CN115838495A - 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 poly ionic liquid, obtains polymer film by utilizing industrial mature blade coating technology, then soaks the polymer film into a mixed reaction solution formed by 1,2-dicarbonyl compound-aldehyde compound and acid, and can prepare covalent cross-linking functional polyelectrolyte porous membrane with high charge density at room temperature by one step. The covalently crosslinked polyion liquid porous membrane has controllable thickness, pore size, mechanical properties and designable structure and shape. The method can realize the large-scale preparation of the covalent crosslinking functional polyelectrolyte porous film under the room temperature condition. The self-supporting covalent crosslinking polyion liquid porous membrane prepared by the invention has excellent chemical and thermal stability, and has wide practical application prospect in the energy field of seawater 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
Due to the characteristics of pore effect and electric charge, the Polyelectrolyte Porous Membrane (PPM) has great application prospect in the fields of adsorption separation, lubrication, optics, nano-electronic devices, energy storage and the like. However, the conventional polyelectrolyte is difficult to prepare a high-quality polyelectrolyte porous membrane by a phase separation method which is industrially mature at present due to its water solubility. Therefore, in the last two centuries, great efforts have been made by researchers to find a reliable membrane preparation technology to realize industrial preparation of high quality PPM.
The scale preparation method of the polyelectrolyte porous membrane which is developed at present mainly comprises a layer-by-layer self-assembly (LBL), electrostatic crosslinking and hydrogen bond supermolecule crosslinking method, and a part of PPM prepared by the LBL is industrialized. However, PPM prepared by the existing methods has poor structural stability, pores can be dissociated in a high-salt or thermal environment, the application prospect of the PPM is greatly limited, and the LBL preparation process is extremely time-consuming and labor-consuming. Therefore, the development of the PPM which can be prepared in a large scale and has good heat resistance/solvent resistance 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 high polymer, and shows a good application prospect in the field of membrane science.
Disclosure of Invention
The invention aims to solve the problems of labor consumption and time consumption of the existing polyelectrolyte porous membrane synthesis method, salt/thermal instability of a prepared PPM structure and the like, and provides a preparation method of a self-supporting covalent crosslinking functional polyelectrolyte porous membrane which is cheap, easy to obtain, easy to prepare in a large scale, has designable and adjustable aperture, structure and mechanical properties, and has 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 the metal lithium from the seawater under the conditions of environmental friendliness and low energy consumption.
The technical scheme of the invention is as follows:
a preparation method of a self-supporting covalent cross-linking functional polyelectrolyte porous membrane comprises the following steps:
(1) Preparation of amino-containing ionic liquid monomer: 1mol of halogenated amino-containing compound, vinyl-containing compound and good solvent in proportion: (0.5-2) mol: (10-1000) ml, stirring for 2-48 h at 30-90 ℃ in nitrogen or inert gas atmosphere for quaternization, and then recrystallizing in poor solvent to obtain the amino ion-containing liquid monomer;
(2) Preparation of amino-containing hydrophobic mono-component polyion liquid homopolymer: mixing the amino-containing ionic liquid monomer prepared in the step (1), azodiisobutyronitrile and 75% of 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 the atmosphere of nitrogen or inert gas, removing the solvent by rotary evaporation, washing and drying by using ether, adding a sodium hydroxide solution to adjust the pH value to 9-10, dialyzing the obtained solution for 2-5 days, and adding hydrophobic anionic lithium salt (wherein the molar ratio of the amino-containing ionic liquid monomer to the hydrophobic anionic lithium salt is 1 (1-10)) to obtain the amino-containing hydrophobic single-component polyionic liquid homopolymer;
(3) Preparing a mixed reaction solution: adding 1,2-dicarbonyl compound and aldehyde compound into 5-50% acid water solution by mass fraction, heating and dissolving at 25-70 ℃ to obtain mixed reaction solution;
(4) Preparing a polyion liquid film: mixing the hydrophobic single-component polyion 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 polymer solution, coating the polymer solution on a glass plate by using an industrial film scraper, heating at 50-120 ℃ for 2-48 hours, and drying the solvent to obtain the polyion liquid film with the matrix;
(5) Preparing a self-supporting covalent cross-linking functional polyelectrolyte porous membrane: and (3) 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 0-80 ℃ to obtain the self-supported covalent cross-linked functional polyelectrolyte porous membrane.
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, butylsulfone, dioxane, hydroxypropionic acid, ethylamine, ethylenediamine, glycerol, diglyme, 1,3-dioxolane, pyridine, formamide, acetonitrile, propanol or isopropanol;
the poor solvent is one or more of ethanol, acetone, diethyl ether, dioxane, cyclohexane, diglyme, 1,3-dioxolane, pyridine, propanol or isopropanol;
the amino-containing hydrophobic mono-component polyion liquid homopolymer is as follows:
the hydrophobic anionic lithium salt is
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 and/or>
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>
Preferably, the 1,2-dicarbonyl compound is
The aldehyde compound is
/>
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-C18 alkyl,
R 2 Is alkyl with 1-18 carbon atoms; r 3 Is H, C1-C18 alkyl 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、-Ior-H; m is Co, cu, ni, zn, cr, fe, pt, mn, mg, al or Ca.
Preferably, the dosage ratio of the hydrophobic mono-component polyion liquid homopolymer, 1,2-dicarbonyl compound, aldehyde compound and 5-50% mass percent acid aqueous solution is (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, and the porous membrane has a covalent cross-linking three-dimensional interpenetrating hierarchical 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 prepared 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 of the traditional polyion liquid porous membrane preparation, the invention provides a preparation method of a self-supporting covalent crosslinking polyion liquid porous membrane material which is cheap and easy to obtain, is easy to prepare in a large scale, has designed and adjusted aperture, structure and mechanical properties, and has good thermal stability and chemical stability, and the application of the self-supporting covalent crosslinking polyion liquid porous membrane material in ion separation. The covalent cross-linked polyion liquid porous membrane prepared by the method is prepared by one-step reaction in aqueous solution at normal temperature and normal pressure, and is expected to be applied in a large scale.
Drawings
FIG. 1 shows a preparation process of a self-supporting cross-linked functional polyelectrolyte porous membrane: immersing the polyion liquid film and the substrate into a mixed reaction solution of 1,2-dicarbonyl compound, aldehyde compound and 5-50% by mass of acid aqueous solution, and obtaining a self-supporting cross-linked functional polyelectrolyte porous membrane real object diagram after complete reaction;
FIG. 2 is a Scanning Electron Microscope (SEM) photomicrograph of a cross-section of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 1 showing (a) low magnification and (b) high magnification;
FIG. 3 is a diagram of a self-supporting cross-linked functional polyelectrolyte porous membrane embodiment prepared in example 2;
FIG. 4 is a scanning electron microscope photomicrograph of a cross-section of (a) a low magnification and (b) a high magnification self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 2;
FIG. 5 is a diagram of a self-supporting cross-linked functional polyelectrolyte porous membrane embodiment prepared in example 3;
FIG. 6 is a scanning electron microscope photomicrograph of (a) a lower magnification and (b) a higher magnification cross-sectional view of a self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 3;
FIG. 7 is a diagram of a self-supporting cross-linked functional polyelectrolyte porous membrane embodiment prepared in example 4;
FIG. 8 is a scanning electron microscope photomicrograph of a cross-section of (a) a low magnification and (b) a high magnification 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 made in example 5;
FIG. 10 is a scanning electron microscope photomicrograph of a cross-section of (a) low power and (b) high power 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 microscope photomicrograph showing the cross-sections of (a) a low magnification and (b) a high magnification of the 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 microscope photomicrograph of a cross-section of (a) low power and (b) high power self-supporting cross-linked functional polyelectrolyte porous membrane prepared in example 7;
FIG. 15 is a thermogravimetric analysis of a self-supported cross-linked functional polyelectrolyte porous membrane 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 being soaked in different solvents, and the comparison of the original membrane shows no obvious spectrum change, which shows that the self-supporting cross-linked polyelectrolyte porous membrane prepared by the invention has good chemical stability;
FIG. 18 is a pictorial view of a self-supporting cross-linked functional polyelectrolyte porous membrane and bending it;
FIG. 19 is a photograph of an apparatus for electrically driven ion separation using a self-supporting cross-linked functional polyelectrolyte porous membrane;
FIG. 20 is a graph comparing the conductivity change rates for different ionic solutions compared to the no-membrane state for self-supported cross-linked functional polyelectrolyte porous membranes prepared in examples 1-3.
Detailed Description
Compared with the traditional polyion liquid porous membrane preparation method with harsh reaction conditions, complicated preparation process and relatively single chemical structure, the invention provides the preparation method of the functional polyelectrolyte porous membrane with low price, easy obtaining, easy large-scale preparation and mild reaction conditions.
The present invention will be further understood by the following illustrative description and the accompanying drawings, which are given by way of preferred embodiments and illustrative examples, but the details of the embodiments are only for the purpose of illustrating the present invention and do not represent all technical solutions contemplated by the present invention, and therefore, should not be construed as limiting the general technical solutions of the present invention. It will be apparent to the skilled person that insubstantial additions and modifications, for example changes or substitutions in technical features having the same or similar technical effects, without departing from the inventive concept, are within the scope of the present invention.
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 mono-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 (ii) a n is preferably an integer of 100 to 500; m is preferably an integer of 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-imidazolecarboxaldehyde, D-arabinose, D-glucuronic acid-3,6-lactone, or p-dimethylaminobenzaldehyde.
The acid is preferably acetic acid.
The invention also provides the application of the self-supporting covalent cross-linking functional polyelectrolyte porous membrane in ion separation.
In the present invention, the application preferably comprises the steps of: the self-supporting covalent cross-linking functional polyelectrolyte porous membrane is clamped between two chambers of an electrolytic cell, a current-voltage curve is tested under the condition of an external voltage, the electric conductance is obtained by calculating the slope of the current-voltage curve, and the ion separation effect of the membrane is evaluated by comparing the change rate of the electric conductance of the solution under the membrane-existing state and the membrane-free state. In the invention, due to the self charged property of the polyion liquid and the good thermal stability and chemical stability of the covalent cross-linked functional polyelectrolyte porous membrane, the selective separation of ions can be hopefully realized through the electrostatic repulsion action of high valence ions in the solution and the wall of the hole with positive charge.
Examples 1,
The preparation method of the poly (4-aminopropyl-1-vinyl-1,2,4-triazole bis (trifluoromethyl) sulfonyl imide salt) ionic liquid/3,4-dihydroxybenzaldehyde/methylglyoxal cross-linked functional polyelectrolyte porous membrane is as shown in figure 2, the self-supporting covalent cross-linked 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 is as follows:
(1) A250 ml flask was charged with 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. Reacting for 24 hours at 80 ℃ to obtain the ionic liquid monomer.
(2) Dissolving 10g of the ionic liquid monomer prepared in the step (1) in 200mL of ethanol/water =3:1 (v/v), adding 0.3g of azobisisobutyronitrile, and reacting at 80 ℃ for 48h to obtain the hydrophilic mono-component polyionic liquid homopolymer.
(3) And (3) dissolving 5g of the hydrophilic mono-component polyion liquid homopolymer prepared in the step (2) in 20ml of water, adding NaOH to adjust the pH value to 9-10, dialyzing the solution for two days, and adding 10ml of 6g of bis (trifluoromethylsulfonyl) imide lithium salt aqueous solution to obtain the hydrophobic mono-component polyion liquid homopolymer.
(4) And (3) dissolving 1g of the hydrophobic single-component polyion liquid homopolymer prepared in the step (3) in 10mL of dimethylformamide, carrying out blade coating on a glass plate by using an industrial film scraping machine, heating at 80 ℃ for 5 hours, and drying the solvent to obtain the polyion liquid film.
(5) 2.2ml of a 40% methylglyoxal aqueous solution, 1.65g of 3, 4-dihydroxybenzaldehyde and 60ml of an acetic acid aqueous solution having a mass fraction of 25% were mixed and dissolved at 30 ℃ with stirring to obtain a mixed reaction solution.
(6) As shown in fig. 1, the polyion liquid membrane prepared in the step (4) is soaked into the mixed reaction solution prepared in the step (5) and reacts for 2 hours at 25 ℃ to obtain the poly (4-aminopropyl-1-vinyl-1,2,4-triazole bistrifluoromethylsulfonyl imide salt) ionic liquid/3,4-dihydroxybenzaldehyde/methylglyoxal cross-linked functional polyelectrolyte porous membrane.
Examples 2,
Preparation of poly (4-aminopropyl-1-vinyl-1,2,4-triazole bistrifluoromethylsulfonyl imide salt) ionic liquid/formaldehyde/methylglyoxal cross-linked functional polyelectrolyte porous membrane, in contrast to the self-supporting covalently cross-linked polyelectrolyte porous membrane of example 1: as shown in FIG. 4, the pore diameter was 90nm and the film thickness was 150 μm, and the preparation of the self-supported covalently cross-linked polyelectrolyte porous membrane was different from the preparation method of example 1 in that: in step 5, 1.65g of 3, 4-dihydroxybenzaldehyde and 60ml of 25% acetic acid aqueous solution are mixed to obtain 1ml of 37% formaldehyde aqueous solution and 60ml of 10% acetic acid aqueous solution; in step 6, as shown in fig. 3, the poly (4-aminopropyl-1-vinyl-1,2,4-triazole bistrifluoromethylsulfonyl imide salt) ionic liquid/formaldehyde/methylglyoxal cross-linked functional polyelectrolyte porous membrane is obtained.
Examples 3,
Preparation of poly (4-aminoethyl-1-vinyl-1,2,4-triazole bistrifluoromethylsulfonyl imide salt) ionic liquid/3,4-dihydroxybenzaldehyde/methylglyoxal cross-linked functional polyelectrolyte porous membrane in contrast to the self-supporting covalently cross-linked polyelectrolyte porous membrane of example 1: as shown in FIG. 6, the preparation of the self-supporting covalently cross-linked polyelectrolyte porous membrane having a pore diameter of 250nm and a membrane thickness of 60 μm is different from that of example 1 in that: in step 1, "21.9g of bromopropylamine hydrobromide" was changed to "20.5g of bromoethylamine hydrobromide"; in step 6, as shown in FIG. 5, poly (4-aminopropyl-1-vinyl-1,2,4-triazole bis (trifluoromethyl) sulfonyl imide salt) ionic liquid/3,4-dihydroxybenzaldehyde/methylglyoxal cross-linked functional polyelectrolyte porous membrane is obtained.
Examples 4,
Preparation of poly (4-aminoethyl-1-vinyl-1,2,4-triazole bistrifluoromethylsulfonyl imide salt) ionic liquid/formaldehyde/methylglyoxal cross-linked functional polyelectrolyte porous membrane, in contrast to the self-supporting covalently cross-linked polyelectrolyte porous membrane of example 1: as shown in FIG. 8, the pore diameter was 200nm and the film thickness was 60 μm, and the preparation of the self-supported covalently cross-linked 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 "20.5g of bromoethylamine hydrobromide"; in step 5, 1.65g of 3, 4-dihydroxybenzaldehyde and 60ml of 25% acetic acid aqueous solution are mixed to obtain 1ml of 37% formaldehyde aqueous solution and 60ml of 10% acetic acid aqueous solution; in step 6, as shown in fig. 7, poly (4-aminopropyl-1-vinyl-1,2,4-triazole bistrifluoromethylsulfonyl imide salt) ionic liquid/formaldehyde/glyoxal cross-linked functional polyelectrolyte porous membrane is obtained.
Examples 5,
Preparation of poly (4-aminoethyl-1-vinyl-1,2,4-triazole bistrifluoromethylsulfonyl imide salt) ionic liquid/D-arabinose/glyoxal cross-linked functional polyelectrolyte porous membrane, in contrast to the self-supporting covalently cross-linked polyelectrolyte porous membrane of example 1: as shown in FIG. 10, the pore diameter was 200nm and the film thickness was 50 μm, and the preparation of the self-supported covalently cross-linked 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 "20.5g of bromoethylamine hydrobromide"; in step 5, mixing 2.2ml of 40% methylglyoxal aqueous solution, 1.65g of 3, 4-dihydroxybenzaldehyde and 60ml of 25% acetic acid aqueous solution to obtain 1.7ml of 40% glyoxal aqueous solution, 1.8g D-arabinose and 60ml of 10% acetic acid aqueous solution; in step 6, as shown in fig. 9, poly (4-aminopropyl-1-vinyl-1,2,4-triazole bistrifluoromethylsulfonyl imide salt) ionic liquid/formaldehyde/glyoxal cross-linked functional polyelectrolyte porous membrane is obtained.
Examples 6,
Preparation of poly (3-aminoethyl-1-vinylimidazole bis-pentafluoroethylsulfonylimide) ionic liquid/D-glucurolactone/methylglyoxal cross-linked functional polyelectrolyte porous membrane in contrast to the self-supporting covalently cross-linked polyelectrolyte porous membrane of example 1: as shown in FIG. 12, the pore diameter was 300nm and the film thickness was 200 μm, and the preparation of the self-supported covalently cross-linked polyelectrolyte porous membrane was different from the preparation method of example 1 in that: in step 1, "9.4 g of 1-vinylimidazole and 20.5g of bromoethylamine hydrobromide" was added instead of "9.5 g of 1-vinyl-1,2,4-triazole and 21.9g of bromopropylamine hydrobromide"; in step 3, "adding 10ml of 6g of lithium bis (trifluoromethylsulfonyl) imide salt aqueous solution" was changed to "adding 10ml of 7g of lithium bis (pentafluoroethylsulfonyl) imide salt aqueous solution"; in step 5, 1.65g of 3, 4-dihydroxybenzaldehyde and 60ml of acetic acid aqueous solution with the mass fraction of 25 percent are mixed to obtain 2.1g of D-glucurolactone and 60ml of acetic acid aqueous solution with the mass fraction of 10 percent; in step 6, as shown in fig. 11, a poly (3-aminoethyl-1-vinylimidazole bis-pentafluoroethylsulfonyl imide) ionic liquid/D-glucurolactone/methylglyoxal cross-linked functional polyelectrolyte porous membrane is obtained.
Example 7,
Preparation of poly ((R) -4- (2-aminopropyl) -1-vinyl-1,2,4-triazole bis (2-oxopropionic acid) borate) ionic liquid/2-imidazolecarboxaldehyde/methylglyoxal cross-linked functional polyelectrolyte porous membrane in contrast to the self-supporting covalently cross-linked polyelectrolyte porous membrane of example 1: as shown in FIG. 14, the preparation of the self-supporting covalently cross-linked polyelectrolyte porous membrane having a pore size of 500nm and a membrane thickness of 70 μm was different from that 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, "adding 10ml of 6g of lithium bis (trifluoromethylsulfonyl) imide salt aqueous solution" was changed to "adding 10ml of 5g of lithium bis (2-oxopropionate) borate salt aqueous solution"; in step 5, mixing 1.65g of 3, 4-dihydroxybenzaldehyde and 60ml of 25% acetic acid aqueous solution by mass fraction is changed into mixing 1.2g of 2-imidazole formaldehyde and 60ml of 10% acetic acid aqueous solution by mass fraction; in step 6, as shown in fig. 13, poly ((R) -4- (2-aminopropyl) -1-vinyl-1,2,4-triazole bis (2-oxopropionic acid) borate) ionic liquid/2-imidazolecarboxaldehyde/methylglyoxal cross-linked functional polyelectrolyte porous membrane was obtained.
Examples 8,
The preparation method of the poly ((R) -1- (2-aminopropyl) -4-vinylpyridine) hexafluorophosphate ionic liquid/2-imidazolecarboxaldehyde/methylglyoxal cross-linked functional polyelectrolyte porous membrane comprises the following steps:
(1) A250 ml flask was charged with 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. Reacting for 24 hours at 80 ℃ to obtain the ionic liquid monomer.
(2) Dissolving 10g of the ionic liquid monomer prepared in the step (1) in 200mL of ethanol/water =3:1 (v/v), adding 0.3g of azobisisobutyronitrile, and reacting at 80 ℃ for 48h to obtain the hydrophilic mono-component polyionic liquid homopolymer.
(3) And (3) dissolving 5g of the hydrophilic mono-component polyion liquid homopolymer prepared in the step (2) in 20ml of water, adding NaOH to adjust the pH value to 9-10, dialyzing the solution for two days, and adding 10ml of 6g of lithium hexafluorophosphate aqueous solution to obtain the hydrophobic mono-component polyion liquid homopolymer.
(4) And (3) dissolving 1g of the hydrophobic mono-component polyion liquid homopolymer prepared in the step (3) in 10mL of dimethylformamide, coating the solution on a glass plate by using an industrial film scraper, heating the glass plate at 80 ℃ for 5 hours, and drying the solvent to obtain the polyion liquid film.
(5) 2.2ml of 40% methylglyoxal aqueous solution, 1.2g of 2-imidazolecarboxaldehyde and 60ml of 10% acetic acid aqueous solution by mass are mixed and stirred and dissolved 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-imidazolecarboxaldehyde/methylglyoxal cross-linked functional polyelectrolyte porous membrane.
Examples 9,
Preparation of poly (4- (4-aminophenyl) -1-vinyl-1,2,4-triazole) bis (trifluoromethanesulfonyl) imide ionic liquid/benzaldehyde/2,3-butanedione cross-linked functional polyelectrolyte porous membrane in contrast to the self-supporting covalently cross-linked polyelectrolyte porous membrane of example 8: the preparation of the self-supporting covalently cross-linked polyelectrolyte porous membrane having a pore size of 400nm and a membrane thickness of 200 μm was different from that 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, "adding 10ml of 6g of lithium hexafluorophosphate aqueous solution" was changed to "adding 8g of lithium bis (pentafluoroethanesulfonyl) imide aqueous solution"; in step 5, 2.2ml of 40% methylglyoxal aqueous solution and 1.2g of 2-imidazolecarboxaldehyde are changed into 1.5g of 2, 3-butanedione and 1.9g of benzaldehyde; and 6, obtaining the 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.
Examples 10,
Preparation of poly (3- ((1-ethyl-3-aminoethylimidazole) bis (trifluoromethanesulfonyl) imide) -1-vinylimidazole) bis (trifluoromethanesulfonyl) imide ionic liquid/D-glyceraldehyde/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 diameter was 500nm and the film thickness was 175 μm, and the preparation of the self-supporting covalently cross-linked 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 added to "27g of 3- (1-ethylimidazole) -1-vinylimidazole bromide, 20.5g of bromoethylamine hydrobromide"; in step 3, changing the 'adding 10ml of 6g of lithium hexafluorophosphate aqueous solution' into 'adding 6g of lithium bis (trifluoromethylsulfonyl) imide aqueous solution'; in step 5, "2.2ml of 40% methylglyoxal aqueous solution, 1.2g of 2-imidazole formaldehyde" was changed to "1.4g of 1, 2-cyclohexanedione, 1.2g D-glyceraldehyde"; and step 6, obtaining poly (3- ((1-ethyl-3-aminoethylimidazole) bis (trifluoromethanesulfonyl) imide) -1-vinylimidazole) bis (trifluoromethanesulfonyl) imide ionic liquid/D-glyceraldehyde/1,2-cyclohexanedione cross-linked functional polyelectrolyte porous membrane.
Examples 11,
Preparation of poly (3- (2- (2-aminomethoxyethoxy) ethyl) -1-vinylimidazole) bis (pentafluoroethanesulfonyl) imide ionic liquid/L-glucuronic acid-3,6-lactone/methylglyoxal cross-linked functional polyelectrolyte porous membrane in contrast to the self-supporting covalently cross-linked polyelectrolyte porous membrane of example 8: the pore diameter was 320nm and the film thickness was 130 μm, and the preparation of the self-supporting covalently cross-linked polyelectrolyte porous membrane was different from the preparation method of example 8 in that: in step 1, "adding 10.5g of 4-vinyl-pyridine and 21.9g of (R) -2-amino 1-bromopropylamine hydrobromide" was changed to "adding 9.4g of vinylimidazole and 24.6g of 2- (2-aminomethoxyethoxy) bromoethane hydrobromide"; in step 3, "adding 10ml of 6g of lithium hexafluorophosphate aqueous solution" was changed to "adding 8g of lithium bis (2-oxo- (3-phenyl) butanoate) borate aqueous solution"; in step 5, changing 1.2g 2-imidazole formaldehyde into 3.8g D-glucuronic acid-3,6-lactone; in the step 6, poly (3- (2- (2-amino methoxy ethoxy) ethyl) -1-vinyl imidazole) bis (pentafluoroethanesulfonyl) imide ionic liquid/L-glucuronic acid-3,6-lactone/methylglyoxal cross-linked functional polyelectrolyte porous membrane is obtained.
Examples 12,
Preparation of 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 crosslinked functional polyelectrolyte porous membrane in contrast to the self-supporting covalently crosslinked polyelectrolyte porous membrane of example 8: the preparation of the self-supporting covalently cross-linked polyelectrolyte porous membrane having a pore size of 600nm and a membrane thickness of 250 μm was different from that of example 8 in that: in step 1, "Add 10.5g 4-vinyl-pyridine, 21.9g (R) -2-amino 1-bromopropylamine hydrobromide" changed to "Add 27g 3- (1-propyl-1,2,4-triazole) -1-vinyl-1,2,4-triazole bromide, 20.49g bromoethylamine hydrobromide"; in step 3, the procedure "adding 10ml of 6g of lithium hexafluorophosphate aqueous solution" was changed to "adding 6g of lithium bis (trifluoromethylsulfonyl) imide aqueous solution"; in step 5, "2.2ml of 40% methylglyoxal aqueous solution, 1.2g of 2-imidazole formaldehyde" was changed to "1.4g of 1, 2-cyclohexanedione, 1.8g of p-dimethylaminobenzaldehyde"; in the step 6, 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.
Examples 13,
Preparation of poly (3-aminobutyl-1- (4-vinyl) phenylimidazole) bis (2-oxopropionic acid) boronic acid ionic liquid/terephthalaldehyde/3,4-hexanedione 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 700nm and the film thickness was 310 μm, and the preparation of the self-supporting covalently cross-linked polyelectrolyte porous membrane was different from the preparation method of example 8 in that: in step 1, "10.5g of 4-vinyl-pyridine and 21.9g of (R) -2-amino 1-bromopropylamine hydrobromide" were added to "18.4 g of 1- (4-vinyl) phenylimidazole and 23.3g of bromobutylamine hydrobromide"; in step 3, "adding 10ml of 6g of lithium hexafluorophosphate aqueous solution" was changed to "adding 5g of lithium bis (2-oxopropionate) borate aqueous solution"; in step 5, 2.2ml of 40% methylglyoxal aqueous solution and 1.2g of 2-imidazolecarboxaldehyde are changed into 2.6g of 3, 4-hexanedione and 3.1g of terephthalaldehyde; and 6, obtaining the poly (3-aminobutyl-1- (4-vinyl) phenylimidazole) bis (2-oxopropionic acid) boric acid ionic liquid/terephthalaldehyde/3,4-hexanedione cross-linked functional polyelectrolyte porous membrane.
Examples 14,
Preparation of poly (3- (4-methyl-1-aminobenzene) -4-methyl- (5-vinyl) thiazole) bistrifluoromethylsulfonyl imide salt) ionic liquid/2,4-dihydroxybenzaldehyde/methylglyoxal cross-linked functional polyelectrolyte porous membrane in contrast to the self-supporting covalently cross-linked polyelectrolyte porous membrane of example 8: the preparation of the self-supporting covalently cross-linked polyelectrolyte porous membrane having a pore diameter of 350nm and a membrane thickness of 260 μm was different from that of example 8 in that: in step 1, "Add 10.5g 4-vinyl-pyridine, 21.9g (R) -2-amino 1-bromopropylamine hydrobromide" changed to "Add 12.5g 4-methyl- (5-vinyl) thiazole, 26.7g p-Aminobenzyl bromide hydrobromide"; in step 3, "adding 10ml of 6g of lithium hexafluorophosphate aqueous solution" is changed into "adding 6g of bis (trifluoromethylsulfonyl) imide lithium aqueous solution"; in step 5, 1.2g of 2-imidazolecarboxaldehyde was changed to 1.8g of 2, 4-dihydroxybenzaldehyde; in the step 6, poly (3- (4-methyl-1-aminobenzene) -4-methyl- (5-vinyl) thiazole) bistrifluoromethylsulfonyl imide) ionic liquid/2,4-dihydroxy benzaldehyde/methylglyoxal cross-linked functional polyelectrolyte porous membrane is obtained.
In order to evaluate the thermal stability of the self-supported covalent cross-linked polyelectrolyte porous membrane prepared by the invention, examples 1-4 are taken as examples, thermogravimetric analysis is performed, fig. 15 shows thermogravimetric test data of the prepared self-supported covalent cross-linked functional polyelectrolyte porous membrane, the decomposition temperature of the membrane is higher than 250 ℃, and the co-cross-linked membrane prepared by the invention is proved to have good thermal stability.
Meanwhile, in order to evaluate the chemical stability, salt tolerance, and acid and alkali tolerance of the self-supporting covalent cross-linking polyelectrolyte porous membrane prepared in the present invention, the polyelectrolyte porous membrane prepared in example 1 is respectively soaked in dimethylformamide, absolute ethyl alcohol, acetonitrile, 1mol/l NaCl salt solution, aqueous hydrochloric acid solution with pH =2, and aqueous NaOH solution with pH =12, as shown in fig. 16, after soaking for seven days, the morphology of the membrane still remains intact, and in addition, compared with the infrared spectrogram (fig. 17) of the original membrane and the membrane after soaking treatment, no obvious infrared peak change is observed, further proving that the self-supporting covalent cross-linking polyelectrolyte porous membrane prepared in the present invention has excellent chemical stability, which also overcomes the defects of poor structural stability of the traditional electrostatic cross-linking and supramolecular cross-linking PPMs and structural disintegration under high-salt or thermal environment.
In addition, as shown in FIG. 18, the self-supporting covalently cross-linked polyelectrolyte porous membrane prepared according to the invention also achieved clipping and some degree of bending, with tunable shape and mechanical strength.
Application example
Taking example 1,2,3 as representative, the ion separation performance and the influence of the membrane structure on the separation effect were tested, and as shown in fig. 19, the prepared self-supporting covalently cross-linked polyion liquid porous membrane was sandwiched between electrolytic Chi Liangge chambers, and high valence ions (Ca) in the membrane state were found by comparing the electric conductance in different solutions in the membrane-free state under the electric drive 2+ 、Mg 2+ 、Al 3+ ) The conductivity of the solution is obviously reduced relative to that of the membrane-free state, which proves that the membrane 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 membrane, so that ion separation with different valence states to a certain extent can be realized through the structural design and the pore diameter adjustment of the membrane (figure 20). The functional membrane provides a technical support for extracting lithium metal from seawater.
Claims (10)
1. A preparation method of a self-supporting covalent cross-linking functional polyelectrolyte porous membrane is characterized by comprising the following steps:
(1) Preparation of amino-containing ionic liquid monomer: 1mol of halogenated amino-containing compound, vinyl-containing compound and good solvent in proportion: (0.5-2) mol: (10-1000) ml, stirring for 2-48 h at 30-90 ℃ in nitrogen or inert gas atmosphere for quaternization, and then recrystallizing in poor solvent to obtain the amino ion-containing liquid monomer;
(2) Preparation of amino-containing hydrophobic mono-component polyion liquid homopolymer: mixing the amino-containing ionic liquid monomer prepared in the step (1), azodiisobutyronitrile and 75% of ethanol aqueous solution according to the mass ratio of 1: (0.01-0.1): (10-100), stirring for 12-72 h at 60-100 ℃ in the atmosphere of nitrogen or inert gas, removing the solvent by rotary evaporation, washing and drying by using ether, adding a sodium hydroxide solution to adjust the pH value to 9-10, dialyzing the obtained solution for 2-5 days, and adding a hydrophobic anion lithium salt to obtain the amino-containing hydrophobic single-component polyion liquid homopolymer;
(3) Preparing a mixed reaction solution: adding 1,2-dicarbonyl compound and aldehyde compound into 5-50% acid water solution by mass fraction, heating and dissolving at 25-70 ℃ to obtain mixed reaction solution;
(4) Preparing a polyion liquid film: mixing the hydrophobic single-component polyion 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, coating 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 a polyion liquid film with the matrix;
(5) Preparing a self-supporting covalent cross-linking functional polyelectrolyte porous membrane: and (3) 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 0-80 ℃ to obtain the self-supported covalent cross-linked functional polyelectrolyte porous membrane.
2. The method of 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, butylsulfone, dioxane, hydroxypropionic acid, ethylamine, ethylenediamine, glycerol, diglyme, 1,3-dioxolane, pyridine, formamide, acetonitrile, propanol or isopropanol;
the poor solvent is one or more of ethanol, acetone, diethyl ether, dioxane, cyclohexane, diglyme, 1,3-dioxolane, pyridine, propanol or isopropanol;
the amino-containing hydrophobic mono-component polyion liquid homopolymer is as follows:
the hydrophobic anionic 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,
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 of claim 1, wherein the 1,2-dicarbonyl compound, aldehyde compound and acid in the mixed reaction solution are combined in a plurality of ways.
4. The method of claim 3, wherein the 1,2-dicarbonyl compound is the self-supported covalently crosslinked functional polyelectrolyte porous membrane
The aldehyde compound is
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-C18 alkyl,
R 2 Is C1-C18 alkyl; r 3 Is H, C1-C18 alkyl,
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.
5. The method for preparing the self-supporting polyelectrolyte porous membrane with covalent cross-linking function according to claim 1, wherein the dosage ratio of the hydrophobic single-component polyion liquid homopolymer, 1,2-dicarbonyl compound, aldehyde compound, 5-50% mass fraction acid aqueous solution is (0.02-2) mol:1mol:1mol: (500-10000) ml.
6. The method of claim 1, wherein the molar ratio of amino-containing ionic liquid monomer to hydrophobic anionic lithium salt is 1: (1-10).
7. The method of preparing the self-supporting covalently cross-linked functional polyelectrolyte porous membrane according to any one of claims 1 to 6, wherein the obtained self-supporting covalently cross-linked functional polyelectrolyte porous membrane has a three-dimensional interpenetrating multi-level pore structure with a pore size of 10nm to 10 μm.
8. The method of preparing a self-supporting covalently cross-linked functional polyelectrolyte porous membrane according to any one of claims 1 to 6, wherein the thickness of the self-supporting covalently cross-linked functional polyelectrolyte porous membrane is from 20nm to 1cm.
9. A self-supporting covalently cross-linked functional polyelectrolyte porous membrane obtainable by the method of any one of claims 1 to 6.
10. Use of the covalently cross-linked functional polyelectrolyte porous membrane obtained by the production method according to any one of claims 1 to 6 for ion separation.
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