CN116082555A - Ion-conducting copolymer, preparation method thereof and anion exchange membrane - Google Patents
Ion-conducting copolymer, preparation method thereof and anion exchange membrane Download PDFInfo
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Abstract
The application provides an ion-conducting copolymer, a preparation method thereof and an anion exchange membrane, and belongs to the technical field of electrochemistry. The ion-conducting copolymer provided by the application has better electrochemical performance and stability, so that the anion-exchange membrane prepared by the ion-conducting copolymer also has better electrochemical performance (including ion conductivity of the anion-exchange membrane) and stability, and is beneficial to widening the application range of the anion-exchange membrane to a great extent. The preparation method of the ion-conducting copolymer can realize accurate adjustment and control of quaternary ammonium salt sites in the ion-conducting copolymer, can effectively avoid residues of halomethylation functional groups in the copolymerization process, can improve the electrochemical performance and quality controllability of the ion-conducting copolymer, and is further beneficial to improving the electrochemical performance of the anion-exchange membrane prepared subsequently, so that the proportion of each unit in the prepared ion-conducting polymer is accurate and controllable.
Description
Technical Field
The application relates to the technical field of electrochemistry, in particular to an ion conduction copolymer, a preparation method thereof and an anion exchange membrane.
Background
Anion exchange membranes are a class of polymeric membranes containing basic active groups that are selectively permeable to anions, also known as ion-permselective membranes. Anion exchange membranes play an important role in the electrochemical technology fields of electrolysis, electrodialysis, fuel cells, etc.
However, the existing anion exchange membrane has bottlenecks in improving electrochemical performance, stability and the like, and the existing anion exchange membrane cannot have better electrochemical performance (such as lower ion conductivity and the like) and stability due to the limitations of a polymer molecular structure and/or a preparation method, so that the anion exchange membrane cannot meet the higher requirements of technological development, and the application of the anion exchange membrane is greatly limited.
Disclosure of Invention
The invention aims to provide an ion-conducting copolymer, a preparation method thereof and an anion exchange membrane, which aim to improve the electrochemical performance and stability of the anion exchange membrane at the same time, so that the anion exchange membrane can have better electrochemical performance and stability.
In a first aspect, the present application provides an ion-conducting copolymer having the expression formula: am-Bn-Cq, the ionic conduction copolymer has the following structural formula:
Wherein m is more than 0, n is more than or equal to 0, q is more than or equal to 0, and n and q are not simultaneously 0.
R 1 + The positively charged cyclic amine group is at least one selected from the group consisting of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium.
X is at least one selected from the group consisting of a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, a trifluoromethanesulfonic acid group and a methanesulfonyloxy group.
R 2 Selected from halogen substituted alkyl groups.
In the technical scheme, the structural units in the ion-conducting copolymer are regulated and controlled, so that the electrochemical performance (including ion conductivity) and stability (including mechanical strength and electrochemical durability) of the ion-conducting copolymer can be improved at the same time, and further, the anion-exchange membrane prepared by the ion-conducting copolymer also has better electrochemical performance (including ion conductivity of the anion-exchange membrane) and stability (including mechanical strength and electrochemical durability of the anion-exchange membrane), and the application range of the anion-exchange membrane is widened to a great extent.
With reference to the first aspect, in an alternative embodiment of the present application, the positively charged cyclic amine group is selected from at least one of imidazolium and piperidinium; and/or the positively charged cyclic amine group is selected from at least one of tetramethylimidazolium and N-methylpiperidinium; and/or X is selected from chlorine atoms; and/or R 2 At least one selected from chloromethyl, bromomethyl and iodomethyl.
In the above technical scheme, when the positively charged cyclic amine groups in the A units, X in the A units, and/or R in the C units in the ion-conducting copolymer 2 When the groups are selected, the electrochemical performance and the stability of the ion-conducting copolymer are further improved, the electrochemical performance and the stability of the anion-exchange membrane prepared subsequently are further improved, and the application range of the anion-exchange membrane is widened.
With reference to the first aspect, in an alternative embodiment of the present application, q=0, and the ratio of n to m is (1:2) - (9:1).
In the above technical scheme, when q=0, the ion-conducting copolymer is a binary copolymerization system, and the molar ratio of the A unit and the B unit in the binary copolymerization system is regulated and controlled, so that the electrochemical performance, quality controllability and stability of the anion exchange membrane prepared subsequently are further improved simultaneously.
With reference to the first aspect, in an alternative embodiment of the present application, the ratio of n to m is (1:1) - (4:1).
In the technical scheme, as q=0, the ion-conducting copolymer is a binary copolymerization system, the molar ratio of the A unit to the B unit in the binary copolymerization system is regulated and controlled, so that the electrochemical performance, quality controllability and stability of the anion exchange membrane prepared subsequently are further improved simultaneously.
With reference to the first aspect, in an alternative embodiment of the present application, q=0, the positively charged cyclic amine group is selected from tetramethylimidazolium, and the ratio of n to m is (1.5:1) - (3:1).
In the above technical scheme, when q=0, the ion-conducting copolymer is a binary copolymerization system, in the binary copolymerization system, the positively charged cyclic amine group in the a unit is selected as tetramethylimidazolium, and meanwhile, the ratio of n to m is regulated to be (1.5:1) - (3:1), and the co-cooperation is carried out on the selection of the positively charged cyclic amine group in the a unit and the ratio of the a unit to the B unit, so that the electrochemical performance (especially the electrochemical performance in alkaline electrolyzed water experiments), the quality controllability and the stability of the subsequently prepared anion exchange membrane can be improved together.
With reference to the first aspect, in an alternative embodiment of the present application, the ratio of n to m is (1.85:1) - (2.5:1).
In the technical scheme, the method is favorable for further jointly improving the electrochemical performance (particularly the electrochemical performance in alkaline electrolyzed water experiments), quality controllability and stability of the anion exchange membrane prepared later.
In an alternative embodiment of the present application, in combination with the first aspect, m, n and q are all greater than 0, and the total weight of the C units in the ion-conducting copolymer is less than or equal to 0.295% of the total mass of the ion-conducting copolymer, wherein the ratio of the total of n and q to m is (1:1) - (4:1).
In the technical scheme, when m, n and q are all greater than 0, the ion-conducting copolymer is a ternary polymerization system, and the mass ratio of the C unit in the ternary polymerization system is regulated and controlled, so that the electrochemical performance (particularly the electrochemical performance in an alkaline electrolyzed water experiment), the quality controllability and the stability of the anion exchange membrane prepared later are improved.
In a second aspect, the present application provides a method of preparing an ion-conducting copolymer comprising: carrying out copolymerization reaction on the first component and the second component; wherein the first component is a first monomer, and the second component comprises a second monomer and/or a third monomer.
Wherein the structural formula of the first monomer is as follows:
R 1 + is a positively charged cyclic amine group selected from at least one of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium; x is at least one selected from the group consisting of a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, a trifluoromethanesulfonic acid group and a methanesulfonyloxy group.
The second monomer is styrene.
The structural formula of the third monomer is as follows:
R 2 selected from halogen substituted alkyl groups.
In the technical scheme, the ionic conduction copolymer is prepared by directly copolymerizing the first component (the ionic monomer) and the second component, compared with the mode of preparing the ionic conduction copolymer by copolymerizing the non-ionic monomer subjected to halomethylation and then carrying out quaternary ammonium salt on the halomethylation functional group in the copolymer, the method can realize the precise adjustment of quaternary ammonium salt sites in the prepared ionic conduction copolymer, can effectively avoid the residue of the halomethylation functional group in the copolymerization process, can improve the electrochemical performance of the ionic conduction copolymer, and is further beneficial to improving the electrochemical performance of the anion exchange membrane prepared subsequently; the ion-conducting copolymer prepared by the preparation method provided by the application can be directly subjected to a crosslinking reaction to prepare the anion-exchange membrane without purification treatment, so that the proportion of each unit in the prepared ion-conducting polymer is accurate and controllable, and the preparation method is simple and easy to operate and easy to realize industrial production.
With reference to the second aspect, in an alternative embodiment of the present application, the molar ratio of the second component to the first component is (1:2) - (9:1). In the technical scheme, the molar ratio of the first component to the second component is regulated and controlled, so that the electrochemical performance and the stability of the anion exchange membrane prepared subsequently are further improved simultaneously.
And/or, the copolymerization reaction is carried out under the mixed solvent containing the first solvent and the second solvent, and the volume ratio of the first solvent to the second solvent in the mixed solvent is (1:4) - (4:1); wherein the first solvent is selected from at least one of benzene, toluene, ethylbenzene, mesitylene, petroleum ether and n-hexane, and the second solvent is selected from at least one of methanol, ethanol and isopropanol. Under the above conditions, the first solvent can improve the solubility of the second component, and the second solvent can improve the solubility of the first component, so that the copolymerization reaction can be better carried out, and the controllability of the copolymerization reaction is improved.
And/or the copolymerization is carried out in the presence of an initiator in a molar amount of 0.1 to 3.0% of the total molar amount of the first component and the second component. Under the condition, the copolymerization reaction can be better carried out, and the controllability of the copolymerization reaction is improved.
And/or the temperature of the copolymerization reaction is 60-100 ℃, and the time of the copolymerization reaction is 6-18h. In the technical scheme, the copolymerization reaction can be better carried out, and the controllability of the copolymerization reaction is improved.
And/or the copolymerization is carried out in the presence of an initiator, wherein the initiator is azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide tert-butyl ester or methyl ethyl ketone peroxide.
In a third aspect, the present application provides an anion exchange membrane, the anion exchange membrane comprising a porous support layer and a filler filled in pores of the porous support layer, wherein the filler is made of a cross-linked product of the ion-conducting copolymer provided in the first aspect; or, the anion exchange membrane comprises a membrane matrix, and the membrane matrix is made of the cross-linked product of the ion-conducting copolymer provided in the first aspect.
In the above technical solution, the crosslinked product of the ion-conducting copolymer provided in the above first aspect has a network structure with three-dimensional space, which is beneficial to improving the mechanical strength of the anion-exchange membrane; the ion-conducting copolymer provided in the first aspect has better electrochemical performance and stability, and is also beneficial to the anion-exchange membrane to have better electrochemical performance (including ion conductivity of the anion-exchange membrane) and stability (including mechanical strength and electrochemical durability of the anion-exchange membrane); in addition, when the anion exchange membrane comprises a porous support layer and a filler filled in the pores of the porous support layer, the material of the filler is the cross-linked product of the ion-conducting copolymer provided in the first aspect, since the anion exchange membrane has the porous support layer, the long-term stability of the anion exchange membrane is further improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting the scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance spectrum of a first monomer prepared in example 1 of the present application.
FIG. 2 is a nuclear magnetic resonance spectrum of a first monomer prepared in example 12 of the present application.
FIG. 3 is a nuclear magnetic resonance spectrum of a first monomer prepared in example 13 of the present application.
Detailed Description
The application provides an ion-conducting copolymer, which has the expression formula: am-Bn-Cq, the ionic conduction copolymer has the following structural formula:
wherein m is more than 0, n is more than or equal to 0, q is more than or equal to 0, and n and q are not simultaneously 0; r is R 1 + Is a positively charged cyclic amine group selected from at least one of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium; x is at least one selected from hydroxyl, chlorine, bromine, iodine, p-toluenesulfonyloxy, trifluoromethanesulfonic acid and methanesulfonyloxy; r is R 2 Selected from halogen substituted alkyl groups.
The structural unit in the ion-conducting copolymer is regulated and controlled, so that the electrochemical performance (including ion conductivity) and stability (including mechanical strength and electrochemical durability) of the ion-conducting copolymer can be improved at the same time, and the anion-exchange membrane prepared by the ion-conducting copolymer also has better electrochemical performance (including ion conductivity of the anion-exchange membrane) and stability (including mechanical strength and electrochemical durability of the anion-exchange membrane), so that the application range of the anion-exchange membrane is widened to a great extent.
Wherein R in the present application 1 + Is a positively charged cyclic amine group, R is a group that is more positive than a cyclic amine group (e.g., methylamine, etc.) that is not cyclic 1 + The ionic conduction copolymer is positively charged cyclic amine group, so that the decomposition of the ionic conduction copolymer under the strong alkaline condition can be effectively avoided, and the alkali stability is improved.
The positively charged cyclic amine group is selected from at least one of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium. When the positively charged cyclic amine group in the A unit in the ion-conducting copolymer is selected from the groups, the electrochemical performance and stability of the ion-conducting copolymer can be improved at the same time, so that the electrochemical performance and stability of the anion-exchange membrane prepared subsequently can be further improved, and the application range of the anion-exchange membrane is widened.
X is at least one selected from hydroxyl group, chlorine atom, bromine atom, iodine atom, p-toluenesulfonyloxy group (OTs), trifluoromethanesulfonic group (OTf) and methanesulfonyloxy group (OMs). When X in the A unit in the ion-conducting copolymer is selected from the groups, the electrochemical performance and stability of the ion-conducting copolymer can be improved at the same time, so that the electrochemical performance and stability of the anion-exchange membrane prepared subsequently can be further improved, and the application range of the anion-exchange membrane is widened.
R 2 Selected from halogen substituted alkyl groups. When R in the C unit of the ion-conducting copolymer 2 When the groups are selected, the electrochemical performance and stability of the ion-conducting copolymer can be improved at the same time, so that the electrochemical performance and stability of the anion-exchange membrane prepared subsequently can be further improved, and the application range of the anion-exchange membrane is widened.
It will be appreciated that in the present application, the structural formula corresponding to the unit a is formula i, the structural formula corresponding to the unit B is formula ii, and the structural formula corresponding to the unit C is formula iii.
The formula I is as follows:
the formula II is as follows:
formula III is as follows:
furthermore, it is understood that the ion-conducting copolymers corresponding to Am-Bn-Cq, am-Bn, and Am-Cq are all within the scope of the present application.
In some alternative embodiments, the positively charged cyclic amine group is selected from at least one of imidazolium and piperidinium, which facilitates further enhancement of the ion conductivity of the ion-conducting copolymer.
Further, the positively charged cyclic amine group is at least one selected from tetramethylimidazolium and N-methylpiperidinium, which is favorable for further improving the ion conductivity and stability of the ion-conducting copolymer at the same time.
In some alternative embodiments, X is selected from chlorine atoms, which can reduce the cost of the ion-conducting copolymer and facilitate industrial production.
In some alternative embodiments, R 2 Selected from halogen substituted C1-C5 alkyl groups.
Illustratively, R is 2 May be selected from halogen substituted methyl, propyl, ethyl, butyl or pentyl.
Further, R 2 At least one selected from chloromethyl, bromomethyl and iodomethyl. When R in the C unit of the ion-conducting copolymer 2 When the groups are selected, the electrochemical performance and stability of the ion-conducting copolymer can be improved at the same time, so that the electrochemical performance and stability of the anion-exchange membrane prepared subsequently can be further improved, and the application range of the anion-exchange membrane is widened.
In some embodiments of the present application, the ion-conducting copolymer has a number average molecular weight of 1 to 10W. If the number average molecular weight of the ion-conducting copolymer is large, the mechanical strength of the ion-conducting copolymer is not improved; if the number average molecular weight of the ion-conducting copolymer is small, the viscosity of the ion-conducting copolymer is large, which is unfavorable for improving the film forming effect.
Further, the ion-conducting copolymer has a number average molecular weight of 5 to 8W.
Illustratively, m ranges from 41 to 243, n ranges from 121 to 595, and q ranges from 0 to 2.
In some embodiments of the present application, the total weight of C cells in the ion-conducting copolymer is less than or equal to 0.295% of the total mass of the ion-conducting copolymer. Under the above conditions, the electrochemical performance (especially the electrochemical performance under alkaline conditions) of the ion-conducting copolymer can be improved, so that the electrochemical performance (especially the electrochemical performance in alkaline electrolyzed water experiments) of the anion-exchange membrane prepared later can be improved, and the quality controllability of the anion-exchange membrane prepared later can be improved.
As an example, the total weight of C units in the ion-conducting copolymer may be less than or equal to the total mass of the ion-conducting copolymer by a value of any one point value or a range value between any two of 0, 0.01%, 0.02%, 0.05%, 0.1%, 0.15%, 0.17%, 0.2%, 0.22%, 0.25% and 0.295%.
When the total weight of the C units in the ion-conducting copolymer is less than or equal to 0.295% of the total mass of the ion-conducting copolymer, the ratio of the total amount of n and q to m is (1:2) - (9:1), which is beneficial to further improving the electrochemical performance and stability of the anion-exchange membrane prepared subsequently.
As an example, the ratio of the total amount of n and q to m may be any one of the point values or range values between any two of 1:2, 1:1.5, 1:1.25, 1:1.2, 1:1.1, 1.2:1, 1.25:1, 1.5:1, 1.7:1, 1.85:1, 2:1, 2.15:1, 2.25:1, 2.3:1, 2.35:1, 2.4:1, 2.5:1, 2.7:1, 3:1, 3.5:1, 4:1, 5:1, 7:1 and 9:1.
Further, the ratio of the total of n and q to m is (1:1) - (4:1); still further, the ratio of the total of n and q to m is (1.5:1) - (3:1); further, the ratio of the total of n and q to m is (1.85:1) - (2.5:1).
In some alternative embodiments, the amount of material of the C units in the ion-conducting copolymer is less than or equal to 0.95% of the amount of material of the a units. Under the above conditions, the electrochemical performance (especially the electrochemical performance under alkaline conditions) of the ion-conducting copolymer can be improved, so that the electrochemical performance (especially the electrochemical performance in alkaline electrolyzed water experiments) of the anion-exchange membrane prepared later can be improved, and the quality controllability of the anion-exchange membrane prepared later can be improved.
As an example, the amount of the substance of the C unit in the ion-conducting copolymer may be any one point value or a range value between any two of 0, 0.01%, 0.02%, 0.05%, 0.1%, 0.15%, 0.2%, 0.5%, 0.7%, 0.75% and 0.95% of the amount of the substance of the a unit.
In some alternative embodiments, q=0 and the ratio of n to m is (1:2) - (9:1). When q=0, the ion conduction copolymer is a binary copolymerization system, and the molar ratio of the A unit and the B unit in the binary copolymerization system is regulated and controlled, so that the electrochemical performance, quality controllability and stability of the anion exchange membrane prepared subsequently are further improved simultaneously. If the content of the B unit is high, the stability and mechanical strength of the molecular skeleton of the ion-conducting copolymer are low; if the content of the B unit is low, the ion conductivity of the ion conductive copolymer is low.
Further, when q=0, the ratio of n to m is (1:1) - (4:1); still further, when q=0, the ratio of n to m is (1.5:1) - (3:1); further, when q=0, the ratio of n to m is (1.85:1) - (2.5:1).
In some preferred embodiments, q=0, the positively charged cyclic amine group is selected from tetramethylimidazolium, and the ratio of n to m is (1.5:1) - (3:1). When q=0, the ion conduction copolymer is a binary copolymerization system, positive cyclic amine groups in an A unit in the binary copolymerization system are selected as tetramethylimidazolium, and meanwhile, the ratio of n to m is regulated to be (1.5:1) - (3:1), and the selection of the positive cyclic amine groups in the A unit and the ratio of the A unit to the B unit are cooperatively matched, so that the electrochemical performance (particularly the electrochemical performance in an alkaline electrolyzed water experiment), the quality controllability and the stability of the anion exchange membrane prepared later are improved together.
Further, q=0, the positively charged cyclic amine group is selected from tetramethylimidazolium, and the ratio of n to m is (1.85:1) - (2.5:1).
When q=0 and the ratio of n to m is (1.5:1) - (3:1), preferred ion conducting copolymers of the present application have the following structural formula:
in some preferred embodiments, m, n, and q are all greater than 0, and the total weight of the C units in the ion-conducting copolymer is less than or equal to 0.295% of the total mass of the ion-conducting copolymer. When m, n and q are all greater than 0, the ion-conducting copolymer is a ternary polymerization system, and the mass ratio of a C unit in the ternary polymerization system is regulated and controlled, so that the electrochemical performance (particularly the electrochemical performance in an alkaline electrolyzed water experiment), quality controllability and stability of the subsequently prepared anion exchange membrane are improved.
As an example, when m, n, and q are each greater than 0, the total weight of C units in the ion-conducting copolymer may be a value of any one point value or a range value between any two of 0.01%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, and 0.295% of the total mass of the ion-conducting copolymer.
Further, when m, n, and q are all greater than 0, and the total weight of the C units in the ion-conducting copolymer is less than or equal to 0.295% of the total mass of the ion-conducting copolymer, the ratio of the total of n and q to m is (1:1) - (4:1); still further, the ratio of the total of n and q to m is (1.5:1) - (3:1); further, the ratio of the total of n and q to m is (1.85:1) - (2.5:1).
In some preferred embodiments, m, n, and q are all greater than 0, and the amount of the substance of the C unit in the ion-conducting copolymer is less than or equal to 0.95% of the amount of the substance of the a unit. When m, n and q are all greater than 0, the ion-conducting copolymer is a ternary polymerization system, and the mass ratio of a C unit in the ternary polymerization system is regulated and controlled, so that the electrochemical performance (particularly the electrochemical performance under alkaline conditions), quality controllability and stability of the subsequently prepared anion exchange membrane are improved.
The existing ion-conducting polymer is generally prepared by the following steps: firstly, adopting a halomethylated nonionic monomer to carry out copolymerization, and then carrying out quaternization on the halomethylated functional group in the copolymer. For anion exchange membranes, the anions in the anion exchange membrane are replaced by hydroxide ions after quaternization, and the transmembrane transport of hydroxide ions is critical for the electrical conductivity of the ion conducting polymer.
However, the inventors found that in the above preparation method, as the copolymerization reaction proceeds, the viscosity of the system increases, and therefore, a part of the halomethylated functional groups which are not available for the reaction are entangled and wrapped by the polymer chain, and therefore, a part of the halomethylated functional groups in the copolymerization system are not reacted due to the influence of kinetic factors. The residual halomethylated functional groups do not promote conductivity, but rather inhibit pi interactions between cyclic amine functional groups, limiting the formation of microcrystalline regions, thereby affecting the enhancement of conductivity of the ion-conducting copolymer itself. In addition, the halomethylation functional groups which do not undergo quaternization can make the composition and final structure of the ion-conducting copolymer difficult to control, and further can affect the parallelism (the variability of different production lot products) and quality controllability of the subsequently prepared anion exchange membrane. Meanwhile, the quaternary ammonium salt is often required to be purified more complicated after the nonionic monomer is copolymerized, so that the industrial production is not facilitated.
In order to solve the above problems, the present application also provides a method for preparing an ion-conducting polymer, including: carrying out copolymerization reaction on the first component and the second component; wherein the first component is a first monomer, and the second component comprises a second monomer and/or a third monomer.
Wherein the structural formula of the first monomer is as follows:
R 1 + is a positively charged cyclic amine group selected from at least one of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium; x is at least one selected from the group consisting of a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, a trifluoromethanesulfonic acid group and a methanesulfonyloxy group.
The second monomer is styrene.
The structural formula of the third monomer is as follows:
R 2 selected from halogen substituted alkyl groups.
According to the method, compared with the mode of preparing the ion-conducting copolymer by directly copolymerizing a first component (being an ionic monomer) and a second component and then copolymerizing a halogen-methylated nonionic monomer, the method can realize accurate adjustment and control of quaternary ammonium salt sites in the prepared ion-conducting copolymer, can effectively avoid residues of the halogen-methylated functional group in the copolymerization process, can improve the electrochemical performance of the ion-conducting copolymer, and is further beneficial to improving the electrochemical performance of a subsequently prepared anion exchange membrane; the ion-conducting copolymer prepared by the preparation method provided by the application can be directly subjected to a crosslinking reaction to prepare the anion-exchange membrane without purification treatment, so that the proportion of each unit in the prepared ion-conducting polymer is accurate and controllable, and the preparation method is simple and easy to operate and easy to realize industrial production.
Regarding the positively charged cyclic amine group in the first monomer, the X group in the first monomer, and R in the third monomer 2 For the selection of the groups, please refer to the above, and the description is omitted here.
In some alternative embodiments, the molar ratio of the second component to the first component is (1:2) - (9:1). The molar ratio of the first component to the second component is regulated and controlled, so that the electrochemical performance and the stability of the anion exchange membrane prepared subsequently are further improved simultaneously.
As an example, the molar ratio of the second component to the first component may be any one of the point values or a range between any two of the point values of 1:2, 1:1.5, 1:1.25, 1:1.2:1, 1.25:1, 1.5:1, 1.7:1, 1.85:1, 2:1, 2.15:1, 2.25:1, 2.3:1, 2.35:1, 2.4:1, 2.5:1, 2.7:1, 3:1, 3.5:1, 4:1, 5:1, 7:1, and 9:1.
Further, the molar ratio of the second component to the first component is (1:1) - (4:1); still further, the molar ratio of the second component to the first component is (1.5:1) - (3:1); still further, the molar ratio of the second component to the first component is (1.85:1) - (2.5:1).
In some alternative embodiments, the copolymerization is performed in a mixed solvent comprising a first solvent and a second solvent; in the mixed solvent, the volume ratio of the first solvent to the second solvent is (1:4) - (4:1); wherein the first solvent is selected from at least one of benzene, toluene, ethylbenzene, mesitylene, petroleum ether and n-hexane, and the second solvent is selected from at least one of methanol, ethanol and isopropanol. Under the above conditions, the first solvent can improve the solubility of the second component, and the second solvent can improve the solubility of the first component, so that the copolymerization reaction can be better carried out, and the controllability of the copolymerization reaction is improved.
Further, the first solvent is selected from toluene and the second solvent is selected from ethanol. Toluene may further increase the solubility of the second component and ethanol may further increase the solubility of the first component.
Further, the volume ratio of the first solvent to the second solvent is (1:2) - (2:1), which is beneficial to further improving the solubility of the first component and the second component.
As an example, the volume of the second monomer is 10 to 30% of the volume of the mixed solvent. Further, the volume of the second monomer is 15-25% of the volume of the mixed solvent.
In some alternative embodiments, the copolymerization is carried out in the presence of an initiator in a molar amount of 0.1 to 3.0% of the total molar amount of the first component and the second component. Under the condition, the copolymerization reaction can be better carried out, and the controllability of the copolymerization reaction is improved.
Further, the molar amount of the initiator is 0.5 to 2.0% of the total molar amount of the first component and the second component.
As an example, the initiator is selected from one of radical type initiator or redox type initiator containing peroxide initiator and azo type initiator. For example, the initiator is azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide, t-butyl benzoyl peroxide, or methyl ethyl ketone peroxide.
Further, the initiator is Azobisisobutyronitrile (AIBN). The reaction temperature of AIBN is suitable and the reaction rate is controllable.
In some alternative embodiments, the temperature of the copolymerization is 60-100deg.C and the time of the copolymerization is 6-18 hours. Under the above conditions, the copolymerization reaction can be better carried out, which is beneficial to improving the controllability of the copolymerization reaction.
Further, the temperature of the copolymerization reaction is 70-90 ℃, and the time of the copolymerization reaction is 9-15h.
The application also provides an anion exchange membrane, which comprises a porous supporting layer and a filler filled in the pores of the porous supporting layer, wherein the filler is made of the cross-linked ion-conducting copolymer; or the anion exchange membrane comprises a membrane matrix, and the material of the membrane matrix is the cross-linked product of the ion conduction copolymer.
In the technical scheme, the material of the filler or the membrane matrix is the cross-linked product of the ion-conducting copolymer provided by the application, and the cross-linked product of the ion-conducting copolymer has a three-dimensional network structure, so that the mechanical strength of the anion-exchange membrane is improved; the ion-conducting copolymer provided by the application has better electrochemical performance and stability, and is also beneficial to ensuring that the anion-exchange membrane also has better electrochemical performance (including the ion conductivity of the anion-exchange membrane) and stability (including the mechanical strength and electrochemical durability of the anion-exchange membrane).
In addition, when the anion exchange membrane comprises a porous supporting layer and a filler filled in the pores of the porous supporting layer, the material of the filler is the cross-linked product of the ion-conducting copolymer provided by the application, the anion exchange membrane is provided with the porous supporting layer, so that the long-time stability of the anion exchange membrane is further improved.
As an example, the porous support layer may be woven or nonwoven.
In some alternative embodiments of the present application, the porous support layer comprises at least one of polypropylene, polyethylene, polysulfone, polyphenylene sulfide, polyamide, polyethersulfone, polyethylene terephthalate, polyetheretherketone, sulfonated polyetheretherketone, expanded polytetrafluoroethylene, chlorotrifluoroethylene, a copolymer of ethylene and tetrafluoroethylene, a copolymer of ethylene and chlorotrifluoroethylene, polyimide, polyetherimide, and meta-aramid. The porous support layer is made of the materials, so that the long-time stability of the anion exchange membrane is guaranteed.
Further, the porous support layer is made of expanded polytetrafluoroethylene, which is favorable for further improving the long-time stability of the anion exchange membrane.
As an example, when the anion exchange membrane includes a porous support layer and a filler filled in the pores of the porous support layer, the filler is made of the cross-linked product of the ion-conducting copolymer provided above, the preparation method of the anion exchange membrane includes: the crosslinks of the ion-conducting copolymer are cast into the pores of the porous support layer.
Further, the preparation method of the anion exchange membrane further comprises the following steps: casting the cross-linked product of the ion-conducting copolymer into the pores of the porous supporting layer, drying, and then soaking the dried system in 30wt% KOH solution to obtain the hydroxide anion exchange membrane. Wherein, the drying temperature can be about 80 ℃.
When the anion exchange membrane comprises a membrane matrix, the membrane matrix is made of the cross-linked product of the ion-conducting copolymer provided by the above, the preparation method of the anion exchange membrane comprises the following steps: casting the cross-linked product of the ion-conducting copolymer onto a planar substrate, and drying to obtain a film-like substance positioned on the planar substrate; the film-like substance was immersed in a 30wt% KOH solution to thereby obtain a hydroxide anion-exchange membrane. Wherein the planar substrate may be PE, PET, PTFE or glass or the like.
In this application, the ion-conducting copolymer is crosslinked at a temperature of 60 to 100 ℃.
In some alternative embodiments, the temperature of the crosslinking reaction is 70-90 ℃. The crosslinking temperature is favorable for improving the crosslinking degree and further favorable for improving the mechanical strength of the anion exchange membrane.
In some alternative embodiments, the crosslinking reaction is carried out in the presence of a crosslinking agent containing at least two carbon-carbon double bonds. Furthermore, the cross-linking agent is Divinylbenzene (DVB), the DVB has low cost and good cross-linking effect, and other functional groups are not introduced.
Illustratively, the molar amount of the crosslinking agent is from 0.1 to 2% of the molar amount of the ion-conducting copolymer; further, the molar amount of the crosslinking agent is 0.5 to 1.5% of the molar amount of the ion-conducting copolymer. If the amount of the crosslinking agent is too large, the viscosity of the formed anion exchange membrane may be too high to be good for the coating; if the amount of the crosslinking agent is too low, the crosslinking effect is reduced.
In some alternative embodiments, the solvent used during the crosslinking reaction is the same as the solvent used during the copolymerization of the ion-conducting copolymer described above, and will not be described in detail herein.
In order to enhance the crosslinking effect so that the crosslinking reaction is more sufficient, in some embodiments of the present application, the crosslinking reaction is classified into preliminary crosslinking and re-crosslinking; wherein the temperature of the primary crosslinking and the secondary crosslinking are respectively and independently 60-100 ℃, and the time of the primary crosslinking and the secondary crosslinking are respectively and independently 6-18h; the molar amount of the crosslinking agent used in the primary crosslinking is 0.1-2% of the molar amount of the ion-conducting copolymer, and the molar amount of the crosslinking agent used in the secondary crosslinking is 1-2% of the molar amount of the ion-conducting copolymer.
Further, the temperature of the primary crosslinking and the secondary crosslinking are respectively and independently 70-90 ℃, and the time of the primary crosslinking and the secondary crosslinking are respectively and independently 9-15h; the molar amount of the crosslinking agent used in the primary crosslinking is 0.5-1.5% of the molar amount of the ion-conducting copolymer, and the molar amount of the crosslinking agent used in the secondary crosslinking is 1-1.5% of the molar amount of the ion-conducting copolymer.
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a method for preparing an ion-conducting copolymer, which comprises the following steps:
(1) And (3) reacting tetramethylimidazole and p-chloromethyl styrene with a molar ratio of 1:1.2 by taking acetonitrile as a solvent at 80 ℃ for 36 hours, centrifuging, pulping and purifying the solid to obtain a first monomer.
(2) Styrene, the first monomer obtained in the step (1) and AIBN were dissolved in a mixed solvent containing 400. Mu.L of toluene and 400. Mu.L of ethanol, reacted at 80℃for 12 hours to obtain an ion-conducting copolymer (referred to as a polymer solution) dispersed in the mixed solvent, and the polymer solution was reprecipitated by ethyl acetate to obtain a solid ion-conducting polymer.
Wherein the molar ratio of the styrene to the first monomer is 2:1, the mass of the first monomer is 400mg, and the molar amount of AIBN is 1% of the total molar amount of the styrene and the first monomer.
Example 2
This example provides a method for preparing an ion-conducting copolymer, which differs from example 1 in that: the molar ratio of styrene to first monomer in step (2) of example 1 was changed to 1:2.
Example 3
This example provides a method for preparing an ion-conducting copolymer, which differs from example 1 in that: the molar ratio of styrene to first monomer in step (2) of example 1 was changed to 9:1.
Example 4
This example provides a method for preparing an ion-conducting copolymer, which differs from example 1 in that: the molar ratio of styrene to first monomer in step (2) of example 1 was changed to 1.5:1.
Example 5
This example provides a method for preparing an ion-conducting copolymer, which differs from example 1 in that: the molar ratio of styrene to first monomer in step (2) of example 1 was changed to 3:1.
Example 6
This example provides a method for preparing an ion-conducting copolymer, which differs from example 1 in that: the molar ratio of styrene to first monomer in step (2) of example 1 was changed to 1:3.
Example 7
This example provides a method for preparing an ion-conducting copolymer, which differs from example 1 in that: the molar ratio of styrene to first monomer in step (2) of example 1 was changed to 10:1.
Example 8
This example provides a method for preparing an ion-conducting copolymer, which differs from example 1 in that: step (2) is different from step (2), in this embodiment, step (2) is as follows:
styrene, the first monomer obtained in the step (1), p-vinylbenzyl chloride and AIBN were dissolved in a mixed solvent containing 400. Mu.L of toluene and 400. Mu.L of ethanol, and reacted at 80℃for 12 hours to obtain an ion-conducting copolymer dispersed in the mixed solvent.
Wherein the molar ratio of the styrene to the first monomer is 2:1, the mass of the first monomer is 400mg, and the mass of the p-vinylbenzyl chloride is 0.1% of the total mass of the styrene and the first monomer; the molar amount of AIBN was 1% of the total molar amount of styrene and first monomer.
Example 9
This example provides a method for preparing an ion-conducting copolymer, which differs from example 8 in that: in this example, the mass of p-vinylbenzyl chloride was 0.295% of the total mass of styrene and the first monomer.
Example 10
This example provides a method for preparing an ion-conducting copolymer, which differs from example 8 in that: in this example, the mass of p-vinylbenzyl chloride was 5% of the total mass of styrene and the first monomer.
Example 11
The embodiment provides a method for preparing an ion-conducting copolymer, which comprises the following steps:
(1) 1.72g of styrene, 1.26g of 4-chloromethylstyrene and 29.6mg of AIBN were dissolved in 2.5g of chlorobenzene solvent and reacted for 22 hours at 65℃under nitrogen. And (5) purifying by methanol reprecipitation, and drying at 60 ℃ to obtain white powder.
(2) 1.5g of the white powder obtained in the step (1), 0.520g of 1,2,4, 5-tetramethylimidazole, 30mg of DVB, 0.45mg of AIBN, 2.55g of absolute ethyl alcohol and 1.874g of absolute toluene were mixed, reacted for 1 hour at 78 ℃ under a nitrogen atmosphere, then cooled to 55 ℃ and reacted for 71 hours, and the ion conductive copolymer dispersed in a solvent (denoted as a polymer solution) was reprecipitated from the polymer solution by a methanol solution to obtain the ion conductive copolymer.
Example 12
This example provides a method for preparing an ion-conducting copolymer, which differs from example 1 in that: the mass of the first monomer in step (2) of example 1 was changed to 363mg by substituting tetramethylimidazole in step (1) of example 1 with N-methylpiperidine.
Example 13
This example provides a method for preparing an ion-conducting copolymer, which differs from example 1 in that: the tetramethylimidazole in step (1) of example 1 was replaced with pyridine, and the mass of the first monomer in step (2) of example 1 was changed to 334mg.
Example 14
The embodiment provides a preparation method of an anion exchange membrane, which comprises the following steps:
(1) The polymer solution of example 1 was directly added with 5. Mu.L of DVB and a mixed solvent containing 600. Mu.L of toluene and 600. Mu.L of ethanol, and subjected to a preliminary crosslinking reaction at 80℃for 12 hours. Then, 5. Mu.L of DVB was added to the reaction system, and the reaction was again carried out at 80℃for 12 hours.
(2) Casting the re-crosslinked system onto a planar substrate made of PET material, drying at 80 ℃ for 12 hours to form a film-shaped substance, then soaking the film-shaped substance in 30wt% KOH solution for 12 hours, completely replacing chloride ions into hydroxyl ions, and demolding to obtain the anion exchange membrane.
Examples 15 to 26
Examples 15 to 26 respectively provide a method for producing an anion exchange membrane, examples 15 to 26 differ from example 14 in that: the polymer solutions in examples 15 to 26 were selected from the polymer solutions in examples 2 to 13, respectively.
Example 27
This example provides a method for preparing an anion exchange membrane, which differs from example 14 in that: flatly paving an expanded polytetrafluoroethylene film (E-PTFE) with the thickness of 50 mu m and the porosity of 70% on a glass substrate, filling a re-crosslinked system into the pores of the expanded polytetrafluoroethylene film by adopting a coating mode, drying at 80 ℃ for 12 hours to form a film-shaped substance with a filler in the pores of the expanded polytetrafluoroethylene film, soaking the film-shaped substance in 30wt% KOH solution for 12 hours, completely replacing chloride ions into hydroxide ions, and demolding to obtain the anion exchange film.
Comparative example 1
This comparative example provides a method for preparing an ion-conducting copolymer, which is different from example 1 in that: the mass of the first monomer in step (2) of example 1 was changed to 305mg by substituting tetramethylimidazole in step (1) of example 1 with methylamine.
Comparative example 2
This comparative example provides a method for preparing an anion exchange membrane, and the comparative example differs from example 14 in that: the polymer solution in comparative example 1 was used as the polymer solution in comparative example.
Experimental example 1
The first monomer and ion-conducting copolymer prepared in example 1 were structurally characterized and the nuclear magnetic hydrogen spectrum is shown in FIG. 1.
The structural formula of the first monomer in example 1 should be as follows:
as can be seen from fig. 1, the nuclear magnetic hydrogen spectrum of the first monomer prepared in example 1 is consistent with the expected structure; 1H NMR (500 MHz, DMSO) delta 7.52-7.47 (m, 2H), 7.14 (d, j=8.1 Hz, 2H), 6.74 (dd, j=17.7, 10.9 Hz, 1H), 5.85 (d, j=17.7 Hz, 1H), 5.43 (s, 2H), 5.29 (d, j=11.0 Hz, 1H), 3.66 (s, 3H), 3.42 (s, 2H), 3.17 (s, 1H), 2.63 (s, 3H), 2.24 (s, 3H), 2.13 (s, 3H); the first monomer structure synthesized by the reaction accords with the expected structure.
Experimental example 2
The first monomer and ion-conducting copolymer prepared in example 12 were structurally characterized and the nuclear magnetic hydrogen spectrum is shown in FIG. 2.
The structural formula of the first monomer in example 12 should be as follows:
as can be seen from fig. 2, the nuclear magnetic hydrogen spectrum of the first monomer prepared in example 12 is consistent with the expected structure; 1H NMR (500 MHz, DMSO) delta 7.61 (d, j=7.9 Hz, 2H), 7.52 (d, j=7.9 Hz, 2H), 6.80 (dd, j=17.7, 10.9 Hz, 1H), 5.95 (d, j=17.7 Hz, 1H), 5.38 (d, j=10.9 Hz, 1H), 4.58 (s, 2H), 3.30 (m, 4H), 2.92 (s, 3H), 1.85 (m, 4H), 1.68-1.40 (m, 2H); the first monomer structure synthesized by the reaction conforms to the expected structure, with the peak portion at 3.30 being capped by the water peak.
Experimental example 3
The first monomer and ion-conducting copolymer prepared in example 13 were structurally characterized and the nuclear magnetic hydrogen spectrum is shown in FIG. 3.
The structural formula of the first monomer in example 13 should be as follows:
as can be seen from fig. 3, the nuclear magnetic hydrogen spectrum of the first monomer prepared in example 13 is consistent with the expected structure; 1H NMR (500 MHz, DMSO) δ9.34 (s, 2H), 8.64 (t, j=7.8 Hz, 1H), 8.20 (t, j=7.0 Hz, 2H), 7.72-7.46 (m, 4H), 6.75 (dd, j=17.6, 10.9 Hz, 1H), 6.02 (s, 2H) 5.91-5.81 (d, 1H), 5.32 (d, j=10.9 Hz, 1H); the first monomer structure synthesized by the reaction accords with the expected structure.
Experimental example 4
The electrochemical properties and alkali stability of the anion exchange membranes prepared in examples 14 to 27 were measured, respectively, and the measurement results are shown in Table 1.
The electrochemical performance test method comprises the following steps: electrochemical testing was performed with a zero gap cell. The cathode electrode and the anode electrode are respectively made of active nickel materials with foam nickel substrates, electrolyte is 30wt% potassium hydroxide solution, and 200sccm of electrolyte is respectively introduced into the two sides of the cathode and the anode. Electrochemical performance and alkaline stability tests were performed at different current densities using an Autolab PGSTAT128N electrochemical workstation.
TABLE 1
Description: in table 1 "/" indicates that no such experimental test was performed.
In Table 1, the anion exchange membranes prepared in examples 14-20 all have better electrochemical properties; as can be seen from the comparison of examples 14 to 20, the electrochemical properties and stability of the prepared anion exchange membrane can be simultaneously influenced by controlling the ratio of the monomers for preparing the ion-conducting copolymer.
The anion exchange membranes prepared in examples 21-23 all had better electrochemical properties, but the anion exchange membranes prepared in examples 21-23 all had slightly poorer overall properties (electrochemical properties and stability) than the anion exchange membrane prepared in example 14, indicating that the "binary system ion-conducting copolymer prepared with styrene and the first monomer" is advantageous for further improving the electrochemical properties and long-term stability of the anion exchange membrane compared to the "ternary system ion-conducting copolymer prepared with styrene, the first monomer and p-vinylbenzyl chloride".
As can be seen from the comparison of example 24 and example 14, the use of the "copolymerization of ionic monomer (i.e., first monomer) with styrene monomer" is advantageous for improving the electrochemical performance and long-term stability of the anion exchange membrane, compared to the "copolymerization of halomethylated nonionic monomer (i.e., 4-chloromethylstyrene) with styrene monomer followed by quaternization of the halomethylated functional groups in the copolymer to prepare the ion-conducting copolymer".
As can be seen from the comparison of the example 25 and the example 14, compared with the case that the cyclic amine group in the first monomer is N-methylpiperidine and the cyclic amine group in the first monomer is tetramethyl imidazole, the electrochemical performance and the long-time stability of the anion exchange membrane are further improved.
As can be seen from the comparison of examples 14 and examples 25 to 26, the cyclic amine group in the first monomer is selected from N-methylpiperidine and tetramethylimidazole, which is advantageous for further improving the electrochemical performance of the anion exchange membrane, compared to the cyclic amine group in the first monomer which is selected from pyridine.
As can be seen from a comparison of example 27 and example 14, in the case of "the anion-exchange membrane having the expanded polytetrafluoroethylene membrane as the porous support layer", not only the electrochemical performance of the anion-exchange membrane can be effectively maintained, but also the long-term stability of the anion-exchange membrane can be further improved.
In summary, the ion-conducting copolymer provided by the application has better electrochemical performance and long-time stability, so that the anion-exchange membrane prepared by crosslinking the ion-conducting copolymer also has better electrochemical performance (including ion conductivity of the anion-exchange membrane) and stability (including mechanical strength and electrochemical durability of the anion-exchange membrane), and is beneficial to widening the application range of the anion-exchange membrane to a great extent. The preparation method of the ion-conducting copolymer can realize accurate adjustment and control of quaternary ammonium salt sites in the ion-conducting copolymer, can effectively avoid residues of halomethylation functional groups in the copolymerization process, can improve the electrochemical performance and quality controllability of the ion-conducting copolymer, and is further beneficial to improving the electrochemical performance of the anion-exchange membrane prepared subsequently.
The embodiments described above are some, but not all, of the embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Claims (10)
1. An ion-conducting copolymer, characterized in that the ion-conducting copolymer has the expression formula: am-Bn-Cq, the structure of the ion-conducting copolymer is as follows:
wherein m is more than 0, n is more than or equal to 0, q is more than or equal to 0, and n and q are not simultaneously 0;
R 1 + is a positively charged cyclic amine group selected from at least one of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium;
x is at least one selected from hydroxyl, chlorine, bromine, iodine, p-toluenesulfonyloxy, trifluoromethanesulfonic acid and methanesulfonyloxy;
R 2 selected from halogen substituted alkyl groups.
2. The ion conducting copolymer of claim 1, wherein the positively charged cyclic amine groups are selected from at least one of imidazolium and piperidinium;
And/or the positively charged cyclic amine group is selected from at least one of tetramethylimidazolium and N-methylpiperidinium;
and/or X is selected from chlorine atoms;
and/or R 2 At least one selected from chloromethyl, bromomethyl and iodomethyl.
3. The ion conducting copolymer of claim 1 or 2, wherein q = 0 and the ratio of n to m is (1:2) - (9:1).
4. The ion conducting copolymer of claim 3, wherein the ratio of n to m is (1:1) - (4:1).
5. An ion-conducting copolymer according to claim 3, wherein q = 0, the positively charged cyclic amine groups are selected from tetramethylimidazolium, and the ratio of n to m is (1.5:1) - (3:1).
6. The ion conducting copolymer of claim 5, wherein the ratio of n to m is (1.85:1) - (2.5:1).
7. The ion conducting copolymer of claim 1, wherein m, n and q are each greater than 0, the total weight of C units in the ion conducting copolymer being less than or equal to 0.295% of the total mass of the ion conducting copolymer;
wherein the ratio of the total of n and q to m is (1:1) - (4:1).
8. A method of preparing an ion-conducting copolymer comprising: carrying out copolymerization reaction on the first component and the second component; wherein the first component is a first monomer, and the second component comprises a second monomer and/or a third monomer;
Wherein the structural formula of the first monomer is as follows:
R 1 + is a positively charged cyclic amine group selected from at least one of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium;
x is at least one selected from hydroxyl, chlorine, bromine, iodine, p-toluenesulfonyloxy, trifluoromethanesulfonic acid and methanesulfonyloxy;
the second monomer is styrene;
the structural formula of the third monomer is as follows:
R 2 selected from halogen substituted alkyl groups.
9. The method of claim 8, wherein the molar ratio of the second component to the first component is (1:2) - (9:1);
and/or, the copolymerization is carried out under a mixed solvent containing a first solvent and a second solvent; and in the mixed solvent, the volume ratio of the first solvent to the second solvent is (1:4) - (4:1); wherein the first solvent is selected from at least one of benzene, toluene, ethylbenzene, mesitylene, petroleum ether and n-hexane, and the second solvent is selected from at least one of methanol, ethanol and isopropanol;
and/or, the copolymerization is carried out in the presence of an initiator in a molar amount of 0.1 to 3.0% of the total molar amount of the first component and the second component;
And/or the temperature of the copolymerization reaction is 60-100 ℃, and the time of the copolymerization reaction is 6-18h;
and/or the copolymerization is carried out in the presence of an initiator, wherein the initiator is azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide tert-butyl ester or methyl ethyl ketone peroxide.
10. An anion exchange membrane, characterized in that the anion exchange membrane comprises a porous supporting layer and a filler filled in pores of the porous supporting layer, wherein the filler is made of a cross-linked product of the ion-conducting copolymer according to any one of claims 1 to 7;
or, the anion exchange membrane comprises a membrane matrix, and the membrane matrix is made of the cross-linked product of the ion-conducting copolymer as claimed in any one of claims 1 to 7.
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| CN117106209A (en) * | 2023-08-23 | 2023-11-24 | 固碳新能源科技(苏州)有限公司 | Ion-conducting cross-linked material, preparation method thereof, anion exchange membrane and application thereof |
| CN117487052A (en) * | 2023-12-27 | 2024-02-02 | 固碳新能源科技(苏州)有限公司 | Ion-conducting polymer, method for producing ion-conducting cross-linked substance, anion-exchange membrane and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117106209A (en) * | 2023-08-23 | 2023-11-24 | 固碳新能源科技(苏州)有限公司 | Ion-conducting cross-linked material, preparation method thereof, anion exchange membrane and application thereof |
| CN117487052A (en) * | 2023-12-27 | 2024-02-02 | 固碳新能源科技(苏州)有限公司 | Ion-conducting polymer, method for producing ion-conducting cross-linked substance, anion-exchange membrane and use thereof |
| CN117487052B (en) * | 2023-12-27 | 2024-04-12 | 固碳新能源科技(苏州)有限公司 | Ion-conducting polymer, method for producing ion-conducting cross-linked substance, anion-exchange membrane and use thereof |
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| CN116082555B (en) | 2023-09-08 |
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