CN111229174A - Preparation method and application of Li-IIMs (lithium-ion organic Compounds) ion imprinting membrane - Google Patents
Preparation method and application of Li-IIMs (lithium-ion organic Compounds) ion imprinting membrane Download PDFInfo
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Abstract
The invention belongs to the technical field of functional material preparation, and particularly relates to a preparation method and application of a Li-IIMs (lithium-ion-exchange membranes) ion imprinted membrane. According to the invention, polydimethylsiloxane is modified through self-polymerization reaction of dopamine to form a strong-viscosity dopamine layer, then succinic anhydride is hydrolyzed on the surface of a dopamine-functionalized substrate to form carboxyl, and the carboxyl modified PDMS is further modified to construct ester modified PDMS; further taking calix [4] arene as a ligand and ethylene diamine tetraacetic acid as an eluent to prepare the Li-IIMs imprinted membrane. Compared with the traditional preparation method of the membrane material, the imprinted membrane prepared by the invention has the advantages of easy recovery, convenient subsequent separation, no secondary pollution to separated substances and the like, and well overcomes the defects of difficult recovery, easy generation of secondary pollution and the like of the existing lithium ion separation polymer.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a preparation method and application of a Li-IIMs (lithium-ion-exchange membranes) ion imprinted membrane.
Background
In recent decades, lithium has received much attention due to its wide application in lithium ion battery reactor control and in the energy industry. With increasing lithium demand, researchers have been working on finding large sources of lithium, such as extracting lithium ions (Li) from seawater+). Various extraction methods (solar evaporation, solvent extraction and chemical precipitation) have been applied to the extraction of Li+. However, these methods are still far from satisfactory due to similar ionic radii and properties at very low concentrations compared to other competing ions. Thus, a highly selective Li has been found+Separation and recovery techniques are of critical importance.
Ion Imprinting (IIT) is of particular interest because of its predetermined selectivity for template ions. Ion Imprinted Polymers (IIPs) with complementary cavity structures and oriented towards a defined template ion are a good choice based on IIT through interactions. IIPs have recently attracted a wide range of interest in the fields of electrochemical sensors, solid-phase extraction and water treatment, and can be used for the application of Li in aqueous solutions+Selective separation of (3). In some cases, high diffusion resistance, difficult separation operations and weak reproducibility make the application of IIPs more challenging. Membrane-based separation technology is considered one of the most cost-effective methods in the separation field because it is easy to scale up, low in energy consumption, and easy to operate in a continuous process. Thus, IIP is combined with Membrane Separation Technology (MST) to form ion imprinted membranes (IIM) Selective separation of Li from the Mixed solution+A promising strategy of (1). However, related research reports are lacked at present.
Disclosure of Invention
In view of the above, the present invention aims to overcome the technical defects in the prior art, solve the problems of easy loss of the ligand, low reuse rate, low adsorption capacity, etc. of the conventional ion imprinted membrane, and greatly improve the separation efficiency of target ion lithium ions.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a Li-IIMs ion imprinted membrane, which comprises the following steps:
(1) preparation of polydimethylsiloxane film:
uniformly stirring polydimethylsiloxane and curing agent B in 184 silicon rubber to obtain a mixture, placing the cubic sugar on the surface of the mixture, performing vacuum filtration, drying, curing in a water bath, and drying again to obtain a polydimethoxysilane film;
(2) polydopamine modification of polydimethylsiloxane membranes:
immersing the polydimethoxysilane film prepared in the step (1) in a trihydroxymethylaminomethane solution for pretreatment, then immersing in a dopamine solution, performing oscillation polymerization at room temperature, washing with ethanol and water, and drying to obtain a polydimethoxysilane film modified by polydopamine;
(3) carboxylation of polydimethylsiloxane films:
alkalizing the polydopamine modified polydimethoxysilane membrane in the step (2), adding the processed polydimethoxysilane membrane into N, N-dimethylformamide solution dissolved with succinic anhydride, stirring, washing with acetone, washing with ethanol, washing with water, and drying to obtain a carboxylated polydimethoxysilane membrane;
(4) preparing a blotting membrane;
immersing the carboxylated polydimethylsiloxane membrane in the step (3) in a solution A mixed with thionyl chloride and N, N-dimethylformamide, performing ultrasonic dispersion, cleaning with tetrahydrofuran, and performing vacuum drying; then adding the mixture into a mixed solution consisting of calix [4] arene, N-dimethylformamide and triethylamine, continuously stirring, washing with water and drying; adding lithium chloride, performing ultrasonic treatment, shaking at room temperature, eluting with ethylenediamine tetraacetic acid aqueous solution, and drying to obtain the Li-IIMs imprinted membrane.
The dosage relation of the polydimethylsiloxane and the curing agent B in the step (1) is 2: 0.2 to 0.5.
The vacuum filtration time in the step (1) is 6-10 h, the drying temperature is 55-65 ℃, and the drying time is 6-12 h; and the temperature for secondary drying is 35-45 ℃.
The polymerization time in the step (2) is 12-36 h; the drying temperature is 35-45 ℃.
The dopamine solution in the step (2) is a trihydroxymethylaminomethane solution containing dopamine.
The volume ratio of the thionyl chloride to the N, N-dimethylformamide of the solution A in the step (4) is 20: 0.5-0.8 mL; the stirring time is 8-12 h.
In the step (4), the dosage ratio of calix [4] arene, N-dimethylformamide and triethylamine in the mixed solution is 0.5 g: 30-60 mL: 0.5 mL.
The concentration of the lithium chloride in the step (4) is 50-120 mg/L.
The ultrasonic dispersion time in the step (4) is 12-36 hours, and the oscillation time is 6-24 hours.
The invention also provides application of the Li-IIMs imprinted membrane prepared by the preparation method in the field of selective adsorption and separation of lithium ions, and particularly application of the Li-IIMs imprinted membrane in selective adsorption and separation of lithium ions in mixed solutions of lithium ions, sodium ions, potassium ions, rubidium ions and the like.
The invention has the advantages and technical effects that:
the method comprises the steps of modifying Polydimethylsiloxane (PDMS) through self-polymerization reaction of dopamine (PDA) to form a strongly-viscous PDA layer, hydrolyzing succinic anhydride on the surface of a PDA-functionalized substrate to form carboxyl, and further modifying the carboxyl-modified PDMS to construct ester-modified PDMS; further using a cup [4]]Li-IIMs stamp prepared by using arene as ligand and ethylene diamine tetraacetic acid as eluentAnd (4) tracing the film. Compared with the traditional preparation method of the membrane material, the preparation method has the advantages that the ester group of the ligand is still on the surface of the membrane after repeated acidic eluent, so that the cyclic use performance of the prepared Li-IIMs imprinted membrane is greatly improved. The blotting membrane prepared by the invention has the advantages of easy recovery, convenient subsequent separation, no secondary pollution to separated substances and the like, and well solves the defects of difficult recovery, easy generation of secondary pollution and the like of the existing lithium ion separation polymer. And has the advantages of high porosity, high flux and high flow rate. The Li-IIMs imprinted membrane prepared by the invention has higher selectivity on lithium ions, can effectively separate lithium ions from sodium ions, potassium ions, rubidium ions and other analogues, and can separate Li from seawater+The method has great potential.
Drawings
FIG. 1 is an infrared characteristic peak spectrum of the Li-IIMs imprinted membrane prepared in example 1 at different stages;
FIG. 2 is a graph of competitive adsorption of Li-IIMs and Li-NIMs prepared in example 1 at different times; in the figure, the left figure is the competitive adsorption figure of Li-IIMs, and the right figure is the competitive adsorption figure of Li-NIMs;
FIG. 3 is a graph of competitive adsorption of Li-IIMs and Li-NIMs prepared in example 2 at different times; in the figure, the left figure is the competitive adsorption figure of Li-IIMs, and the right figure is the competitive adsorption figure of Li-NIMs;
FIG. 4 is a graph of competitive adsorption of Li-IIMs and Li-NIMs prepared in example 3 at different times; in the figure, the left figure is the competitive adsorption figure of Li-IIMs, and the right figure is the competitive adsorption figure of Li-NIMs.
Detailed Description
The invention discloses a Li-IIMs imprinted membrane and a preparation method and application thereof. Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. The embodiments described below are only a part of the embodiments of the present invention, and not all of them. While the methods and products of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications of the methods described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of the present invention without departing from the spirit and scope of the invention.
Unless otherwise specified, the reagents involved in the examples of the present invention are all commercially available products, and all of them are commercially available. The 184 silicone rubber is derived from SYLGARD184, dow corning.
The specific method for testing the adsorption performance of the invention is as follows:
(1) selective adsorption experiment
Weighing 5 parts of Li-IIMs imprinted membrane in each example, putting the membrane into a glass test tube, respectively adding 10mL of mixed solution of 25, 50, 100, 150, 200 and 250 mg/L rubidium ions, calcium ions, magnesium ions and cesium ions, standing and adsorbing for 3 hours at room temperature, measuring the concentration of lithium ions, sodium ions, potassium ions and rubidium ions which are not adsorbed in the solution by an inductively coupled plasma emission spectrometer after adsorption is finished, and calculating the adsorption capacity (Qe, mg/g) according to the result:
Q= (C0- C) × V / m (1)
wherein C is0(mg/L) and C (mg/L) are the concentrations of the same molecule in the solution before and after adsorption, respectively, V (mL) is the volume of the adsorption solution, and m (g) is the mass of the added Li-IIMs.
(2) Permselectivity experiments
Firstly, a combined cross-flow permeation device is self-made, a square groove with the size of 10 mm multiplied by 5 mm is formed in the surface of a hard plastic pipe, the square groove identical to that of the plastic pipe is cut on a double-layer plastic film, a Li-IIMs is clamped at the inner groove of the double-layer plastic film, and the groove of the double-layer plastic film clamped with the Li-IIMs is aligned with the groove of the hard plastic pipe and then is fixed on the periphery of the hard plastic pipe; then, connecting soft silicone tubes to two sides of a self-made cross-flow permeation device respectively and connecting the soft silicone tubes with a peristaltic pump, pumping a mixed solution of lithium ions, sodium ions, potassium ions and rubidium ions with the concentration of 200 mg/L into a pipeline, and setting the flow rate to be 100 mL/h; sampling was performed at 5, 10, 30, 45, 60, 90, 120, 180 min at the cross-flow permeation device and the concentrations of lithium, sodium, potassium and rubidium ions permeating the Li-IIMs were determined by inductively coupled plasma emission spectroscopy.
Example 1
(1) Preparation of polydimethylsiloxane film:
placing 2 g of polydimethylsiloxane in a culture dish, uniformly coating, adding 0.2 g of curing agent B in 184 g of silicon rubber, uniformly stirring to obtain a mixture, placing edible sugar on the surface of the mixture, performing vacuum filtration for 6 hours at room temperature, filtering the mixture into the sugar, and drying in a 65 ℃ oven for 6 hours; soaking in water bath for curing, changing water every 6h, and drying at 40 ℃ after 3 times to obtain a polydimethoxysilane film;
(2) polydopamine modification of polydimethylsiloxane membranes:
0.1211 g of tris (hydroxymethyl) aminomethane is dissolved in 100 mL of deionized water, and the pH value is quickly adjusted to 8.5 to obtain tris (hydroxymethyl) aminomethane solution; adding 0.2 g of dopamine into another part of the trihydroxymethyl aminomethane solution to obtain a dopamine solution; immersing the polydimethoxysilane film prepared in the step (1) in a trihydroxymethylaminomethane solution for pretreatment for 5min, then immersing in a dopamine solution, shaking for 12h at room temperature, washing with ethanol and water, and drying at 40 ℃ to obtain a polydimethoxysilane film modified by polydopamine;
(3) carboxylation of polydimethylsiloxane films:
immersing the polydopamine modified polydimethylsiloxane membrane in the step (2) in a 20% (w/v) sodium hydroxide aqueous solution for alkalization, adding the polydopamine modified polydimethylsiloxane membrane into 75 mL of N, N-dimethylformamide solution dissolved with 3g of succinic anhydride, stirring for 8 hours, washing with acetone, washing with ethanol, washing with water, and drying at 60 ℃ to obtain a carboxylated polydimethylsiloxane membrane;
(4) preparing a blotting membrane;
immersing the carboxylated polydimethylsiloxane membrane in the step (3) in a solution A mixed with 20 mL of thionyl chloride and 0.5 mL of N, N-dimethylformamide, ultrasonically dispersing for 12h, washing with tetrahydrofuran, and vacuum drying at 60 ℃; then adding the mixture into a mixed solution consisting of 0.5g of ligand calix [4] arene, 30 mL of N, N-dimethylformamide and 0.5 mL of triethylamine, continuously stirring, washing with water, and drying at 70 ℃; adding 100 mL of lithium chloride with the concentration of 50 mg/L, uniformly performing ultrasonic treatment, shaking for 6h at room temperature, eluting with 0.2mol/L of ethylenediamine tetraacetic acid aqueous solution, and drying to obtain the Li-IIMs imprinted membrane.
In the embodiment, non-imprinted lithium ion imprinted membranes Li-NIMs are prepared at the same time, and the difference between the non-imprinted lithium ion imprinted membranes Li-NIMs and the non-imprinted membranes Li-IIMs is that the ligand calix [4] arene is not added in the preparation process.
The application does not limit the ligand calix [4] arene, and in order to further explain the technical scheme, the preparation method of the ligand calix [4] arene in the embodiment is as follows:
firstly, dissolving 13.3 g of p-tert-butylcalix [4] arene, 9.02 g of phenol and 14 g of anhydrous aluminum chloride in 125 mL of anhydrous toluene to prepare a reaction solution, and continuously stirring for 1 h under the nitrogen atmosphere until the reaction solution is changed from turbid to clear; pouring the reaction solution into 100 mL of ice water under the stirring state, cooling the solution in an ice salt bath, continuously stirring, dropwise adding 4 mol/L hydrochloric acid until the whole reaction system is clear, and separating out an organic phase and a water phase; each time with toluene extraction 3 times, combined organic phase, dried with anhydrous sodium sulfate, filter, remove anhydrous sodium sulfate, rotary evaporation to remove toluene, adding methanol white solid precipitation. And (3) after suction filtration, washing with methanol for three times, drying the obtained sample to obtain a white solid, and recrystallizing with chloroform and methanol to obtain calix [4] arene.
FIG. 1 is the infrared characteristic peak spectra of the Li-IIMs imprinted membrane prepared in this example at different stages; as can be seen in fig. 1, the C = O double bond and the C — O bond are significantly shifted after the target is adsorbed, and the target is eluted and returned to the position before the adsorption. As can be seen, ester groups in the prepared Li-IIMs imprinted membrane are not damaged in the elution process, and the recycling performance of the Li-IIMs imprinted membrane is greatly improved.
FIG. 2 is a schematic diagram showing competitive adsorption of Li-IIMs and Li-NIMs prepared in the present example at different times; in the figure, the left figure is the competitive adsorption figure of Li-IIMs, and the right figure is the competitive adsorption figure of Li-NIMs; fig. 2 shows that the adsorption capacity of the lithium ion imprinted membrane prepared in the embodiment on lithium ions in a mixed solution with a concentration of 25-250 mg/L is higher than that of sodium ions, potassium ions and rubidium ions, that is, the lithium ion imprinted membrane has a selective adsorption and separation effect on lithium ions. The prepared Li-NIMs non-imprinted membrane has no selectivity on lithium ions and competitive ions (sodium ions, potassium ions and rubidium ions) thereof, and the aim of selective adsorption and separation cannot be achieved.
Example 2
(1) Preparation of polydimethylsiloxane film:
placing 2 g of polydimethylsiloxane in a culture dish, uniformly coating, adding 0.2 g of curing agent B in 184 silicon rubber, uniformly stirring to obtain a mixture, placing edible cube sugar on the surface of the mixture, carrying out vacuum filtration for 8 hours at room temperature, carrying out vacuum filtration on the mixture in a cube sugar oven at 60 ℃, drying for 10 hours in an oven, immersing in a water bath for curing, changing water every 6 hours, and drying at 45 ℃ after 3 times of water, thus obtaining a polydimethoxysilane membrane;
(2) polydopamine modification of polydimethylsiloxane membranes:
immersing the polydimethoxysilane film prepared in the step (1) in a trihydroxymethylaminomethane solution for pretreatment for 3min, then immersing in a dopamine solution, shaking for 24h at room temperature, washing with ethanol and water, and drying at 40 ℃ to obtain a polydimethoxysilane film modified by polydopamine;
(3) carboxylation of polydimethylsiloxane films:
immersing the polydopamine modified polydimethylsiloxane membrane in the step (2) in a 20% (w/v) sodium hydroxide aqueous solution for alkalization, adding the polydopamine modified polydimethylsiloxane membrane into 75 mL of N, N-dimethylformamide solution dissolved with 3g of succinic anhydride, stirring for 10 hours, washing with acetone, washing with ethanol, washing with water, and drying at 60 ℃ to obtain a carboxylated polydimethylsiloxane membrane;
(4) preparing a blotting membrane;
immersing the carboxylated polydimethylsiloxane membrane in the step (3) in a solution A mixed with 20 mL of thionyl chloride and 0.8mL of N, N-dimethylformamide, ultrasonically dispersing for 24h, washing with tetrahydrofuran, and vacuum drying at 60 ℃; then adding the mixture into a mixed solution consisting of 0.5g of ligand calix [4] arene, 60 mL of N, N-dimethylformamide and 0.5 mL of triethylamine, continuously stirring, washing with water, and drying at 70 ℃; adding 100 mL of lithium chloride with the concentration of 120 mg/L, uniformly performing ultrasonic treatment, shaking at room temperature for 12h, eluting with 0.2mol/L of ethylenediamine tetraacetic acid aqueous solution, and drying to obtain the Li-IIMs imprinted membrane.
In the embodiment, non-imprinted lithium ion imprinted membranes Li-NIMs are prepared at the same time, and the difference between the non-imprinted lithium ion imprinted membranes Li-NIMs and the non-imprinted membranes Li-IIMs is that the ligand calix [4] arene is not added in the preparation process.
FIG. 3 is a schematic diagram showing competitive adsorption of Li-IIMs and Li-NIMs prepared in the present example at different times; in the figure, the left figure is the competitive adsorption figure of Li-IIMs, and the right figure is the competitive adsorption figure of Li-NIMs; fig. 3 shows that the adsorption capacity of the lithium ion imprinted membrane prepared in the embodiment on lithium ions in a mixed solution with a concentration of 25-250 mg/L is higher than that of sodium ions, potassium ions and rubidium ions, that is, the lithium ion imprinted membrane has a selective adsorption and separation effect on lithium ions. The prepared Li-NIMs non-imprinted membrane has no selectivity on lithium ions and competitive ions (sodium ions, potassium ions and rubidium ions) thereof, and the aim of selective adsorption and separation cannot be achieved.
Example 3
(1) Preparation of polydimethylsiloxane film:
placing 2 g of polydimethylsiloxane in a culture dish, uniformly coating, adding 0.5g of curing agent B in 184 silicon rubber, uniformly stirring to obtain a mixture, placing edible cube sugar on the surface of the mixture, carrying out vacuum filtration for 10 hours at room temperature, carrying out vacuum filtration on the mixture into the cube sugar, drying the mixture in an oven at 55 ℃ for 12 hours, immersing the mixture in a water bath for curing, changing water every 6 hours, and drying at 35 ℃ after 3 times to obtain a polydimethoxysilane membrane;
(2) polydopamine modification of polydimethylsiloxane membranes:
immersing the polydimethoxysilane film prepared in the step (1) in a trihydroxymethylaminomethane solution for pretreatment for 6min, then immersing in a dopamine solution, shaking for 36h at room temperature, washing with ethanol and water, and drying at 40 ℃ to obtain a polydimethoxysilane film modified by polydopamine;
(3) carboxylation of polydimethylsiloxane films:
immersing the polydopamine modified polydimethylsiloxane membrane in the step (2) in a 20% (w/v) sodium hydroxide aqueous solution for alkalization, adding the polydopamine modified polydimethylsiloxane membrane into 75 mL of N, N-dimethylformamide solution dissolved with 3g of succinic anhydride, stirring for 12h, washing with acetone, washing with ethanol, washing with water, and drying at 60 ℃ to obtain a carboxylated polydimethylsiloxane membrane;
(4) preparing a blotting membrane;
immersing the carboxylated polydimethylsiloxane membrane in the step (3) in a solution A mixed with 20 mL of thionyl chloride and 0.5 mL of N, N-dimethylformamide, ultrasonically dispersing for 36h, washing with tetrahydrofuran, and vacuum drying at 60 ℃; then adding the mixture into a mixed solution consisting of 0.5g of ligand calix [4] arene, 30 mL of N, N-dimethylformamide and 0.5 mL of triethylamine, continuously stirring, washing with water, and drying at 70 ℃; adding 100 mL of lithium chloride with the concentration of 100 mg/L, uniformly performing ultrasonic treatment, shaking for 24h at room temperature, drying, eluting the template by using 0.2mol/L of ethylenediamine tetraacetic acid aqueous solution, and drying to obtain the Li-IIMs imprinted membrane.
In the embodiment, non-imprinted lithium ion imprinted membranes Li-NIMs are prepared at the same time, and the difference between the non-imprinted lithium ion imprinted membranes Li-NIMs and the non-imprinted membranes Li-IIMs is that the ligand calix [4] arene is not added in the preparation process.
FIG. 4 is a schematic diagram of competitive adsorption of Li-IIMs and Li-NIMs prepared in this example at different times; in the figure, the left figure is the competitive adsorption figure of Li-IIMs, and the right figure is the competitive adsorption figure of Li-NIMs; fig. 3 shows that the adsorption capacity of the lithium ion imprinted membrane prepared in the embodiment on lithium ions in a mixed solution with a concentration of 25-250 mg/L is higher than that of sodium ions, potassium ions and rubidium ions, that is, the lithium ion imprinted membrane has a selective adsorption and separation effect on lithium ions. The prepared Li-NIMs non-imprinted membrane has no selectivity on lithium ions and competitive ions (sodium ions, potassium ions and rubidium ions) thereof, and the aim of selective adsorption and separation cannot be achieved.
The above examples are only for illustrating the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (10)
1. The preparation method of the Li-IIMs ion imprinting film is characterized by comprising the following steps of:
(1) preparation of polydimethylsiloxane film:
uniformly stirring polydimethylsiloxane and curing agent B in 184 silicon rubber to obtain a mixture, placing the cubic sugar on the surface of the mixture, performing vacuum filtration, drying, curing in a water bath, and drying again to obtain a polydimethoxysilane film;
(2) polydopamine modification of polydimethylsiloxane membranes:
immersing the polydimethoxysilane film prepared in the step (1) in a trihydroxymethylaminomethane solution for pretreatment, then immersing in a dopamine solution, performing oscillation polymerization at room temperature, washing with ethanol and water, and drying to obtain a polydimethoxysilane film modified by polydopamine;
(3) carboxylation of polydimethylsiloxane films:
alkalizing the polydopamine modified polydimethoxysilane membrane in the step (2), adding the processed polydimethoxysilane membrane into N, N-dimethylformamide solution dissolved with succinic anhydride, stirring, washing with acetone, washing with ethanol, washing with water, and drying to obtain a carboxylated polydimethoxysilane membrane;
(4) preparing a blotting membrane;
immersing the carboxylated polydimethylsiloxane membrane in the step (3) in a solution A mixed with thionyl chloride and N, N-dimethylformamide, performing ultrasonic dispersion, cleaning with tetrahydrofuran, and performing vacuum drying; then adding the mixture into a mixed solution consisting of calix [4] arene, N-dimethylformamide and triethylamine, continuously stirring, washing with water and drying; adding lithium chloride, performing ultrasonic treatment, shaking at room temperature, eluting with ethylenediamine tetraacetic acid aqueous solution, and drying to obtain the Li-IIMs imprinted membrane.
2. The method according to claim 1, wherein the polydimethylsiloxane in step (1) is used in an amount of 2: 0.2 to 0.5.
3. The preparation method according to claim 1, wherein the vacuum filtration time in the step (1) is 6-10 h, the drying temperature is 55-65 ℃, and the drying time is 6-12 h; and the temperature for secondary drying is 35-45 ℃.
4. The method according to claim 1, wherein the polymerization time in the step (2) is 12 to 36 hours; the drying temperature is 35-45 ℃.
5. The method according to claim 1, wherein the dopamine solution in step (2) is a dopamine-containing tris solution; the stirring time is 8-12 h.
6. The method according to claim 1, wherein the volume ratio of thionyl chloride to N, N-dimethylformamide in the solution A in the step (4) is 20: 0.5-0.8 mL.
7. The production method according to claim 1, wherein the amount ratio of calix [4] arene, N-dimethylformamide and triethylamine in the mixed solution in step (4) is 0.5 g: 30-60 mL: 0.5 mL.
8. The method according to claim 1, wherein the concentration of lithium chloride in the step (4) is 50 to 120 mg/L.
9. The preparation method according to claim 1, wherein the ultrasonic dispersion time in the step (4) is 12-36h, and the oscillation time is 6-24 h.
10. The method for preparing a Li-IIMs ion imprinted membrane as defined in any one of claims 1 to 9, wherein the prepared Li-IIMs ion imprinted membrane is adapted to selective adsorption and separation of lithium ions.
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