CN114149580B - Rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane and preparation method and application thereof - Google Patents
Rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of porous functional materials, and provides a rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane and a preparation method and application thereof. The rigid twisted microporous polymer provided by the invention has a rigid structure, contains twisted elements, is stable in structure and good in film forming property, and has good ion selectivity after being acidified by strong oxidizing acid. The sulfonated polyether sulfone membrane and the acidified rigid twisted microporous polymer membrane are compounded to form the porous composite membrane with the asymmetric structure and the pore diameter difference; the composite membrane has higher porosity, high ion flux and good ion selectivity, can form a typical ion rectification effect, and realizes high output power and stable salt difference power generation. In addition, the acidification rigidity distortion microporous polymer membrane and the sulfonated polyether sulfone membrane are compounded in an interfacial solvent volatilization mode, the steps are simple, the formed heterogeneous composite membrane can accelerate the transfer of ions, and heterogeneous same charge ions enter the membrane, so that the internal consumption of the membrane is reduced.
Description
Technical Field
The invention relates to the technical field of preparation of porous functional materials, in particular to a rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane and a preparation method and application thereof.
Background
Natural energy is an important material basis for social development, renewable energy is reasonably constructed and utilized, and the primary condition for realizing sustainable development is achieved.
Sea water is natural energy with more capacity in the current ecological environment, salt difference power generation is one of the current efficient means for utilizing sea water resources, and salt difference is the concentration difference of the sea water and fresh water resources, so that a chemical potential difference is formed between the sea water and the fresh water. The main working principle of salt-difference power generation is to convert the reverse electroosmosis difference into electric energy. In the process of salt-difference power generation, the most critical factor is the ion-selective membrane.
The key factors of the ion selective membrane itself are the ion selectivity of the membrane and the membrane flux. Most of the current ion selective membranes are resin membranes which have the advantages of high economical efficiency, high flux, good recycling effect and long service life, but the ion selectivity of the resin membranes is poor, so that the application of the resin membranes in ion exchange is limited.
Rigid twisted microporous polymers have a unique structure and have been of interest to researchers. Polymers cannot be efficiently stacked when densely formed due to the presence of various rigid, twisted cellular structures within the molecule, thereby creating a large number of micropores (mostly below 2 nm) that are often used as the best channels for gas separation. The membrane formed by the rigid twisted microporous polymer is a membrane formed by a rigid skeleton which is stably connected through polymerization, and the rigid twisted structure of the polymer and the fixed modified ion group exchange sites can easily realize high-efficiency ion transfer.
At present, it is reported that a covalent organic framework/graphene oxide composite film is used as an ion selective film in a salt difference power generation device, specifically, graphene oxide nanosheets are stacked into a compact graphene oxide film through vacuum filtration, the prepared covalent organic framework crystal material is subjected to solvent ultrasonic treatment to form nanosheets, and then the nanosheets are deposited on the graphene oxide film to form the composite ion selective film. It has also been reported that rigid twisted microporous polymer membranes are mixed with a covalent organic framework/metal organic framework to form mixed matrix membranes. The lower thin film pore channel or the interlayer of the composite film material is easy to block to a certain degree, so that the ion flux is reduced, and the ion selectivity of the composite film is influenced.
Disclosure of Invention
The invention aims to provide a rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane and a preparation method and application thereof. The rigid twisted microporous polymer provided by the invention has the advantages of stable structure, good film forming property and good ion selectivity after acidification, and the ion selective porous composite film with an asymmetric structure can be obtained by compounding the acidified rigid microporous polymer film and the sulfonated polyether sulfone film, and has good ion selectivity and high film flux.
In order to achieve the above object, the present invention provides the following technical solutions:
a rigid twisted microporous polymer having the general structural formula shown in formula I:
in formula I: n represents the degree of polymerization, A is any one of the structures shown by A-1 to A-5:
in A-2, R 1 、R 2 、R 3 And R 4 Independently H, Br, methyl or CN;
in A-4, R 5 、R 6 、R 7 And R 8 Independently is H or methyl;
b is any one of structures shown by B-1 to B-5:
the invention provides a preparation method of the rigid twisted microporous polymer, which comprises the following steps:
mixing a first monomer, a second monomer, a catalyst and an organic solvent to carry out polycondensation reaction to obtain a rigid twisted microporous polymer with a structure shown in a formula I;
the first monomer is any one of monomers with structures shown as i-1 to i-5:
r in the formula i-2 1 、R 2 、R 3 And R 4 The same as in the formula A-2; r in the formula i-4 5 、R 6 、R 7 And R 8 The kind of (B) is the same as in the formula A-4;
the second monomer is any one of monomers having a structure represented by formulas ii-1 to ii-5:
preferably, the catalyst is one or more of alkali metal salt and alkali metal hydroxide.
Preferably, the temperature of the polycondensation reaction is 40-150 ℃ and the time is 72-120 h.
The invention also provides an acidified rigid twisted microporous polymer, which is obtained by acidifying the rigid twisted microporous polymer with the structure shown in the formula I, wherein the acidic reagent for acidification is strong oxidizing acid.
The invention also provides a rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane, which comprises a sulfonated polyether sulfone membrane and an acidified rigid twisted microporous polymer membrane arranged on the surface of the sulfonated polyether sulfone membrane; the acidified rigid twisted microporous polymer membrane is prepared from the acidified rigid twisted microporous polymer according to the above scheme.
Preferably, the sulfonated polyether sulfone membrane is prepared by adopting a sulfonated polyether sulfone compound with a structure shown in formula III:
in formula III: m and n are the degree of polymerization;
c is the following structure:
d is any one of the following structures:
the invention also provides a preparation method of the rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane, which comprises the following steps:
dissolving a rigid twisted microporous polymer with a structure shown in a formula I in an organic solvent to obtain a rigid twisted microporous polymer solution;
coating the rigid twisted microporous polymer solution on a substrate, volatilizing and removing a solvent in the obtained wet film, and then separating the substrate to obtain a rigid twisted microporous polymer film;
acidifying the rigid twisted microporous polymer membrane with a strong oxidizing acid to obtain an acidified rigid twisted microporous polymer membrane;
coating an organic solvent on the surface of the sulfonated polyether sulfone membrane, then covering the acidified rigid twisted microporous polymer membrane on the surface of the sulfonated polyether sulfone membrane, and then volatilizing and removing the organic solvent to obtain the rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane.
Preferably, the strong oxidizing acid comprises one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and hypochlorous acid.
The invention also provides application of the rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane in a salt-difference power generation device.
The invention provides a rigid twisted microporous polymer, which has a structural general formula shown in formula I. The rigid twisted microporous polymer provided by the invention has a rigid structure and contains twisted elements, and can always keep a stable structure in the subsequent cationic modification (namely acidification) process.
The invention also provides an acidified rigid twisted microporous polymer, which is obtained by acidifying the rigid twisted microporous polymer with the structure shown in the formula I, wherein the acidic reagent for acidification is strong oxidizing acid. According to the invention, the rigid twisted microporous polymer is subjected to cation modification through acidification, strong oxidizing acid radical groups are introduced into the polymer, and the acid radical groups are connected to the main chain of the polymer skeleton, so that the main chain of the polymer is negatively charged, and only cations are allowed to pass through when ions pass through, therefore, the acidified rigid twisted microporous polymer provided by the invention has good ion selectivity. In addition, the acidified rigid twisted microporous polymer provided by the invention has good thermal stability, chemical stability and film-forming property, and has high commercial application value.
The invention also provides a rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane, which comprises a sulfonated polyether sulfone membrane and an acidified rigid twisted microporous polymer membrane arranged on the surface of the sulfonated polyether sulfone membrane. The sulfonated polyether sulfone membrane and the acidified rigid twisted microporous polymer membrane are compounded to form the porous composite membrane with the asymmetric structure and the pore diameter difference; the composite membrane has rigid and highly-twisted microporous polymers, so that the composite membrane has high porosity (5-10%), high water and ion flux, can form a typical ion rectification effect, and realizes high output power and stable salt difference power generation; the two charged films are effectively compounded to form a heterostructure, so that the transmission of ions with different charges is accelerated, and the entry of ions with the same charges is inhibited, thereby reducing internal consumption.
The invention also provides a preparation method of the rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane. Firstly, preparing a rigid twisted microporous polymer membrane, then acidifying the polymer membrane to obtain an acidified rigid twisted microporous polymer membrane, and compounding the acidified rigid twisted microporous polymer membrane with a sulfonated polyether sulfone membrane in a manner of interfacial solvent volatilization, namely, coating an organic solvent on the surface of the sulfonated polyether sulfone membrane, attaching the acidified rigid twisted microporous polymer membrane to the surface of the sulfonated polyether sulfone membrane, partially liquefying the acidified rigid twisted microporous polymer membrane at the moment of attachment, adhering to the sulfonated polyether sulfone membrane, and forming a mutual traction acting force between the acidified rigid twisted microporous polymer membrane and the sulfonated polyether sulfone membrane, thereby forming the ion selective porous composite membrane with an asymmetric structure. The preparation method provided by the invention has the advantages of simple steps, easy operation, high flux of the obtained composite membrane and good ion selectivity.
Drawings
Fig. 1 is a nuclear magnetic spectrum of the rigid twisted microporous polymer prepared in example 1 and the carboxylic acid modified rigid twisted microporous polymer prepared in example 3;
FIG. 2 is an IR spectrum of a carboxylic acid modified rigid twisted microporous polymer prepared in example 3;
FIG. 3 is a scanning electron microscope surface image of a carboxylic acid modified rigid twisted microporous polymer membrane prepared in example 3;
FIG. 4 is a nuclear magnetic spectrum of the polyethersulfone compound and sulfonated polyethersulfone compound prepared in example 4;
FIG. 5 is an IR spectrum of sulfonated polyethersulfone compound prepared in example 4;
FIG. 6 is a scanning electron microscope surface image of the sulfonated polyethersulfone membrane prepared in example 5;
FIG. 7 is a cross-sectional image of a carboxylic acid modified rigid twisted microporous polymer-sulfonated polyethersulfone compound composite membrane prepared in example 5;
FIG. 8 is a graph of current-voltage curves for a salt-differential device prepared in example 6 under 100-fold concentration conditions;
FIG. 9 is a graph of ionic current rectification for the rigid twisted microporous polymer-sulfonated polyethersulfone porous composite membrane prepared in example 5 in the same electrolyte solution;
fig. 10 is a current-voltage graph of the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyethersulfone composite membrane prepared in example 5 in the same electrolyte solution.
Detailed Description
The invention provides a rigid twisted microporous polymer, which has a structural general formula shown as formula I:
in formula I: n represents the degree of polymerization, A is any one of the structures represented by A-1 to A-5:
in A-2, R 1 、R 2 、R 3 And R 4 Independently H, Br, methyl or CN;
in A-4, R 5 、R 6 、R 7 And R 8 Independently is H or methyl;
b is any one of structures shown by B-1 to B-5:
in the invention, the value of n in the formula I is preferably 600-1600, preferably 800-1400.
In the present invention, when A has a structure represented by A-1 and B has a structure represented by B-2 in formula I, the structural formula of the rigid twisted microporous polymer is represented as formula I-1:
in the present invention, when A has a structure represented by A-2 and B has a structure represented by B-2 in formula I, the structural formula of the rigid twisted microporous polymer is represented as formula I-2:
in the present invention, when A has a structure represented by A-3 and B has a structure represented by B-2 in formula I, the structural formula of the rigid twisted microporous polymer is represented as formula I-3:
in the present invention, when A has a structure represented by A-4 and B has a structure represented by B-2 in formula I, the structural formula of the rigid twisted microporous polymer is represented as formula I-4:
in the present invention, when A has a structure represented by A-5 and B has a structure represented by B-2 in formula I, the structural formula of the rigid twisted microporous polymer is represented as formula I-5:
the remaining structural formulas are not listed.
The invention also provides a preparation method of the rigid twisted microporous polymer, which comprises the following steps:
mixing a first monomer, a second monomer, a catalyst and an organic solvent to carry out polycondensation reaction to obtain a rigid twisted microporous polymer with a structure shown in a formula I;
the first monomer is any one of monomers with structures shown as i-1 to i-5:
the second monomer is any one of monomers having a structure represented by formulas ii-1 to ii-5:
in the present invention, the kind of the first monomer and the second monomer may be selected according to the structure of the target polymer, and specifically, when the first monomer is I-1 and the second monomer is ii-2, the resulting polymer has the structure represented by the above formula I-1, and when the first monomer is I-2 and the second monomer is ii-2, the resulting polymer has the structure represented by the above formula I-2; when the first monomer is I-3 and the second monomer is ii-2, the obtained polymer has a structure shown in the formula I-3; when the first monomer is I-4 and the second monomer is ii-2, the obtained polymer has a structure shown in the formula I-4; when the first monomer is I-5 and the second monomer is ii-2, the obtained polymer has a structure shown in the formula I-5; the rest cases are not listed.
In the present invention, the molar ratio of the first monomer to the second monomer is preferably 0.8 to 1.4:0.8 to 1.4, more preferably 0.9 to 1.1: 0.9 to 1.1. In particular embodiments of the invention, it is preferred to control the molar amount of one of the monomers to be in slight excess to ensure that the other monomer is sufficiently reacted to promote polymer synthesis.
In the invention, the catalyst is preferably one or more of alkali metal salt and alkali metal hydroxide; the alkali metal salt is preferably an alkali metal carbonate, more preferably potassium carbonate and/or sodium carbonate; the alkali metal hydroxide is preferably potassium hydroxide and/or sodium hydroxide; the amount of the catalyst is preferably 1-2 times of the total molar amount of the first monomer and the second monomer.
In the invention, the organic solvent for the polycondensation reaction is preferably a polar organic solvent which has good solubility to the monomer, and in the specific embodiment of the invention, the organic solvent is preferably subjected to anhydrous and anaerobic treatment, so that the reverse promotion effect of water on the polycondensation reaction is avoided, and the influence on the polycondensation reaction is reduced; in the present invention, the polar organic solvent is preferably one or more selected from N, N-dimethylformamide, N-dimethylacetamide, acetonitrile, methanol, ethanol, propanol, acetone, dioxane, tetrahydrofuran, N-butanol, ethyl acetate, diethyl ether, dichloromethane, and chloroform.
In the invention, the temperature of the polycondensation reaction is preferably 40-150 ℃, more preferably 50-80 ℃, and the reaction time is preferably 72-120 h, more preferably 80-96 h; the polycondensation reaction is preferably carried out under the protection of inert gas, and specifically, the feeding process of the monomer and the solvent and the polycondensation reaction are preferably carried out under the protection of inert gas; the inert gas is preferably argon; the polycondensation reaction is preferably carried out under the condition of stirring, and the stirring rotating speed is not specially required, and the stirring rotating speed can be adjusted according to the volume of the reactor.
After the polycondensation reaction is completed, the present invention preferably subjects the obtained reaction solution to a post-treatment to obtain a rigid twisted microporous polymer. In the present invention, when the target product is a rigid twisted microporous polymer having a structure represented by formula I-1, formula I-2, formula I-3, or formula I-4, the post-treatment preferably comprises the steps of: adding the reaction solution into water, separating out a solid product, filtering, washing and drying the obtained solid product to obtain a crude product; recrystallizing the crude product to obtain the rigid twisted microporous polymer. In the invention, the drying is preferably vacuum drying, the temperature of the vacuum drying is preferably 80-120 ℃, the time of the vacuum drying is preferably 12-24 h, and in the specific embodiment of the invention, the vacuum drying is preferably carried out until the weight is constant; the recrystallization is preferably: dissolving the crude product in a polar organic solvent until the crude product is saturated to obtain a saturated crude product solution, and then adding a solvent for recrystallization into the saturated crude product solution to separate out a sheet product, namely a recrystallized product; in a specific embodiment of the present invention, the number of recrystallization is preferably 3 to 5; the solvent for recrystallization is preferably methanol or an acetone-methanol mixed solvent, and the volume ratio of acetone to methanol in the acetone-methanol mixed solvent is preferably 2: 1. In the present invention, when the target product is a rigid twisted microporous polymer having a structure represented by formula I-5, the post-treatment preferably comprises the steps of: heating the reaction liquid to be viscous, then pouring the reaction liquid into methanol, filtering and precipitating the reaction liquid in the methanol twice, and drying the obtained precipitate in vacuum to obtain the target product.
The invention also provides an acidified rigid twisted microporous polymer, which is obtained by acidifying the rigid twisted microporous polymer with the structure shown in the formula I, wherein the acidic reagent for acidification is strong oxidizing acid. In the present invention, the strong oxidizing acid preferably includes one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and hypochlorous acid; in the present invention, when the acidic reagent is hydrochloric acid, a carboxyl group is introduced into the rigid twisted microporous polymer by acidification, specifically, a CN group in the rigid twisted microporous polymer is modified into a carboxyl group, when the acidic reagent is sulfuric acid, phosphoric acid, nitric acid, and hypochlorous acid, a sulfonic acid group, a phosphoric acid group, a nitric acid group, or a hypochlorous acid group is introduced into the rigid twisted microporous polymer by acidification, and the sulfonic acid group, the phosphoric acid group, the nitric acid group, or the hypochlorous acid group is specifically attached to a benzene ring structure of the rigid twisted microporous polymer, and by controlling the degree of acidification, the number of the above acidic groups of the benzene ring structure can be controlled.
In a specific embodiment of the present invention, when the polymer having the structure shown in formula I-1 is acidified with hydrochloric acid, the structure of the resulting acidified rigid twisted microporous polymer is represented as formula II-1;
when the polymer with the structure shown in the formula I-2 is acidified by hydrochloric acid, the structure of the obtained acidified rigid twisted microporous polymer is shown as the formula II-2;
when the polymer with the structure shown in the formula I-3 is acidified by hydrochloric acid, the structure of the obtained acidified rigid twisted microporous polymer is shown as the formula II-3;
when the polymer with the structure shown in the formula I-4 is acidified by hydrochloric acid, the structure of the obtained acidified rigid twisted microporous polymer is shown as the formula II-4;
when the polymer having the structure shown in formula I-5 above is acidified with hydrochloric acid, the structure of the resulting acidified rigid twisted microporous polymer is shown as formula II-5:
in a specific embodiment of the present invention, when the polymer having the structure shown in formula I-1 is acidified with sulfuric acid, the structures of the resulting acidified rigid twisted microporous polymers at different degrees of acidification are shown as formula II-6, formula II-7, and formula II-8; in the embodiment of the present invention, it is preferable to control the acidification degree by acidification time, and the longer the acidification time is, the more sulfonic acid groups are introduced, and at most three sulfonic acid groups (as shown in formula II-8) can be introduced;
the rest cases are not listed.
The invention also provides a rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane, which comprises a sulfonated polyether sulfone membrane and an acidified rigid twisted microporous polymer membrane arranged on the surface of the sulfonated polyether sulfone membrane; the acidified rigid twisted microporous polymer membrane is prepared from the acidified rigid twisted microporous polymer in the scheme, and is specifically prepared by preparing the membrane from the rigid twisted microporous polymer in the scheme and then acidifying the membrane.
In the invention, the pore diameter of the acidified rigid twisted microporous polymer membrane is preferably 0.8-1.8 nm, and the pore diameter of the sulfonated polyether sulfone membrane is preferably 150-300 nm.
In the invention, the thickness of the acidified rigid twisted microporous polymer membrane is preferably 10-30 μm, the thickness of the sulfonated polyether sulfone membrane is preferably 30-300 μm, and the total thickness of the rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane is preferably 40-330 μm.
In the present invention, the rigid twisted microporous polymer-sulfonated polyethersulfone porous composite membrane allows only cations to pass through, has excellent ion selectivity, and is high in water and ion flux. In a specific embodiment of the invention, the ion flux of the rigid twisted microporous polymer-sulfonated polyether sulfone is 1S/cm-20S/cm.
In the invention, the sulfonated polyethersulfone membrane is prepared by using a sulfonated polyethersulfone compound with a structure shown in formula III:
in formula III: m and n are the degree of polymerization;
c is the following structure:
d is any one of the following structures:
in the formula III, m is preferably 200-400, more preferably 250-350, and n is preferably 200-400, more preferably 250-350.
In the present invention, the method for preparing the sulfonated polyethersulfone compound having the structure described by formula III preferably comprises the steps of:
mixing a monomer I, a monomer II, a monomer III, a water-carrying agent, a catalyst and an organic solvent for polycondensation reaction to obtain a polyether sulfone compound;
and sulfonating the polyether sulfone compound to obtain a sulfonated polyether sulfone compound.
In the present invention, the structural formula of the I monomer is as follows:
in the present invention, the second monomer is any one of the monomers of the following structures:
in the present invention, the structural formula of the III monomer is as follows:
In the invention, the molar ratio of the monomer I, the monomer II and the monomer III is preferably 0.8-1.4: 0.8-1.4; the catalyst is preferably potassium carbonate, sodium carbonate, potassium chloride or sodium chloride; the dosage of the catalyst is preferably 1.3 to 1.5 times of the molar weight of the first monomer; the water-carrying agent is preferably toluene; the organic solvent is preferably sulfolane, N-dimethylformamide and N, N-dimethylacetamide; the polycondensation reaction is preferably carried out under reflux conditions; the temperature of the polycondensation reaction is preferably 175-185 ℃, more preferably 180 ℃, and the time of the polycondensation reaction is preferably 5-20 h.
In the specific embodiment of the invention, preferably, the monomer I, the monomer II, the monomer III catalyst, the water-carrying agent and the organic solvent are mixed and heated to 145 ℃ for reaction to remove water, and after the water in the system is completely taken out by the toluene, the temperature is raised to 175-185 ℃ for polycondensation reaction.
After the polycondensation reaction is completed, the present invention preferably subjects the obtained reaction liquid to a post-treatment, which preferably comprises the steps of: pouring the reaction liquid into deionized water, separating out a solid product, filtering and collecting the solid product, crushing the solid product, washing the crushed solid product with boiling water and ethanol in sequence, and drying the solid product to constant weight to obtain a polyether sulfone compound; the drying is preferably vacuum drying, the temperature of the vacuum drying is preferably 120 ℃. In the invention, the number average molecular weight of the polyether sulfone compound is preferably 30000-80000.
In the present invention, the sulfonation treatment is preferably: mixing the polyether sulfone compound and concentrated sulfuric acid for sulfonation reaction; the temperature of the sulfonation reaction is preferably room temperature, the time is preferably 10-30 h, and the sulfonation reaction is preferably carried out under a closed condition; and after the sulfonation reaction is finished, pouring the obtained reaction liquid into deionized water to separate out a solid material, filtering, collecting and crushing the solid material, washing the solid material to be neutral by using the deionized water, and drying the solid material to obtain the sulfonated polyether sulfone compound. In the present invention, the drying is preferably vacuum drying, the temperature of the vacuum drying is preferably 120 ℃, and the time is preferably 48 h.
The invention also provides a preparation method of the rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane, which comprises the following steps:
dissolving a rigid twisted microporous polymer with a structure shown in a formula I in an organic solvent to obtain a rigid twisted microporous polymer solution;
coating the rigid twisted microporous polymer solution on a substrate, volatilizing and removing a solvent in the obtained wet film, and then separating the substrate to obtain a rigid twisted microporous polymer film;
acidifying the rigid twisted microporous polymer membrane with a strong oxidizing acid to obtain an acidified rigid twisted microporous polymer membrane;
coating an organic solvent on the surface of the sulfonated polyethersulfone membrane, then covering the acidified rigid twisted microporous polymer membrane on the surface of the sulfonated polyethersulfone membrane, and then volatilizing and removing the organic solvent to obtain the ion-selective porous composite membrane.
The rigid twisted microporous polymer with the structure shown in the formula I is dissolved in an organic solvent to obtain a rigid twisted microporous polymer solution. In the present invention, the organic solvent for dissolution is preferably a polar organic solvent, more preferably chloroform; the mass concentration of the rigid twisted microporous polymer solution is preferably 1.5-4%, and more preferably 2-3%. In a specific embodiment of the present invention, the rigid twisted microporous polymer is preferably added to the polar organic solvent and stirred until there is no solid powder in the system.
After the rigid twisted microporous polymer solution is obtained, the rigid twisted microporous polymer solution is coated on a substrate, the solvent in the obtained wet film is volatilized and removed, and then the substrate is separated, so that the rigid twisted microporous polymer film is obtained. In the present invention, the substrate is preferably a glass sheet; the present invention preferably sonicates the glass sheet in deionized water three times for 20min each before use, and then in ethanol three times for 20min each to ensure crystallinity of the rigid twisted microporous polymer. The rigid twisted microporous polymer solution is preferably dripped onto a treated glass sheet, and then the glass sheet is placed on a culture dish to wait for the volatilization of an organic solvent; according to the invention, a funnel is preferably covered above the glass sheet in the solvent volatilization process, and cotton is used for blocking the bottom of the funnel so as to slow down the volatilization speed of the organic solvent and prevent the polymer film from cracking caused by the overhigh volatilization speed of the organic solvent; in a specific embodiment of the present invention, the time period for the solvent to evaporate is preferably 1 day.
After the solvent is volatilized, a proper amount of deionized water is preferably added into the culture dish, so that the water surface submerges the glass sheet, and the rigid twisted microporous polymer membrane automatically falls off after being submerged for a period of time, thereby realizing the separation of the substrate.
After obtaining the rigid twisted microporous polymer membrane, the invention uses strong oxidizing acid to acidify the rigid twisted microporous polymer membrane to obtain the acidified rigid twisted microporous polymer membrane. In the present invention, the kind of the strong oxidizing acid is consistent with the above scheme, and is not described herein again. In the invention, the pH value of the acidification is preferably 4-5, the acidification time is preferably adjusted according to the type of acid, specifically, when the strong oxidizing acid is hydrochloric acid, the acidification time is preferably 1-8 h, more preferably 2-6 h, and the acidification temperature is 100-180 ℃, more preferably 120-160 ℃; when the strong oxidizing acid is sulfuric acid, the time for acidification is preferably 2-6 min, specifically 2min, 4min or 6min, when the time for acidification is 2min, the structure of the obtained acidified rigid twisted microporous polymer is shown as the formula II-6, when the time for acidification is 4min, the structure of the obtained acidified rigid twisted microporous polymer is shown as the formula II-7, and when the time for acidification is 6min, the structure of the obtained acidified rigid twisted microporous polymer is shown as the formula II-8. In the present invention, when the strong oxidizing acid is sulfuric acid, phosphoric acid, nitric acid or hypochlorous acid, the acidification may be performed at room temperature.
In the specific embodiment of the invention, preferably, the rigid twisted microporous polymer membrane is firstly added into deionized water, then strong oxidizing acid is gradually added, the pH value of the system is adjusted to 4-5, then the reaction system is heated to boiling, and acidification is carried out under the boiling condition; the invention controls the pH value of acidification in the range, can ensure that the structure of the polymer is not damaged, and prevents the influence on the self property and subsequent application property of the membrane.
In the embodiment of the present invention, when the strong oxidizing acid is hydrochloric acid, it is preferable to further include, before the acidification: soaking the rigid twisted microporous polymer film in a sodium hydroxide solution for 4-6 hours, preferably for 5 hours; the soaking temperature is preferably 110-130 ℃, and more preferably 120 ℃; the mass fraction of the sodium hydroxide solution is preferably 30%; the solvent of the sodium hydroxide solution is preferably a mixed solvent of ethanol and water; after soaking, taking out the membrane and repeatedly washing the membrane to be neutral; the method comprises the steps of soaking a membrane in a sodium hydroxide solution to enable a polymer to form a sodium carboxylate (-COONa) form, and changing sodium ions into hydrogen ions to (-COOH) by adding hydrochloric acid when acidifying with hydrochloric acid subsequently, so that introduction of carboxyl is realized.
In the specific embodiment of the present invention, when the strongly oxidizing acid is sulfuric acid, phosphoric acid, nitric acid, or hypochlorous acid, the acidification is performed by adding water and then adding acid as described above.
After acidification is complete, the present invention preferably washes the resulting acidified rigid twisted microporous polymer membrane to neutrality.
After the acidified rigid twisted microporous polymer membrane is obtained, the surface of the sulfonated polyether sulfone membrane is coated with an organic solvent, then the acidified rigid twisted microporous polymer membrane is covered on the surface of the sulfonated polyether sulfone membrane, and the organic solvent is volatilized and removed, so that the rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane is obtained. In the invention, the sulfonated polyethersulfone membrane is preferably prepared by a suction filtration method, and specifically comprises the following steps: mixing a sulfonated polyether sulfone compound and an organic solvent, performing ultrasonic treatment, standing the obtained mixed system, taking supernatant, and performing suction filtration on the supernatant through an organic filter membrane to obtain the organic filter membrane with the sulfonated polyether sulfone membrane; and drying the organic filter membrane with the sulfonated polyether sulfone membrane to obtain the sulfonated polyether sulfone membrane. In the invention, the temperature of the ultrasound is preferably room temperature, and the time is preferably 1 h; the standing time is preferably 1 h; the drying is preferably vacuum drying, the temperature of the vacuum drying is preferably 50 ℃, and the time is preferably 24 hours.
After the sulfonated polyether sulfone membrane is obtained, coating an organic solvent on the surface of the sulfonated polyether sulfone membrane; the organic solvent is preferably one or more of N, N-dimethylformamide, N-dimethylacetamide, acetonitrile, methanol, ethanol, propanol, acetone, dioxane, tetrahydrofuran, N-butanol, ethyl acetate, diethyl ether, dichloromethane and chloroform, and more preferably trichloromethane; the coating mode is preferably spin coating; after the spin coating is finished, covering the acidified rigid twisted microporous polymer membrane on the surface of the sulfonated polyether sulfone membrane, and then placing the obtained double-layer membrane structure in a closed bottle to volatilize the organic solvent.
The invention also provides application of the ion selective porous composite membrane in the scheme in a salt-difference power generation device. The present invention has no special requirement on the specific method for the application, and the method is well known to those skilled in the art. In the laboratory embodiment of the invention, preferably, the ion selective porous composite membrane is placed in a double-chamber electrolytic cell, electrolytes with different concentrations are respectively added into two electrolytic chambers of the electrolytic cell, then a pair of electrodes are inserted, and the electrodes are connected with a picometer to form a salt-difference power generation device; in the present invention, the electrode is preferably a silver/silver chloride electrode, a saturated calomel electrode, a graphite (C) electrode, a platinum (Pt) electrode or a copper electrode. In the invention, the electrolyte is preferably a sodium chloride aqueous solution or a potassium chloride aqueous solution, and more preferably a potassium chloride aqueous solution; the concentration of the electrolyte is preferably 1-10000 mmol/L, and more preferably 10-1000 mmol/L.
The following examples are given to illustrate the embodiments of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of a rigid twisted microporous polymer of the structure shown in formula I-1:
6.8g of spiral biindane, 4g of tetrafluoroterephthalonitrile and 5.52g of potassium carbonate are added into a double-neck flask under the conditions of no water, no oxygen and inert gas protection, and a stirrer with a proper size is added into the flask. After weighing the solid medicine, injecting anhydrous and oxygen-free organic solvent N, N-dimethylformamide into a yellow rubber tube of a double-neck flask through an injector, and sealing a pinhole at the yellow rubber tube after the organic solvent is added. After all the organic solvent is added, when stirring is started, the solution in the flask is red, and the mixed system is heated to 65 ℃ for reaction for 72 hours; after the reaction time is over, the mixed system is bright yellow, and the system after the reaction is cooled to room temperature; then carrying out solid precipitation on the obtained product through a proper amount of deionized water, filtering, repeating the operation for three times, removing the organic solvent in the system, and then putting the obtained solid product in a vacuum drying oven at the temperature of 80 ℃ until the weight is constant to obtain dry powder with the yield of 72%.
To the above dry powder was added chloroform until the powder was in a saturated solution state. Adding a large amount of methanol into a saturated solution while stirring, wherein a large amount of bright yellow flaky solids appear at the moment, the process is called product heavy precipitation, the purity of the product can be increased, the precipitated flaky solids are filtered, collected and dried in vacuum at 120 ℃ to constant weight to obtain yellow flaky solids, namely the rigid twisted microporous polymer with the structure shown in the formula I-1, and the yield is 82%; if a product with higher purity is needed, the above-mentioned re-precipitation step can be repeated to obtain the product.
Example 2
Preparation of rigid twisted microporous polymer membranes:
0.295g of the rigid twisted microporous polymer prepared in example 1 and 10mL of chloroform were mixed and stirred at room temperature until no solid powder was visible in the mixed system. And (3) preparing a glass sheet, ultrasonically cleaning the glass sheet in deionized water for 3 times, 20min each time, and ultrasonically cleaning the glass sheet in ethanol for 3 times, 20min each time, so as to ensure the crystallinity of the rigid twisted microporous polymer. The well-mixed solution is dripped onto a glass sheet, then the glass sheet is placed on a culture dish, the volatilization of the chloroform solvent is waited, the volatilization rate of the solvent needs to be slowed down in the process, the funnel is used for covering the upper part of the culture dish, and the bottom of the funnel is plugged by cotton, so that the rigid twisted microporous polymer membrane is prevented from cracking. After the culture dish is placed for one day, a proper amount of deionized water is added into the culture dish, the water level exceeds that of the glass sheet, after a period of time, the rigid twisted microporous polymer membrane can automatically fall off and independently form a membrane, and at the moment, the rigid twisted microporous polymer membrane can be safely taken out after the deionized water in the culture dish is sucked out.
Example 3
Preparation of carboxylic acid modified rigid twisted microporous polymer membranes:
soaking the rigid twisted microporous polymer membrane in example 2 in 30% sodium hydroxide ethanol and water solution, reacting for 5h at 120 ℃, taking out the membrane from the reaction vessel after the reaction is finished, and repeatedly washing until the solution is neutral; putting the microporous polymer membrane into an adaptive container, adding a proper amount of deionized water, adjusting the pH of the whole system to be 4-5 by gradually adding hydrochloric acid, heating the reaction system to boiling for 2 hours to obtain a carboxylic acid modified rigid twisted microporous polymer membrane, and washing the obtained carboxylic acid modified rigid twisted microporous polymer membrane until the solution is neutral for later use, wherein the structure of the carboxylic acid modified rigid twisted microporous polymer is shown as the formula II-1.
Fig. 1 is a nuclear magnetic spectrum of the rigid twisted microporous polymer prepared in example 1 and the carboxylic acid modified rigid twisted microporous polymer prepared in example 3; FIG. 2 is an IR spectrum of a carboxylic acid modified rigid twisted microporous polymer prepared in example 3; as can be seen from FIGS. 1-2, both the rigid distorted microporous polymer and the carboxylic acid-modified rigid distorted microporous polymer have target structures.
Fig. 3 is a scanning electron microscope surface image of the carboxylic acid modified rigid twisted microporous polymer membrane prepared in this example. As can be seen from fig. 3, the resulting carboxylic acid-modified rigid twisted microporous polymer film was denser and no cracks were generated.
Example 4
Preparing a sulfonated polyether sulfone compound, wherein the structural formula of the sulfonated polyether sulfone compound is as follows:
adding 40.0mmol (10.18g) of 4,4' -difluoro diphenyl sulfone, 32.0mmol (5.96g) of 4,4' -dihydroxy biphenyl, 8.0mmol (2.00g) of 4,4' -dihydroxy diphenyl sulfone and 60mL of sulfolane into a three-neck bottle under the condition of protection of inert gas in an anhydrous and oxygen-free environment, heating the obtained mixed system to 145 ℃ under the condition of stirring, and carrying out reflux reaction for 4 hours, wherein the toluene fully carries away water generated in the system; after the reaction is finished, heating the obtained system to 180 ℃ for reaction for 9 hours, and clearly observing that the viscosity of the system does not change any more after the reaction time is finished; pouring the obtained product system into deionized water, separating out solid materials, filtering through a membrane filter, crushing the obtained solid materials, washing 3 times with boiling water in a single-neck flask, and then washing 3 times with ethanol; and after washing, drying in vacuum at 120 ℃ to constant weight to obtain a white solid, namely the polyether sulfone compound, wherein the inherent viscosity of the polyether sulfone compound is 0.87, the number average molecular weight is 112.8kDa, and the dispersity index is 1.4.
Sulfonating the polyether sulfone compound, weighing 8.5g of the dried compound and 150mL of concentrated sulfuric acid with the concentration of 98 wt%, adding into a single-neck flask, and carrying out closed stirring reaction for 12 hours at room temperature (25 ℃); and pouring the obtained product system (brown yellow viscous liquid) into deionized water to separate out solid materials, crushing the solid materials, washing the solid materials to be neutral by the deionized water, and performing vacuum drying for 48 hours at the temperature of 120 ℃ to obtain light yellow solid, namely the sulfonated polyether sulfone compound.
Fig. 4 shows nuclear magnetic spectra of the polyethersulfone compound and the sulfonated polyethersulfone compound prepared in this example.
FIG. 5 is an IR spectrum of sulfonated polyethersulfone compound prepared in this example.
As can be seen from FIGS. 4 to 5, the sulfonated polyethersulfone obtained has a target structure.
Example 5
6.250mg of the sulfonated polysulfone ether compound prepared in example 4 was mixed with 10mL of N, N-dimethylformamide, and the mixture was subjected to sonication at room temperature (25 ℃ C.) for 1 hour, after the sonication was completed, the mixed system was allowed to stand for 1 hour, the supernatant was collected by a dropper and put into a filter flask, and then filtration was performed with an organic filter membrane, and finally the filter membrane with the sulfonated polysulfone ether membrane was dried under vacuum at 50 ℃ for 24 hours to obtain a sulfonated polysulfone ether membrane.
The carboxylic acid modified rigid twisted microporous polymer membrane prepared in example 3 was composited with a sulfonated polyethersulfone membrane: coating a proper amount of trichloromethane on a sulfonated polymer membrane, carrying out spin coating at room temperature, then coating a carboxylic acid modified rigid twisted microporous polymer membrane on a sulfonated polysulfone ether compound membrane, and then placing the sulfonated polysulfone ether compound membrane in a sealed bottle to volatilize the trichloromethane, thereby obtaining the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane, wherein the thickness of the composite membrane is 60 mu m, the aperture of the carboxylic acid modified rigid twisted microporous polymer membrane is 1.18nm, the aperture of the sulfonated polyether sulfone compound membrane is about 225nm, and the porosity of the composite membrane is 5.8%.
Fig. 6 is a scanning electron microscope surface image of the sulfonated polyethersulfone membrane prepared in this example.
Fig. 7 is a cross-sectional image of the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyethersulfone compound composite membrane prepared in this example. As can be seen from fig. 7, good recombination is formed between the two films, and the composite film exhibits an asymmetric structure of a difference in pore size.
Example 6
Assembling a salt-difference power generation device according to a mature structure, specifically, placing the ion-selective composite porous membrane prepared in the example 5 in a double-chamber electrolytic cell, respectively adding potassium chloride aqueous solutions with the concentrations of 10mmol/L and 1mol/L as electrolytes, inserting a pair of Ag/AgCl electrodes and connecting the Ag/AgCl electrodes with a picometer (namely an ammeter with the precision of picometer (10-12A)), so as to form the salt-difference power generation device; and applying voltage by using the Ag/AgCl electrode, and testing the current under different voltage conditions by using a Peak to Meter.
Fig. 8 is a current-voltage curve diagram of the salt-difference power generation device prepared in the embodiment under the condition of 100 times concentration, and as can be seen from fig. 8, the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyethersulfone porous composite membrane prepared in the invention can obtain 0.10 v under the condition of 100 times concentration, which indicates that the porous composite membrane has high ion selectivity and can generate power by using the salt difference energy well.
Example 7
According to the structure of the salt difference power generation device, an ion current rectifier is built; the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane prepared in example 5 is placed on an ionic current rectification test device, and potassium chloride salt solutions with the same concentration are respectively added into a double-chamber electrolytic cell, wherein the concentration is 0.1 mmol/L. Inserting a pair of Ag/AgCl electrodes into the electrolyte of the double-chamber electrolytic cell and connecting the Ag/AgCl electrodes with a picometer to form an ionic current rectifying device; the voltage is applied through the electrodes, and the current under a certain voltage condition is obtained.
Fig. 9 is an ionic current rectification graph of the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyethersulfone composite membrane porous composite membrane in the same electrolyte solution. As can be seen from fig. 9, the ion current rectification ratio of the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyethersulfone porous composite membrane prepared in example 5 was about 3 in 0.1mmol/L potassium chloride solution. The composite membrane provided by the invention has a better ionic current rectification effect.
Fig. 10 is a current-voltage graph of the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyethersulfone composite membrane synthesized in example 5 in the same electrolyte solution. As is apparent from FIG. 10, the ion flux of the composite membrane prepared in example 5 was about 2S/cm in a 0.01mmol/L potassium chloride solution.
Example 8
Preparation of a rigid twisted microporous polymer of the structure shown in formula I-2:
1,4- (3',4' -dihydroxyphenyl) -2,3,5, 6-tetraphenylbenzene, (500mg,0.84mmol), a mixture of 2,3,5, 6-tetrafluoroterephthalonitrile (167mg,0.84mmol) and anhydrous DMF (20mL) were stirred under a dry nitrogen atmosphere. The mixture was heated to 65 ℃ and anhydrous K was added 2 CO 3 (0.92g, 6.68mmol) after which the mixture is stirred for 96 h. After completion of the reaction, water (100mL) was added, filtered and the filter cake was washed repeatedly with water and acetone. The solid was dissolved in chloroform (20mL), poured into a flask containing a mixture of acetone/methanol (2/1, 80mL volume ratio) and the solid product precipitated and dried under high vacuum overnight to give a yellow solid, a rigid twisted microporous polymer of the structure shown in formula I-2 (699mg, 92% molecular weight based on repeat units).
Rigid twisted microporous polymer membranes were prepared according to the method of example 2 using the rigid twisted microporous polymer prepared in this example, under otherwise identical conditions to example 2, except that the rigid twisted microporous polymer was replaced with the rigid twisted microporous polymer having the structure of formula I-2 prepared in this example.
Example 9
Soaking the rigid twisted microporous polymer membrane in example 8 in 30% sodium hydroxide ethanol and water solution, reacting for 5h at 140 ℃, taking out the membrane from the reaction vessel after the reaction is finished, and repeatedly washing until the solution is neutral; and (2) putting the microporous polymer membrane into an adaptive container, adding a proper amount of deionized water, adjusting the pH of the whole system to be 4-5 by gradually adding hydrochloric acid, and finally heating the reaction system to boil for 2 hours. And washing the obtained carboxylic acid modified rigid twisted microporous polymer membrane until the solution is neutral for later use.
Example 10
The sulfonated polyether sulfone polymer membrane obtained in example 5 and the carboxylic acid modified rigid twisted microporous polymer membrane obtained in example 9 were selected for compounding. Coating a proper amount of trichloromethane on a sulfonated polymer membrane, carrying out spin coating at room temperature, then coating a microporous polymer membrane on the sulfonated polysulfone ether compound membrane, placing the sulfonated polysulfone ether compound membrane in a sealed bottle to slow down the volatilization of the trichloromethane and increase the acting force between porous composite membranes to obtain the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyether sulfone compound composite membrane with the thickness of 80 mu m, wherein the aperture of the carboxylic acid modified rigid twisted microporous polymer is 1.5nm, the aperture of the sulfonated polyether sulfone compound membrane is about 225nm, and the porosity is 7.7%.
Example 11
Assembling a salt-difference power generation device according to a mature mode, specifically, placing the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane prepared in the example 10 into a double-chamber electrolytic cell, respectively adding potassium chloride aqueous solutions with the concentrations of 10mmol/L and 1mol/L into the two electrolytic chambers as electrolyte, inserting a pair of Ag/AgCl electrodes, and connecting the electrodes with a picoammeter (the precision can reach picoampere (10-12A)), so as to form the salt-difference power generation device; the Ag/AgCl electrode is used for applying voltage, a current under different voltage conditions is tested by using a picometer, and the result shows that the porous composite membrane can obtain 0.15V under the condition of 100 times concentration difference.
Example 12
According to the structure of the salt difference power generation device, an ion current rectifier is built: placing the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane prepared in example 10 on an ionic current rectification test device; potassium chloride salt solutions (0.1mmol/L) with the same concentration are respectively added into the double-chamber electrolytic cell. Inserting a pair of Ag/AgCl electrodes into the electrolyte in the double-chamber electrolytic cell, and connecting the electrodes with a picometer to form an effective circuit to form an ionic current rectifying device; the current was obtained under a constant voltage by applying a voltage to the electrodes, and the result showed that the ion current rectification ratio of the porous composite membrane was about 3.7 in a 0.1mmol/L potassium chloride solution.
Example 13
Preparation of a rigid twisted microporous polymer having the structure shown in formula I-5:
1,1',2,2' -tetrahydroxytetraphenylethylene (250mg, 0.630mmol) and 2,3,5, 6-tetrafluoroterephthalonitrile (126mg, 0.650mmol) were dissolved in 1.5mL DMAc, the solution was heated to 80 ℃ under inert gas, after which K was added 2 CO 3 (230mg, 1.45mmol), reacted for 120h, then the system was further heated to 100 ℃ and the resulting mixture became very viscous in 2-3 min. The solution was poured into methanol while maintaining the reaction system at 100 ℃, filtered and reprecipitated twice in methanol, and dried in a vacuum oven at 120 ℃ for 24 hours to obtain a pale yellow powder (306mg, yield: 95%), which was a rigid twisted microporous polymer having a structure represented by formula I-5.
Rigid twisted microporous polymer membranes were prepared according to the method of example 2 using the rigid twisted microporous polymer prepared in this example, under otherwise identical conditions to example 2, except that the rigid twisted microporous polymer was replaced with the rigid twisted microporous polymer having the structure of formula I-5 prepared in this example.
Example 14
The rigid twisted microporous polymer membrane in example 13 was immersed in 30% sodium hydroxide in ethanol and water, reacted at 140 ℃ for 5h, and washed to neutral after the reaction; and then regulating the pH value of the whole system to be 4-5 by gradually adding hydrochloric acid, finally heating the reaction system to boil for 2 hours, and washing the obtained carboxylic acid modified rigid twisted microporous polymer membrane until the solution is neutral for later use.
Example 15
The sulfonated polyethersulfone polymer membrane obtained in example 5 was selected and compounded with the carboxylic acid-modified rigid twisted microporous polymer membrane obtained in example 14. Coating a proper amount of trichloromethane on a sulfonated polymer membrane, carrying out spin coating at room temperature, then coating a carboxylic acid modified rigid twisted microporous polymer membrane on a sulfonated polysulfone ether compound membrane, placing the sulfonated polysulfone ether compound membrane in a closed bottle to slow down the volatilization of the trichloromethane and increase the acting force between porous composite membranes to obtain the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyether sulfone compound porous composite membrane with the thickness of 100 mu m, wherein the pore diameter of the carboxylic acid modified polymer membrane is 1.2nm, the pore diameter of the sulfonated polyether sulfone compound membrane is about 225nm, and the porosity is 6.3%.
Example 16
Placing the ion selective composite porous membrane prepared in example 15 in a double-chamber electrolytic cell, adding potassium chloride aqueous solution with concentration of 10mmol/L and 1mol/L as electrolyte respectively, inserting a pair of Ag/AgCl electrodes, and connecting the electrodes with a picometer (i.e. an ammeter with precision of picometer (10-12A)) to form a salt-difference power generation device; the Ag/AgCl electrode is used for applying voltage, a current under different voltage conditions is tested by using a Peak meter, and the result shows that the ion selective composite porous membrane can obtain 0.15V under the condition of 100 times concentration difference.
Example 17
According to the structure of the salt difference power generation device, an ion current rectifier is built; placing the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyethersulfone porous composite membrane prepared in example 15 on an ionic current rectification test device; potassium chloride salt solutions (0.1mmol/L) with the same concentration are respectively added into the double-chamber electrolytic cell. Inserting a pair of Ag/AgCl electrodes into electrolyte in a double-chamber electrolytic cell, and connecting the electrodes with a picometer to form an effective circuit to form an ionic current rectifying device; the current was obtained under a constant voltage condition by applying a voltage to the electrodes in a 0.1mmol/L potassium chloride solution, and the result showed that the ion current rectification ratio of the porous composite membrane was about 3.5.
Example 18
A rigid distorted microporous polymer having a structure represented by formula I-3 was prepared according to the method of example 8, under the same conditions as in example 8 except that 1,4- (3',4' -dihydroxyphenyl) -2,3,5, 6-tetraphenylbenzene therein was replaced with a monomer having a structure represented by formula I-3 in a molar amount corresponding to that of 1,4- (3',4' -dihydroxyphenyl) -2,3,5, 6-tetraphenylbenzene in example 8, to prepare a rigid distorted microporous polymer having a structure represented by formula I-3;
a rigid distorted microporous polymer membrane was prepared according to the method of example 8 using a rigid distorted microporous polymer having the structure shown in formula I-3.
According to the method of the embodiments 9 to 10, the polymer membrane prepared from the rigid twisted microporous polymer with the structure shown in the formula I-3 is used as a raw material to prepare the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyether sulfone compound composite membrane, and then the power generation performance and the ionic current rectification performance of the composite membrane are tested according to the methods of the embodiments 11 to 12, so that the obtained composite membrane can realize stable salt difference power generation, and the ionic current rectification effect result shows that the ionic current rectification ratio of the composite membrane is about 4.2.
Example 19
Other conditions are consistent with those of example 18, only the monomer with the structure shown in I-3 is replaced by the monomer with the structure shown in I-4 to prepare the rigid twisted microporous polymer with the structure shown in I-4, the carboxylic acid modified rigid twisted microporous polymer-sulfonated polyether sulfone compound composite membrane is prepared by using the polymer, and then power generation performance and ionic current rectification performance tests are carried out, and the result shows that the obtained composite membrane can realize stable salt difference power generation and has a better ionic current rectification effect, and the ionic current rectification ratio of the composite membrane is about 3.8.
Example 20
The rigid twisted microporous polymer membrane prepared in example 2 was modified with sulfuric acid under the following conditions: the rigid twisted microporous polymer membranes prepared in example 2 were separately immersed in H 2 SO 4 In solution (0.2mol/L) for 2, 4 and 6 minutes, whereby sulfuric acid modified rigid twisted microporous polymer membranes of different acidification degrees were formed. The membrane was then exposed to air for 10s to evaporate the dichloromethane and then washed with methanol, a weak base solution, a weak acid solution, and methanol in that order. And finally, drying the sulfonated rigid twisted microporous polymer membrane in the air for 48 hours to ensure that the solvent is completely removed, wherein the obtained sulfuric acid modified microporous polymer has structures shown in a formula II-6, a formula II-7 and a formula II-8 in sequence according to the sequence from short to long acidification time.
The sulfuric acid modified rigid twisted microporous polymer-sulfonated polyether sulfone compound composite membrane is prepared by using a sulfuric acid modified microporous polymer membrane with a structure shown in a formula II-8 as a raw material according to the method of example 5, and then the power generation performance and the ionic current rectification performance of the composite membrane are tested according to the methods of examples 6 to 7, so that the obtained composite membrane can realize stable salt difference power generation, and a good ionic current rectification effect result shows that the ionic current rectification ratio of the composite membrane is about 6.3.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane is characterized by comprising a sulfonated polyether sulfone membrane and an acidified rigid twisted microporous polymer membrane arranged on the surface of the sulfonated polyether sulfone membrane; the acidified rigid twisted microporous polymer membrane is prepared from an acidified rigid twisted microporous polymer; the acidified rigid twisted microporous polymer is obtained by acidifying a rigid twisted microporous polymer with a structure shown in a formula I, wherein an acidic reagent for acidification is a strong oxidizing acid;
in formula I: n represents the degree of polymerization, A is any one of the structures shown by A-1 to A-5:
in A-2, R 1 、R 2 、R 3 And R 4 Independently H, Br, methyl or CN;
in A-4, R 5 、R 6 、R 7 And R 8 Independently is H or methyl;
b is any one of structures shown by B-1 to B-5:
2. the rigid distorted microporous polymer-sulfonated polyethersulfone porous composite membrane according to claim 1, wherein said rigid distorted microporous polymer is prepared by a method comprising the steps of:
mixing a first monomer, a second monomer, a catalyst and an organic solvent to carry out polycondensation reaction to obtain a rigid twisted microporous polymer with a structure shown in a formula I;
the first monomer is any one of monomers with structures shown as i-1 to i-5:
r in the formula i-2 1 、R 2 、R 3 And R 4 The same as in the formula A-2; r in the formula i-4 5 、R 6 、R 7 And R 8 The same as in the formula A-4;
the second monomer is any one of monomers having a structure represented by formulas ii-1 to ii-5:
3. the rigid twisted microporous polymer-sulfonated polyethersulfone porous composite membrane according to claim 2, wherein said catalyst is one or more of alkali metal salts and alkali metal hydroxides.
4. The rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane according to claim 2 or 3, wherein the polycondensation reaction is carried out at a temperature of 40-150 ℃ for 72-120 h.
5. The rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane according to claim 1, wherein the sulfonated polyether sulfone membrane is prepared from a sulfonated polyether sulfone compound having a structure represented by formula III:
in formula III: m and n are the degree of polymerization;
c is the following structure:
d is any one of the following structures:
6. the preparation method of the rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane according to any one of claims 1 to 5, characterized by comprising the following steps:
dissolving a rigid twisted microporous polymer with a structure shown in a formula I in an organic solvent to obtain a rigid twisted microporous polymer solution;
coating the rigid twisted microporous polymer solution on a substrate, volatilizing and removing a solvent in the obtained wet film, and then separating the substrate to obtain a rigid twisted microporous polymer film;
acidifying the rigid twisted microporous polymer membrane with a strong oxidizing acid to obtain an acidified rigid twisted microporous polymer membrane;
coating an organic solvent on the surface of the sulfonated polyether sulfone membrane, then covering the acidified rigid twisted microporous polymer membrane on the surface of the sulfonated polyether sulfone membrane, and then volatilizing and removing the organic solvent to obtain the rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane.
7. The method according to claim 6, wherein the strong oxidizing acid comprises one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and hypochlorous acid.
8. The use of the rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane according to any one of claims 1 to 5 in a salt-difference power generation device.
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