound is
The aldehyde compound is
Formaldehyde, 2, 4-dihydroxybenzaldehyde, 3, 4-dihydroxybenzaldehyde, 2-imidazolecarboxaldehyde, 5-methylimidazole-4-carbaldehyde, D-glyceraldehyde, L-glyceraldehydeOlein, DL-glyceraldehyde, D-erythrose, L-erythrose, DL-erythrose, D-threose, L-threose, DL-threose, D-ribose, L-ribose, DL-ribose, D-xylose, L-xylose, DL-xylose, D-lyxose, L-lyxose, DL-lyxose, D-allose, L-allose, DL-allose, D-altrose, L-altrose, DL-altrose, D-glucose, L-glucose, D/L-glucose, D-mannose, L-manno, D/L-mannose, D-gulose, L-gulose, D/L-gulose, D-idose, L-idose, D/L-idose, D-galactose, L-galactose, D/L-galactose, D-idose, L-talose, D/L-arabinose, D-arabino, D-lactone, D-arabino, D-glucose, D-gulonolactone, D-6-glucolactone or D-6-glucolactone;
the acid includes acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrobromic acid, and boric acid;
wherein R is 1 Is H, C1-18 alkyl,R 2 Is C1-18 alkyl; r is R 3 Is H, C1-18 alkyl, -/-, and/or>R 4 Is C1-18 alkyl, -OH, -COOH, -CO 2 Et、-OCH 3 、-NO 2 、-SO 3 H、-B(OH) 2 、-N(CH 3 ) 2 -F, -Cl, -Br, -I or-H; m is Co, cu, ni, zn, cr, fe, pt, mn, mg, al or Ca.
Preferably, the water solution of the hydrophobic single-component polyionic liquid homopolymer, the 1, 2-dicarbonyl compound, the aldehyde compound and the acid with the mass fraction of 5-50% is used in the following ratio of (0.02-2) mol:1mol:1mol: (500-10000) ml.
The invention also provides the self-supporting covalent cross-linking functional polyelectrolyte porous membrane prepared by the method, which has a covalent cross-linking three-dimensional interpenetrating multi-level pore structure with good chemical stability and thermal stability, the pore diameter is 10 nm-10 mu m, and the thickness is 20 nm-1 cm.
The invention also provides application of the covalent cross-linking functional polyelectrolyte porous membrane obtained by the preparation method in ion separation.
The invention has the advantages and positive effects that:
compared with the problems of harsh reaction conditions, complex post-treatment, salt/thermal instability and the like in the traditional polyionic liquid porous membrane preparation, the invention provides a preparation method of a self-supporting covalent crosslinking polyionic liquid porous membrane material with low cost, easy acquisition, easy large-scale preparation, design-adjusted pore diameter, structure and mechanical property, good thermal stability and chemical stability and application of the self-supporting covalent crosslinking polyionic liquid porous membrane material in ion separation. The covalent cross-linked polyionic liquid porous membrane prepared by the method is prepared by one-step reaction in water solution at normal temperature and normal pressure, and is expected to be applied in a large scale.
Drawings
FIG. 1 is a process for preparing a self-supporting cross-linked functional polyelectrolyte porous membrane: immersing the polyion liquid film and the matrix into a mixed reaction solution of a 1, 2-dicarbonyl compound, an aldehyde compound and an aqueous solution of 5-50% of acid by mass percent, and obtaining a self-supporting cross-linked functional polyelectrolyte porous film physical diagram after the reaction is completed;
FIG. 2 is a scanning electron micrograph of cross-sections (a) low magnification and (b) high magnification of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 1;
FIG. 3 is a schematic representation of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 2;
FIG. 4 is a scanning electron micrograph of cross-sections (a) low magnification and (b) high magnification of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 2;
FIG. 5 is a schematic representation of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 3;
FIG. 6 is a scanning electron micrograph of cross-sections (a) low magnification and (b) high magnification of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 3;
FIG. 7 is a schematic representation of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 4;
FIG. 8 is a scanning electron micrograph of cross-sections (a) low magnification and (b) high magnification of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 4;
FIG. 9 is a schematic representation of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 5;
FIG. 10 is a scanning electron micrograph of cross-sections (a) low magnification and (b) high magnification of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 5;
FIG. 11 is a schematic representation of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 6;
FIG. 12 is a scanning electron micrograph of cross-sections (a) low magnification and (b) high magnification of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 6;
FIG. 13 is a schematic representation of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 7;
FIG. 14 is a scanning electron micrograph of cross-sections (a) low magnification and (b) high magnification of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 7;
FIG. 15 is a thermogravimetric analysis of the self-supporting cross-linked functional polyelectrolyte porous membranes prepared in examples 1-4;
FIG. 16 is a photograph of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 1 after being immersed in dimethyl sulfoxide, dimethylformamide, ethanol, 1mol/L sodium chloride solution, acetonitrile, acidic and basic aqueous solutions for 7 days;
FIG. 17 is an infrared spectrum of the membrane after soaking treatment with different solvents, and no obvious spectrum change is compared with the original membrane, which shows that the self-supporting crosslinked polyelectrolyte porous membrane prepared by the invention has good chemical stability;
FIG. 18 is a physical view of a self-supporting cross-linked functional polyelectrolyte porous membrane and bending thereof;
FIG. 19 is a photograph of a device for electrically driven ion separation of a self-supporting cross-linked functional polyelectrolyte porous membrane;
FIG. 20 is a graph showing the conductivity change for various ionic solutions in comparison to the membrane-free state for the self-supporting crosslinked functional polyelectrolyte porous membranes prepared in examples 1-3.
Detailed Description
Compared with the traditional preparation of the covalent cross-linking functional polyelectrolyte porous membrane under severe reaction conditions, complicated preparation process and relatively single chemical structure, the preparation method of the covalent cross-linking functional polyelectrolyte porous membrane provided by the invention is low in cost, easy to obtain, easy to prepare in a large scale and mild in reaction conditions, and the prepared covalent cross-linking functional polyelectrolyte porous membrane has adjustable chemical structure, pore diameter, thickness and mechanical property by changing the composition of a polymer and a mixed solution, and in addition, the prepared covalent cross-linking functional polyelectrolyte porous membrane has excellent chemical stability and thermal stability due to the covalent cross-linking polymer network.
The following description and drawings of the preferred embodiments are illustrative of and assist in further understanding the invention, but the details of the embodiments are merely for the purpose of illustrating the invention and do not represent all the technical solutions under the inventive concept and therefore should not be construed as limiting the general technical solutions of the invention. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention, such as by changing or substituting the technical features that have the same or similar technical effects.
In some embodiments, the halogenated compound is preferably: x (CH) 2 ) m NH 2 、X(CH 2 CH 2 O) m NH 2 、
In some embodiments, the vinyl-containing compound is preferably
In some embodiments, the amino-containing hydrophobic one-component polyionic liquid homopolymer is preferably:
wherein R' is preferably- (CH) 2 ) m NH 2 、-(CH 2 CH 2 O) m NH 2 、R is preferably-CH 3 The method comprises the steps of carrying out a first treatment on the surface of the n is preferably an integer from 100 to 500; m is preferably an integer from 1 to 3; x is preferably Br; x' is preferably Br; x' is preferably->PF 6 、CF 3 SO 3 、(CF 3 SO 2 ) 2 N or (CF) 3 CF 2 SO 2 ) 2 N。
In some embodiments, the good solvent is preferably acetonitrile and the poor solvent is preferably ethanol.
In some embodiments, the hydrophobic anionic lithium salt is preferably PF 6 Li、CF 3 SO 3 Li、(CF 3 SO 2 ) 2 NLi or (CF) 3 CF 2 SO 2 ) 2 NLi。
In some embodiments, the 1, 2-dicarbonyl compound is preferably glyoxal,
In some embodiments, the aldehyde compound is preferably formaldehyde, 2, 4-dihydroxybenzaldehyde, 3, 4-dihydroxybenzaldehyde, terephthalaldehyde, benzaldehyde, D-glyceraldehyde, 2-imidazole-formaldehyde, D-arabinose, D-glucuronic acid-3, 6-lactone, or p-dimethylaminobenzaldehyde.
The acid is preferably acetic acid.
The invention also provides application of the self-supporting covalent cross-linking functional polyelectrolyte porous membrane in ion separation.
In the present invention, the application preferably includes the steps of: and (3) sandwiching the self-supporting covalent cross-linking functional polyelectrolyte porous membrane between two chambers of an electrolytic cell, testing a current-voltage curve under the condition of externally applied voltage, obtaining electric conductance by calculating the slope of the current-voltage curve, and evaluating the ion separation effect of the membrane by comparing the change rate of the solution electric conductance under the membrane-containing state and the membrane-free state. In the invention, the ionic liquid is charged, and the covalent cross-linked functional polyelectrolyte porous membrane has good thermal stability and chemical stability, so that the selective separation of ions is expected to be realized through the electrostatic repulsive interaction of high-valence ions in the solution and positively charged pore walls.
Example 1,
Preparation of Poly (4-aminopropyl-1-vinyl-1, 2, 4-triazole bistrifluoromethylsulfonylimine salt) ionic liquid/3, 4-dihydroxybenzaldehyde/methylglyoxal crosslinked functional polyelectrolyte porous membrane, as shown in FIG. 2, the self-supporting covalent crosslinked polyelectrolyte porous membrane has a three-dimensional interpenetrating porous structure, a pore diameter of 120nm and a membrane thickness of 70 μm, and the preparation method comprises the following steps:
(1) 9.5g of 1-vinyl-1, 2, 4-triazole, 21.9g of bromopropylamine hydrobromide, 0.1g of 2, 6-di-tert-butyl 4-methylphenol and 50ml of acetonitrile were placed in a 250ml flask. And reacting for 24 hours at 80 ℃ to obtain the ionic liquid monomer.
(2) 10g of the ionic liquid monomer prepared in the step (1) is dissolved in 200mL of ethanol/water=3:1 (v/v), 0.3g of azobisisobutyronitrile is added, and the reaction is carried out at 80 ℃ for 48 hours, thus obtaining a hydrophilic single-component polyionic liquid homopolymer.
(3) Dissolving 5g of the hydrophilic single-component polyionic liquid homopolymer prepared in the step (2) in 20ml of water, adding NaOH to adjust the pH to 9-10, dialyzing the solution for two days, and adding 10ml of 6g of lithium bis (trifluoromethylsulfonyl) imide aqueous solution to obtain the hydrophobic single-component polyionic liquid homopolymer.
(4) 1g of the hydrophobic single-component polyionic liquid homopolymer prepared in the step (3) is dissolved in 10mL of dimethylformamide, the solution is coated on a glass plate by using an industrial film scraping machine, the solution is heated for 5 hours at 80 ℃, and the solvent is dried, so that the polyionic liquid film is obtained.
(5) 2.2ml of a 40% aqueous solution of methylglyoxal, 1.65g of 3, 4-dihydroxybenzaldehyde and 60ml of a 25% aqueous solution of acetic acid were mixed and dissolved by stirring at 30℃to obtain a mixed reaction solution.
(6) As shown in fig. 1, the polyion liquid film prepared in the step (4) is soaked into the mixed reaction solution prepared in the step (5) to react for 2 hours at 25 ℃ to obtain the poly (4-aminopropyl-1-vinyl-1, 2, 4-triazole bis (trifluoromethyl) sulfonyl imide salt) ionic liquid/3, 4-dihydroxybenzaldehyde/methylglyoxal crosslinked functional polyelectrolyte porous membrane.
EXAMPLE 2,
Preparation of poly (4-aminopropyl-1-vinyl-1, 2, 4-triazole bistrifluoromethylsulfonylimide salt) ionic liquid/formaldehyde/methylglyoxal crosslinked functional polyelectrolyte porous membranes, the difference from the self-supporting covalent crosslinked polyelectrolyte porous membranes of example 1 is: as shown in fig. 4, the pore diameter was 90nm and the membrane thickness was 150 μm, and the preparation of the self-supporting covalently crosslinked polyelectrolyte porous membrane was different from the preparation method of example 1 in that: in step 5, "1.65g of 3, 4-dihydroxybenzaldehyde, 60ml of 25% by mass aqueous acetic acid solution were mixed" to 1ml of 37% by mass aqueous formaldehyde solution, 60ml of 10% by mass aqueous acetic acid solution were mixed "; in step 6, as shown in FIG. 3, a poly (4-aminopropyl-1-vinyl-1, 2, 4-triazole bistrifluoromethylsulfonylimide salt) ionic liquid/formaldehyde/methylglyoxal crosslinked functional polyelectrolyte porous membrane is obtained.
EXAMPLE 3,
Preparation of poly (4-aminoethyl-1-vinyl-1, 2, 4-triazole bistrifluoromethylsulfonylimide salt) ionic liquid/3, 4-dihydroxybenzaldehyde/methylglyoxal crosslinked functional polyelectrolyte porous membranes, the difference from the self-supporting covalent crosslinked polyelectrolyte porous membranes of example 1 is: as shown in fig. 6, the pore diameter was 250nm and the membrane thickness was 60 μm, and the preparation of the self-supporting covalently crosslinked polyelectrolyte porous membrane was different from the preparation method of example 1 in that: in step 1, "21.9g of bromamine hydrobromide" was changed to "20.5g of bromamine hydrobromide"; in step 6, as shown in FIG. 5, a poly (4-aminopropyl-1-vinyl-1, 2, 4-triazole bistrifluoromethylsulfonylimide salt) ionic liquid/3, 4-dihydroxybenzaldehyde/methylglyoxal crosslinked functional polyelectrolyte porous membrane is obtained.
EXAMPLE 4,
Preparation of poly (4-aminoethyl-1-vinyl-1, 2, 4-triazole bistrifluoromethylsulfonylimide salt) ionic liquid/formaldehyde/methylglyoxal crosslinked functional polyelectrolyte porous membranes the difference from the self-supporting covalent crosslinked polyelectrolyte porous membranes of example 1 is: as shown in fig. 8, the pore diameter was 200nm and the membrane thickness was 60 μm, and the preparation of the self-supporting covalently crosslinked polyelectrolyte porous membrane was different from the preparation method of example 1 in that: in step 1, "21.9g of bromamine hydrobromide" was changed to "20.5g of bromamine hydrobromide"; in step 5, "1.65g of 3, 4-dihydroxybenzaldehyde, 60ml of 25% by mass aqueous acetic acid solution were mixed" to 1ml of 37% by mass aqueous formaldehyde solution, 60ml of 10% by mass aqueous acetic acid solution were mixed "; in step 6, as shown in FIG. 7, a poly (4-aminopropyl-1-vinyl-1, 2, 4-triazole bistrifluoromethylsulfonyliminate) ionic liquid/formaldehyde/glyoxal crosslinked functional polyelectrolyte porous membrane is obtained.
EXAMPLE 5,
Preparation of poly (4-aminoethyl-1-vinyl-1, 2, 4-triazole bistrifluoromethylsulfonylimide salt) ionic liquid/D-arabinose/glyoxal crosslinked functional polyelectrolyte porous membrane unlike the self-supporting covalent crosslinked polyelectrolyte porous membrane of example 1: as shown in fig. 10, the pore diameter was 200nm and the membrane thickness was 50 μm, and the preparation of the self-supporting covalently crosslinked polyelectrolyte porous membrane was different from the preparation method of example 1 in that: in step 1, "21.9g of bromamine hydrobromide" was changed to "20.5g of bromamine hydrobromide"; in step 5, "2.2ml of 40% aqueous methylglyoxal solution, 1.65g of 3, 4-dihydroxybenzaldehyde, 60ml of 25% aqueous acetic acid solution by mass fraction" were mixed "to" 1.7ml of 40% aqueous glyoxal solution, 1.8. 1.8g D-arabinose, 60ml of 10% aqueous acetic acid solution by mass fraction "were mixed; in step 6, as shown in FIG. 9, a poly (4-aminopropyl-1-vinyl-1, 2, 4-triazole bistrifluoromethylsulfonyliminate) ionic liquid/formaldehyde/glyoxal crosslinked functional polyelectrolyte porous membrane is obtained.
EXAMPLE 6,
Preparation of poly (3-aminoethyl-1-vinylimidazole bis-pentafluoroethylsulfonimide salt) ionic liquid/D-glucurolactone/methylglyoxal crosslinked functional polyelectrolyte porous membrane unlike the self-supporting covalent crosslinked polyelectrolyte porous membrane of example 1: as shown in fig. 12, the pore diameter was 300nm and the membrane thickness was 200 μm, and the preparation of the self-supporting covalently crosslinked polyelectrolyte porous membrane was different from the preparation method of example 1 in that: in step 1, 9.4g of 1-vinylimidazole, 20.5g of bromoethylamine hydrobromide were added with "9.5 g of 1-vinyl-1, 2, 4-triazole, 21.9g of bromopropylamine hydrobromide" changed to "add; in step 3, "10 ml of 6g of lithium bis (trifluoromethylsulfonyl) imide aqueous solution" was changed to "10 ml of 7g of lithium bis (pentafluoroethylsulfonyl) imide aqueous solution" was added; in step 5, "1.65g of 3, 4-dihydroxybenzaldehyde, 60ml of 25% by mass aqueous acetic acid solution were mixed" to 2.1g of D-glucurolactone, 60ml of 10% by mass aqueous acetic acid solution were mixed "; in step 6, as shown in FIG. 11, a poly (3-aminoethyl-1-vinylimidazole bis-pentafluoroethylsulphonimide salt) ionic liquid/D-glucurolactone/methylglyoxal crosslinked functional polyelectrolyte porous membrane was obtained.
EXAMPLE 7,
Preparation of a poly ((R) -4- (2-aminopropyl) -1-vinyl-1, 2, 4-triazolbis (2-oxopropanoic acid) borate) ionic liquid/2-imidazolecarboxaldehyde/methylglyoxal crosslinked functional polyelectrolyte porous membrane, the difference from the self-supporting covalent crosslinked polyelectrolyte porous membrane of example 1 is: as shown in fig. 14, the pore diameter was 500nm and the membrane thickness was 70 μm, and the preparation of the self-supporting covalently crosslinked polyelectrolyte porous membrane was different from the preparation method of example 1 in that: in step 1, "21.9g of bromopropylamine hydrobromide" was changed to "21.9g of (R) -2-amino-1-bromopropylamine hydrobromide"; in step 3, "10 ml of 6g of lithium bis (trifluoromethylsulfonyl) imide aqueous solution was added" to 10ml of 5g of lithium bis (2-oxopropanoate) borate aqueous solution "was changed; in step 5, "1.65g of 3, 4-dihydroxybenzaldehyde, 60ml of 25% by mass aqueous acetic acid solution were mixed" to 1.2g of 2-imidazolecarboxaldehyde, 60ml of 10% by mass aqueous acetic acid solution were mixed "; in step 6, as shown in FIG. 13, a poly ((R) -4- (2-aminopropyl) -1-vinyl-1, 2, 4-triazol bis (2-oxopropanoic acid) borate) ionic liquid/2-imidazolecarboxaldehyde/methylglyoxal crosslinked functional polyelectrolyte porous membrane was obtained.
EXAMPLE 8,
Preparing a polyelectrolyte porous membrane with a poly ((R) -1- (2-aminopropyl) -4-vinylpyridine) hexafluorophosphate ionic liquid/2-imidazole formaldehyde/methyl glyoxal crosslinking function, wherein the self-supporting covalent crosslinking polyelectrolyte porous membrane has a three-dimensional interpenetrating porous structure, the pore diameter is 120nm, the membrane thickness is 70 mu m, and the preparation method comprises the following steps:
(1) Into a 250ml flask were charged 10.5g of 4-vinyl-pyridine, 21.9g of (R) -2-amino-1-bromopropylamine hydrobromide, 0.1g of 2, 6-di-tert-butyl 4-methylphenol and 50ml of acetonitrile. And reacting for 24 hours at 80 ℃ to obtain the ionic liquid monomer.
(2) 10g of the ionic liquid monomer prepared in the step (1) is dissolved in 200mL of ethanol/water=3:1 (v/v), 0.3g of azobisisobutyronitrile is added, and the reaction is carried out at 80 ℃ for 48 hours, thus obtaining a hydrophilic single-component polyionic liquid homopolymer.
(3) Dissolving 5g of the hydrophilic single-component polyion liquid homopolymer prepared in the step (2) in 20ml of water, adding NaOH to adjust the pH to 9-10, dialyzing the solution for two days, and adding 10ml of 6g of lithium hexafluorophosphate aqueous solution to obtain the hydrophobic single-component polyion liquid homopolymer.
(4) 1g of the hydrophobic single-component polyionic liquid homopolymer prepared in the step (3) is dissolved in 10mL of dimethylformamide, the solution is coated on a glass plate by a commercial film scraping machine, the solution is heated at 80 ℃ for 5 hours, and the solvent is dried, so that the polyionic liquid film is obtained.
(5) 2.2ml of a 40% aqueous solution of methylglyoxal, 1.2g of 2-imidazole formaldehyde, 60ml of a 10% aqueous solution of acetic acid by mass fraction were mixed and dissolved by stirring at 25℃to obtain a mixed reaction solution.
(6) And (3) soaking the polyion liquid film prepared in the step (4) into the mixed reaction solution prepared in the step (5), and reacting for 2 hours at 25 ℃ to obtain the poly ((R) -1- (2-aminopropyl) -4-vinylpyridine) hexafluorophosphate ionic liquid/2-imidazole formaldehyde/methylglyoxal crosslinked functional polyelectrolyte porous membrane.
EXAMPLE 9,
Preparation of poly (4- (4-aminobenzene) -1-vinyl-1, 2, 4-triazole) bis (trifluoromethanesulfonyl) imide ionic liquid/benzaldehyde/2, 3-butanedione cross-linked functional polyelectrolyte porous membrane, unlike the self-supporting covalent cross-linked polyelectrolyte porous membrane of example 8, was: the preparation of the self-supporting covalently crosslinked polyelectrolyte porous membrane with a pore size of 400nm and a membrane thickness of 200 μm differs from the preparation method of example 8 in that: in step 1, the "addition of 10.5g of 4-vinyl-pyridine, 21.9g of (R) -2-amino-1-bromopropylamine hydrobromide" was changed to "addition of 9.5g of 1-vinyl-1, 2, 4-triazole, 26.7g of p-aminobenzyl bromide"; in step 3, "10 ml of 6g of lithium hexafluorophosphate aqueous solution" was changed to "8 g of lithium bis (pentafluoroethanesulfonyl) imide aqueous solution" was added; in step 5, "2.2ml of 40% aqueous methylglyoxal solution, 1.2g of 2-imidazolecarboxaldehyde" was changed to "1.5g of 2, 3-butanedione, 1.9g of benzaldehyde"; in the step 6, the poly (4- (4-aminobenzene) -1-vinyl-1, 2, 4-triazole) bis (trifluoromethanesulfonyl) imine ionic liquid/benzaldehyde/2, 3-butanedione cross-linked functional polyelectrolyte porous membrane is obtained.
EXAMPLE 10,
Preparation of poly (3- ((1-ethyl-3-aminoethylimidazole) bis (trifluoromethanesulfonyl) imine) -1-vinylimidazole) bis (trifluoromethanesulfonyl) imine ionic liquid/D-glyceraldehyde/1, 2-cyclohexanedione cross-linked functional polyelectrolyte porous membrane, unlike the self-supporting covalent cross-linked polyelectrolyte porous membrane of example 8: the pore size was 500nm and the membrane thickness was 175 μm, and the preparation of the self-supporting covalently crosslinked polyelectrolyte porous membrane was different from the preparation method of example 8 in that: in step 1, "10.5 g of 4-vinyl-pyridine, 21.9g of (R) -2-amino-1-bromopropylamine hydrobromide" was changed to "27 g of 3- (1-ethylimidazole) -1-vinylimidazole bromide, 20.5g of bromoethylamine hydrobromide" was added; in step 3, "10 ml of 6g of lithium hexafluorophosphate aqueous solution" was changed to "6 g of lithium bis (trifluoromethylsulfonyl) imide aqueous solution" was added; in step 5, "2.2ml of 40% aqueous methylglyoxal solution, 1.2g of 2-imidazolecarboxaldehyde" was changed to "1.4g of 1, 2-cyclohexanedione, 1.2. 1.2g D-glyceraldehyde"; in step 6, a poly (3- ((1-ethyl-3-aminoethyl imidazole) bis (trifluoromethanesulfonyl) imine) -1-vinylimidazole) bis (trifluoromethanesulfonyl) imine ionic liquid/D-glyceraldehyde/1, 2-cyclohexanedione crosslinked functional polyelectrolyte porous membrane is obtained.
EXAMPLE 11,
Preparation of poly (3- (2- (2-aminomethoxyethoxy) ethyl) -1-vinylimidazole) bis (pentafluoroethanesulfonyl) imide ionic liquid/L-glucuronic acid-3, 6-lactone/methylglyoxal crosslinked functional polyelectrolyte porous membranes, unlike the self-supporting covalent crosslinked polyelectrolyte porous membrane of example 8: the pore size was 320nm and the membrane thickness was 130. Mu.m, and the preparation of the self-supporting covalently crosslinked polyelectrolyte porous membrane was different from the preparation method of example 8 in that: in step 1, the "addition of 10.5g of 4-vinyl-pyridine, 21.9g of (R) -2-amino-1-bromopropylamine hydrobromide" was changed to "addition of 9.4g of vinylimidazole, 24.6g of 2- (2-aminomethoxyethoxy) bromoethane hydrobromide"; in step 3, "10 ml of 6g of lithium hexafluorophosphate aqueous solution" was changed to "8 g of lithium bis (2-oxo- (3-phenyl) butanoic acid) borate aqueous solution" was added; in step 5, "1.2g of 2-imidazolecarboxaldehyde" was changed to "3.8, g D-glucuronic acid-3, 6-lactone"; in the step 6, the poly (3- (2- (2-amino methoxyethoxy) ethyl) -1-vinyl imidazole) bis (pentafluoroethane sulfonyl) imine ionic liquid/L-glucuronic acid-3, 6-lactone/methyl glyoxal crosslinked functional polyelectrolyte porous membrane is obtained.
EXAMPLE 12,
Preparation of poly (3- ((4-aminoethyl-1-propyl-1, 2, 4-triazole) bis (trifluoromethanesulfonyl) imine) -1-vinyl-1, 2, 4-triazole) bis (trifluoromethanesulfonyl) imine ionic liquid/p-dimethylaminobenzaldehyde/1, 2-cyclohexanedione cross-linked functional polyelectrolyte porous membrane, in contrast to the self supporting covalently cross-linked polyelectrolyte porous membrane of example 8: the pore size was 600nm and the membrane thickness was 250 μm, and the preparation of the self-supporting covalently crosslinked polyelectrolyte porous membrane was different from the preparation method of example 8 in that: in step 1, the "addition of 10.5g of 4-vinyl-pyridine, 21.9g of (R) -2-amino-1-bromopropylamine hydrobromide" was changed to "addition of 27g of 3- (1-propyl-1, 2, 4-triazole) -1-vinyl-1, 2, 4-triazole bromine, 20.49g of bromoethylamine hydrobromide"; in step 3, "10 ml of 6g of lithium hexafluorophosphate aqueous solution" was changed to "6 g of lithium bis (trifluoromethylsulfonyl) imide aqueous solution" was added; in step 5, "2.2ml of 40% aqueous methylglyoxal solution, 1.2g of 2-imidazolecarboxaldehyde" was changed to "1.4g of 1, 2-cyclohexanedione, 1.8g of p-dimethylaminobenzaldehyde"; in step 6, a poly (3- ((4-aminoethyl-1-propyl-1, 2, 4-triazole) bis (trifluoromethanesulfonyl) imide) -1-vinyl-1, 2, 4-triazole) bis (trifluoromethanesulfonyl) imide ionic liquid/p-dimethylaminobenzaldehyde/1, 2-cyclohexanedione cross-linked functional polyelectrolyte porous membrane is obtained.
EXAMPLE 13,
Preparation of poly (3-aminobutyl-1- (4-vinyl) phenylimidazole) bis (2-oxopropanoic acid) borate ionic liquid/terephthalaldehyde/3, 4-hexanedione cross-linked functional polyelectrolyte porous membrane, in contrast to the self-supporting covalent cross-linked polyelectrolyte porous membrane of example 8, the following were: the pore size was 700nm and the membrane thickness was 310. Mu.m, and the preparation of the self-supporting covalently crosslinked polyelectrolyte porous membrane was different from the preparation method of example 8 in that: in step 1, "10.5 g of 4-vinyl-pyridine, 21.9g of (R) -2-amino-1-bromopropylamine hydrobromide were added" to 18.4g of 1- (4-vinyl) phenylimidazole, 23.3g of bromobutylamine hydrobromide "; in step 3, "10 ml of 6g of lithium hexafluorophosphate aqueous solution" was changed to "5 g of lithium bis (2-oxopropionic acid) borate aqueous solution" was added; in step 5, "2.2ml of 40% aqueous methylglyoxal solution, 1.2g of 2-imidazolecarboxaldehyde" was changed to "2.6g of 3, 4-hexanedione, 3.1g of terephthalaldehyde"; in the step 6, the polyelectrolyte porous membrane with the crosslinking function of poly (3-aminobutyl-1- (4-vinyl) phenylimidazole) bis (2-oxypropionic acid) boric acid ionic liquid/terephthalaldehyde/3, 4-hexanedione is obtained.
EXAMPLE 14,
Preparation of poly (3- (4-methyl-1-aminobenzene) -4-methyl- (5-vinyl) thiazole) bistrifluoromethylsulfonylimide salt) ionic liquid/2, 4-dihydroxybenzaldehyde/methylglyoxal crosslinked functional polyelectrolyte porous membrane, in contrast to the self-supporting covalent crosslinked polyelectrolyte porous membrane of example 8: the pore size was 350nm and the membrane thickness was 260 μm, and the preparation of the self-supporting covalently crosslinked polyelectrolyte porous membrane was different from the preparation method of example 8 in that: in step 1, the "addition of 10.5g of 4-vinyl-pyridine, 21.9g of (R) -2-amino-1-bromopropylamine hydrobromide" was changed to "addition of 12.5g of 4-methyl- (5-vinyl) thiazole, 26.7g of p-aminobenzyl bromide hydrobromide"; in step 3, "10 ml of 6g of lithium hexafluorophosphate aqueous solution" was changed to "6 g of lithium bis (trifluoromethylsulfonyl) imide aqueous solution" was added; in step 5, 1.2g of 2-imidazolecarboxaldehyde is changed to 1.8g of 2, 4-dihydroxybenzaldehyde; in the step 6, the poly (3- (4-methyl-1-aminobenzene) -4-methyl- (5-vinyl) thiazole) bistrifluoromethyl sulfonyl imide salt) ionic liquid/2, 4-dihydroxybenzaldehyde/methylglyoxal crosslinking functional polyelectrolyte porous membrane is obtained.
In order to evaluate the thermal stability of the self-supporting covalent cross-linked polyelectrolyte porous membranes prepared by the invention, thermal gravimetric analysis was performed by taking examples 1-4 as examples, and fig. 15 shows thermal gravimetric test data of the self-supporting covalent cross-linked polyelectrolyte porous membranes prepared by the invention, and the decomposition temperatures of the membranes are higher than 250 ℃, which proves that the co-cross-linked membrane structures prepared by the invention have good thermal stability.
Meanwhile, in order to evaluate the chemical stability and salt and acid resistance of the self-supporting covalent cross-linked polyelectrolyte porous membrane prepared by the invention, the polyelectrolyte porous membrane prepared by the invention is respectively soaked into dimethylformamide, absolute ethyl alcohol, acetonitrile, 1mol/LNaCl salt solution, pH=2 hydrochloric acid aqueous solution and pH=12 NaOH aqueous solution, and as shown in fig. 16, the morphology of the membrane is still intact after soaking for seven days, and in addition, no obvious infrared peak change is observed compared with the infrared spectrograms (fig. 17) of the original membrane and the membrane after soaking treatment, so that the self-supporting covalent cross-linked polyelectrolyte porous membrane prepared by the invention is further proved to have excellent chemical stability, and the defects of poor structural stability of traditional electrostatic cross-linking and supermolecular cross-linked PPMs and structural disintegration under high-salt or thermal environments are overcome.
In addition, as shown in fig. 18, the self-supporting covalent cross-linked polyelectrolyte porous membrane prepared by the present invention has also been cut and bent to some extent, with adjustable shape and mechanical strength.
Application example
The ion separation performance and the effect of the membrane structure were tested as represented by examples 1,2 and 3, and as shown in FIG. 19, the prepared self-supporting covalent cross-linked polyionic liquid porous membrane was sandwiched between two chambers of an electrolytic cell, and under electric driving, the conductivity in different solutions in the presence or absence of the membrane was compared to that in the presence of the membrane, and the effect of the high valence ions (Ca 2+ 、Mg 2+ 、Al 3+ ) The conductivity of the solution is obviously reduced compared with that of the solution in a film-free state, and the film has higher rejection rate to high-valence cations, and in addition, the rejection rate to the high-valence cations is further improved along with the reduction of the pore diameter of the film, so that the ion separation of different valence states can be realized to a certain extent through the structural design and the pore diameter adjustment of the film (figure 20). The functional film provides a technical support for extracting lithium metal from seawater.
Claims (10)
1. A method for preparing a self-supporting covalent cross-linking functional polyelectrolyte porous membrane, which is characterized by comprising the following steps:
(1) Preparation of amino-containing ionic liquid monomer: mixing amino-containing halogenated compound, vinyl-containing compound and good solvent in a proportion of 1mol: (0.5-2) mol: (10-1000 ml) mixing, stirring for 2-48 h at 30-90 ℃ under nitrogen or inert gas atmosphere to carry out quaternization reaction, and then recrystallizing in poor solvent to obtain the amino-containing ionic liquid monomer;
(2) Preparation of amino-containing hydrophobic one-component polyionic liquid homopolymer: mixing the amino-containing ionic liquid monomer prepared in the step (1), azodiisobutyronitrile and 75% ethanol aqueous solution according to the mass ratio of 1: (0.01-0.1): (10-100), stirring for 12-72 h at 60-100 ℃ under nitrogen or inert gas atmosphere, removing solvent by rotary evaporation, washing and drying by diethyl ether, adding sodium hydroxide solution to adjust pH to 9-10, dialyzing the obtained solution for 2-5 days, and adding hydrophobic anion lithium salt to obtain the amino-containing hydrophobic single-component polyionic liquid homopolymer;
(3) Preparing a mixed reaction solution: adding a 1, 2-dicarbonyl compound and an aldehyde compound into an aqueous solution of 5-50% of acid by mass percent, and heating and dissolving at 25-70 ℃ to obtain a mixed reaction solution;
(4) Preparing a polyion liquid film: mixing the hydrophobic single-component polyionic liquid homopolymer obtained in the step (2) with dimethylformamide or dimethyl sulfoxide according to the proportion of 1g: (1-50) ml, stirring and dissolving at 25-70 ℃ to prepare a polymer solution, scraping the polymer solution on a glass plate by using an industrial film scraping machine, heating at 50-120 ℃ for 2-48 hours, and drying the solvent to obtain the polyion liquid film with the matrix;
(5) Preparation of self-supporting covalent cross-linking functional polyelectrolyte porous membranes: soaking the polyion liquid film prepared in the step (4) into the mixed reaction solution prepared in the step (3), and reacting for 1-48 h at the temperature of 0-80 ℃ to obtain the self-supporting covalent cross-linking functional polyelectrolyte porous film.
2. The method of preparing a self-supporting, covalently cross-linked functional polyelectrolyte porous membrane according to claim 1, wherein the amino-containing halogenated compound is:
the vinyl-containing compound is
The good solvent is one or more of methanol, acetone, tetrahydrofuran, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, sulfolane, dioxane, hydroxy propionic acid, ethylamine, ethylenediamine, glycerol, diethylene glycol dimethyl ether, 1, 3-dioxolane, pyridine, formamide, acetonitrile, propanol or isopropanol;
the poor solvent is one or more of ethanol, acetone, diethyl ether, dioxane, diethylene glycol dimethyl ether, 1, 3-dioxolane, pyridine, propanol or isopropanol;
the amino-containing hydrophobic single-component polyionic liquid homopolymer is as follows:
the hydrophobic anion lithium salt is CF 3 SO 3 Li、(CF 3 SO 2 ) 2 NLi or (CF) 3 CF 2 SO 2 ) 2 NLi；
Wherein R' is R is alkyl with 0-18 carbon atoms; n is an integer of 10 to 1000; m is an integer of 1 to 18; x is Cl, br or I; x' is X, (-) -X> ClO 4 、BF 4 、PF 6 、CF 3 SO 3 、(CF 3 SO 2 ) 2 N or (CF) 3 CF 2 SO 2 ) 2 N; x' is-> CF 3 SO 3 、(CF 3 SO 2 ) 2 N or (CF) 3 CF 2 SO 2 ) 2 N。
3. The method for preparing a self-supporting covalent cross-linking functional polyelectrolyte porous membrane according to claim 1, wherein the mixed reaction solution comprises a plurality of combinations of 1, 2-dicarbonyl compounds, aldehyde compounds and acids.
4. The method of preparing a self-supporting, covalently cross-linked, functional polyelectrolyte porous membrane according to claim 3, wherein the 1, 2-dicarbonyl compound is
The aldehyde compound is
Formaldehyde, 2, 4-dihydroxybenzaldehyde, 3, 4-dihydroxybenzaldehyde, 2-imidazolecarboxaldehyde, 5-methylimidazole-4-carbaldehyde, D-glyceraldehyde, L-glyceraldehyde, D-erythrose, L-erythrose, D-threose, L-threose, D-ribose, L-ribose, D-xylose, L-xylose, D-lyxose, L-lyxose, D-allose, L-altrose, D-glucose, L-glucose, D-mannose, L-mannose, D-gulose, L-gulose, D-idose, L-idose, D-galactose, L-galactose, D-talose, L-arabinose, D-glucuronic acid-3, 6-lactone or L-glucuronic acid-3, 6-lactone;
the acid is acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrobromic acid or boric acid;
wherein R is 1 Is H, C1-18 alkyl,R 2 Is C1-18 alkyl; r is R 3 Is H, C1-18 alkyl, -/-, and/or>R 4 Is C1-18 alkyl, -OH, -COOH, -CO 2 Et、-OCH 3 、-NO 2 、-SO 3 H、-B(OH) 2 、-N(CH 3 ) 2 -F, -Cl, -Br, -I or-H; m is Co, cu, ni, znCr, fe, pt, mn, mg, al or Ca.
5. The method for preparing a self-supporting covalent cross-linking functional polyelectrolyte porous membrane according to claim 1, wherein the dosage ratio of the hydrophobic single-component polyionic liquid homopolymer, the 1, 2-dicarbonyl compound, the aldehyde compound and the aqueous solution of 5-50% of acid by mass is (0.02-2) mol:1mol:1mol: (500-10000) ml.
6. The method for preparing a self-supporting covalent cross-linking functional polyelectrolyte porous membrane according to claim 1, wherein the molar ratio of the amino-containing ionic liquid monomer to the hydrophobic anionic lithium salt is 1: (1-10).
7. The method for producing a self-supporting, covalently crosslinked, functional polyelectrolyte porous membrane according to any one of claims 1 to 6, wherein the obtained self-supporting, covalently crosslinked, functional polyelectrolyte porous membrane has a three-dimensional interpenetrating multi-stage pore structure with a pore diameter of 10nm to 10 μm.
8. The method of preparing a self-supporting, covalently crosslinked functional polyelectrolyte porous membrane according to any one of claims 1-6, wherein the self-supporting, covalently crosslinked functional polyelectrolyte porous membrane has a thickness of 20nm to 1cm.
9. A self-supporting, covalently crosslinked functional polyelectrolyte porous membrane obtainable by the method of any one of claims 1 to 6.
10. Use of the covalent cross-linked functional polyelectrolyte porous membrane obtained by the preparation method of any one of claims 1-6 in ion separation.
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