CN110975944B - Preparation method of polymer anion exchange membrane - Google Patents
Preparation method of polymer anion exchange membrane Download PDFInfo
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- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
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Abstract
The invention belongs to the technical field of preparation of functional polymer materials, and discloses a preparation method of a polymer anion exchange membrane. The method adopts two chloromethylated macromolecules with different heights and different heights, controls the content of an ionizing reagent methylimidazole to ensure that the macromolecules simultaneously contain chloromethyl groups and cationic groups, can form an anion exchange membrane with a bicontinuous phase separation structure after being mixed into the membrane, and then initiates a chloromethyl reaction in the membrane to form a self-crosslinking structure through heating-annealing treatment, so that the ion conduction and the stability of the anion exchange membrane are greatly improved.
Description
Technical Field
The invention belongs to the technical field of preparation of functional polymer materials, and particularly relates to a preparation method of a polymer anion exchange membrane.
Background
Anion exchange membranes are receiving attention from researchers due to their application value in new energy, environmental protection and chemical industries such as fuel cells, flow batteries, electrodialysis, electrolysis industry and the like. Although cation exchange membranes, represented by Nafion (r), a perfluorosulfonic acid membrane, have been widely used commercially, anion exchange membranes have been lacking a high performance ion exchange membrane that can be matched therewith. At the same time, new application fields such as Fuel Cells (FC), reverse osmosis electrodialysis (RO-ED) bring new challenges and higher performance requirements to anion exchange membranes. Currently, anion exchange membranes should further enhance their ionic conductivity and stability. In addition, the cost problem is also considered in the preparation process, and the problem of high cost of the Nafion-type membrane is avoided, so as to promote the industrial development of the related application.
Although Nafion's perfluorosulfonic acid chemical structure has its particularity, it is difficult to find a similar structure in anion exchange membrane materials, but its structure can be used as a reference to optimize anion exchange membrane performance. The microphase-separated structure of Nafion is reported to play an important role in its excellent performance (Nature Materials,2008,7, 75-83). Phase separation occurs inside the Nafion membrane due to the strong difference between the strongly hydrophilic sulfonic acid groups and the strongly hydrophobic perfluorinated backbone, but only nano-scale micro-domains are created due to the blocking of covalent bonds. However, such a structure of Nafion enables the relative concentration of ionic groups and the formation of a continuous ion-conducting channel, thereby significantly improving ion-conducting efficiency. On the other hand, the perfluorinated hydrophobic microdomains also impart good physical stability to the membrane. There are also many researchers trying to mimic the molecular structure of Nafion in negative membranes, for example (Energy and environmental Science,2012,7, 354-360) reported quaternized polysulfone anion exchange membranes with various hydrophobic side chains, achieving microphase separation structures, and improving both the ionic conductivity and stability of the membranes. However, the microphase separation structure is influenced by various factors such as the rigidity, polarity, quantity of hydrophilic and hydrophobic chain segments, the molecular structure of the polymer and the like, and the morphology is difficult to regulate (Energy and Environment Science,2010,3, 1326-1338), so that the performance is good and bad. In addition, the synthesis of the microphase separation membrane usually involves grafting and block copolymerization, is relatively complex and is not beneficial to reducing the cost.
Studies on the phase separation behavior of polymers can also be found in multicomponent polymer systems. Blending achieves phase separation much easier than a single component. The phase separation behavior of binary polymer blends is currently considered to be two, spinodal phase separation based on a spinodal decomposition mechanism and nucleation-growth phase separation based on a nucleation mechanism. The difference between the two is the difference in compatibility between the components. Spinodal phase separation can form a bicontinuous phase separation structure (Progress in Polymer Science,2018, 10, 44041-44049). By providing two phases with different degrees of functionalization, it should be possible to have an amphiphilic-hydrophobic bicontinuous phase separation structure that behaves like Nafion. It is worth noting that Nafion is not good for the physical stability of the membrane because the hydrophilic-hydrophobic water phase interface of the single component is tightly connected by covalent bonds, while the blend membrane of the binary component is obviously weaker in connection at the phase interface. The cross-linking technique is an effective means for improving the physical stability of the membrane, and is currently mainly classified into covalent cross-linking and ionic cross-linking. Ionic crosslinking is not resistant to high temperatures and ionic bonds have a certain influence on ionic conduction, so covalent crosslinking using chemical covalent bonds is the first choice. However, covalent cross-linking techniques often require the addition of additional cross-linking agents to the membrane, which undoubtedly affect the above-mentioned phase separation structure (Chemical Communication,2011, 47, 2856-2858), and furthermore, additional cross-linking reaction steps also often increase the technical complexity and cost.
Disclosure of Invention
The invention focuses on preparing a high-performance anion exchange membrane, and provides a preparation method of a polymer anion exchange membrane.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a preparation method of a polymer anion exchange membrane comprises the steps of carrying out imidization on a polyether-ether-ketone high molecular part with two different chloromethylation degrees, then carrying out blending to prepare the anion exchange membrane with a bicontinuous phase separation structure, and carrying out self-crosslinking on the anion exchange membrane with the bicontinuous phase separation structure through heat treatment to prepare the polymer anion exchange membrane.
Further, the method is carried out according to the following steps:
(1) Slowly adding polyether-ether-ketone into concentrated sulfuric acid at-10 ℃ to prepare a solution with the concentration of 16.67g/L, and then adding chloromethyl octyl ether, wherein the volume ratio of the chloromethyl octyl ether to the concentrated sulfuric acid is 1:12, raising the temperature by 10 ℃, and reacting for 50min to obtain low chloromethylated polyether-ether-ketone;
slowly adding polyether-ether-ketone into concentrated sulfuric acid at-10 ℃ to prepare a solution with the concentration of 16.67g/L, and then adding chloromethyl octyl ether, wherein the volume ratio of the chloromethyl octyl ether to the concentrated sulfuric acid is 1:12, raising the temperature by 10 ℃, and reacting for 18 hours to obtain high chloromethylation polyether-ether-ketone;
(2) Dissolving low chloromethylation polyether-ether-ketone in N, N-dimethyl pyrrolidone to prepare a low chloromethylation polyether-ether-ketone solution; dissolving high chloromethylation polyether-ether-ketone in N, N-dimethyl pyrrolidone to prepare a high chloromethylation polyether-ether-ketone solution; adding 1-methylimidazole into the high chloromethylated polyether-ether-ketone solution for reaction, and then adding the low chloromethylated polyether-ether-ketone solution into a reaction solution for reaction to obtain a membrane casting solution;
(3) Preparing an uncrosslinked anion exchange membrane from the casting solution prepared in the step (2) by adopting a casting method;
(4) Carrying out heat treatment on the uncrosslinked anion exchange membrane prepared in the step (3) to obtain a crosslinked anion exchange membrane;
(5) And (5) immersing the crosslinked anion-exchange membrane prepared in the step (4) into a sodium salt solution containing corresponding anions for ion replacement, and washing away excessive ions by using deionized water to obtain the polymer anion-exchange membrane with the corresponding anions.
Further, the mass ratio of the 1-methylimidazole to the sum of the dry weights of the low chloromethylated polyether ether ketone and the high chloromethylated polyether ether ketone in the step (2) is 1.
Further, the reaction conditions of the 1-methylimidazole and the high chloromethylated polyetheretherketone solution in the step (2) are 1-3h at room temperature.
Further, the reaction temperature of the 1-methylimidazole and the low chloromethylated polyetheretherketone solution in the step (2) is 40-60 ℃, and the reaction time is 9-12h.
Further, the temperature of the heat treatment in the step (4) is 100-120 ℃ and the time is 24-48h.
Further, the sodium salt solution in step (4) is a sodium chloride solution or a sodium hydroxide solution.
The beneficial effects of the invention are:
the invention adopts the spinodal blending and heat treatment technology to successfully prepare the anion exchange membrane with the bicontinuous phase separation and self-crosslinking structure, thereby endowing the membrane with good ionic conductivity and physical stability.
The synthesis process of the polymer used in the method does not relate to the complex grafting and block synthesis processes, a bicontinuous phase separation structure is realized by utilizing spinodal line blending, and a nanoscale ion transfer channel with high ion concentration can be constructed, so that the ion conductivity of the membrane is improved. Aiming at the problem of the physical stability of the membrane, the invention introduces a thermal initiation self-crosslinking process based on chloromethyl, and has the advantages that the original chloromethyl contained in the preparation process of macromolecules is used as a crosslinking agent, the physical stability of the membrane can be improved through simple heat treatment without adding the crosslinking agent in a self-crosslinking structure, the in-situ crosslinking of an anion exchange membrane is realized, and the introduction of an additional crosslinking agent is avoided. In addition, the heat treatment crosslinking process of the method is simple and convenient, the used material is based on commercial high-molecular polyether-ether-ketone, the functionalization method is traditional chloromethylation and imidazolium, the cost is low, and the technology is simple and reliable. The anion exchange membrane prepared by the method can be used in the fields of electrodialysis, electrolysis, fuel cells and the like.
Drawings
FIG. 1 is a scanning electron microscope image of cross-sections of anion exchange membranes prepared at different blending ratios; wherein a represents comparative example 2, b represents example 1, c represents example 2, d represents example 3;
FIG. 2 NMR spectra of high chloromethyl polyetheretherketone after heat treatment;
FIG. 3 is a graph showing the change of chloride ion conductivity at different temperatures for anion exchange membranes prepared in examples;
FIG. 4 is a graph showing the change of swelling degree of each anion-exchange membrane prepared in each example at different temperatures.
Detailed Description
The invention provides a preparation method of a polymer anion exchange membrane, which comprises the steps of carrying out imidazolium treatment on a high molecular part of polyether-ether-ketone with two different chloromethylation degrees, blending to prepare the anion exchange membrane with a bicontinuous phase separation structure, and carrying out self-crosslinking on the anion exchange membrane with the bicontinuous phase separation structure through heat treatment to prepare the polymer anion exchange membrane.
The present invention is further described in detail below by way of specific examples, which will enable one skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Comparative example 1
(1) 4g of polyetheretherketone are dissolved in 240mL of concentrated sulphuric acid at-10 ℃. Then adding 20ml of chloromethyl octyl ether, raising the temperature to 10 ℃, and reacting for 50min to obtain polyether-ether-ketone with low chloromethylation degree;
(2) Dissolving the low chloromethylation polyether-ether-ketone prepared in the step (1) in NMP, wherein the mass concentration is 5wt%. Adding 30mg of 1-methylimidazole into the low chloromethylated polyether-ether-ketone solution to react for 2 hours at room temperature, then adding the low chloromethylated polyether-ether-ketone solution to react for 10 hours at 50 ℃ to obtain a membrane casting solution;
(3) Pouring the casting solution prepared in the step (2) into an ultra-flat culture dish with the diameter of 7cm by adopting a flow extension method, covering a cover, and forming a film in a forced air oven at 60 ℃ for 24 hours to obtain an uncrosslinked anion exchange membrane;
(4) Immersing the cross-linked anion exchange membrane prepared in the step (3) into 1M sodium chloride solution for 24 hours to replace the cross-linked anion exchange membrane with chloride ions; immersing the membrane in 1M sodium hydroxide solution for 24h, and replacing the membrane with hydroxide ions, washing the membrane with deionized water to be neutral, and obtaining the anion exchange membrane corresponding to the ions.
Comparative example 2
Compared with the comparative example 1, the method adds the steps between the step (3) and the step (4): putting the prepared anion exchange membrane into a vacuum oven, performing heat treatment at 120 ℃ for 24h, and then slowly cooling to room temperature to obtain a cross-linked anion exchange membrane; the rest is the same as in comparative example 1.
Example 1
(1) Dissolving 4g of polyether-ether-ketone in 240mL of concentrated sulfuric acid at the temperature of-10 ℃; then adding 20ml of chloromethyl octyl ether, raising the temperature to 10 ℃, and reacting for 50min to obtain polyether-ether-ketone with low chloromethylation degree; reacting for 18h to obtain polyether-ether-ketone with high chloromethylation degree; the polymer is precipitated in ethanol;
(2) Dissolving 25mg of high chloromethylated polyether ether ketone prepared in the step (1) in NMP, and dissolving 225mg of high chloromethylated polyether ether ketone prepared in the step (1) in NMP, wherein the mass concentration of the low chloromethylated polyether ether ketone solution and the high chloromethylated polyether ether ketone solution is 5wt%;
adding 30mg of 1-methylimidazole into the high chloromethylation polyether-ether-ketone solution to react for 2 hours at room temperature, then adding the low chloromethylation polyether-ether-ketone solution to react for 10 hours at 40 ℃ to obtain a membrane casting solution;
(3) Pouring the casting solution prepared in the step (2) into an ultra-flat culture dish with the diameter of 7cm by adopting a flow extension method, covering a cover, and forming a film in a forced air oven at 60 ℃ for 24 hours to obtain an uncrosslinked anion exchange membrane;
(4) Putting the anion exchange membrane prepared in the step (3) into a vacuum oven, performing heat treatment at 120 ℃ for 24 hours, and then slowly cooling to room temperature to obtain a cross-linked anion exchange membrane;
(5) Immersing the cross-linked anion exchange membrane prepared in the step (4) into 1M sodium chloride solution for 24 hours to replace the cross-linked anion exchange membrane with chloride ions; immersing the membrane in 1M sodium hydroxide solution for 24h, and replacing the membrane with hydroxide ions, washing the membrane with deionized water to be neutral, and obtaining the anion exchange membrane corresponding to the ions.
Example 2
(1) Dissolving 4g of polyether-ether-ketone in 240mL of concentrated sulfuric acid at the temperature of-10 ℃; then adding 20ml of chloromethyl octyl ether, raising the temperature to 10 ℃, and reacting for 50min to obtain polyether-ether-ketone with low chloromethylation degree; reacting for 18h to obtain polyether-ether-ketone with high chloromethylation degree; the polymer is precipitated in water;
(2) Dissolving 50mg of high chloromethylated polyether ether ketone prepared in the step (1) in NMP, and dissolving 200mg of high chloromethylated polyether ether ketone prepared in the step (1) in NMP, wherein the mass concentration of the low chloromethylated polyether ether ketone solution and the high chloromethylated polyether ether ketone solution is 4wt%;
adding 27mg of 1-methylimidazole into a high chloromethylation polyether-ether-ketone solution to react for 3 hours at room temperature, then adding a low chloromethylation polyether-ether-ketone solution to react for 9 hours at 50 ℃ to obtain a membrane casting solution;
(3) Pouring the casting solution prepared in the step (2) into an ultra-flat culture dish with the diameter of 7cm by adopting a flow extension method, covering a cover, and forming a film in a forced air oven at 60 ℃ for 24 hours to obtain an uncrosslinked anion exchange membrane;
(4) Putting the anion exchange membrane prepared in the step (3) into a vacuum oven, performing heat treatment for 24 hours at 100 ℃, and then slowly cooling to room temperature to obtain a cross-linked anion exchange membrane;
(5) Immersing the cross-linked anion exchange membrane prepared in the step (4) into 1M sodium chloride solution for 24 hours to replace the cross-linked anion exchange membrane with chloride ions; immersing in 1M sodium hydroxide solution for 24h to replace hydroxide ions, washing with deionized water to neutrality, and making into anion exchange membrane.
Example 3
(1) 4g of polyetheretherketone are dissolved in 240mL of concentrated sulphuric acid at-10 ℃. Then adding 20ml of chloromethyl octyl ether, raising the temperature by 10 ℃, and reacting for 50min to obtain polyether-ether-ketone with low chloromethylation degree; reacting for 18h to obtain the polyether-ether-ketone with high chloromethylation degree. The polymer is precipitated in water;
(2) Dissolving 75mg of high chloromethylated polyether-ether-ketone prepared in the step (1) in NMP, and dissolving 175mg of high chloromethylated polyether-ether-ketone prepared in the step (1) in NMP, wherein the mass concentration of the low chloromethylated polyether-ether-ketone solution and the high chloromethylated polyether-ether-ketone solution is 7wt%;
adding 35mg of 1-methylimidazole into a high chloromethylation polyether-ether-ketone solution to react for 1 hour at room temperature, then adding a low chloromethylation polyether-ether-ketone solution to react for 12 hours at 60 ℃ to obtain a membrane casting solution;
(3) Pouring the casting solution prepared in the step (2) into an ultra-flat culture dish with the diameter of 7cm by adopting a flow extension method, covering a cover, and forming a film in a forced air oven at 60 ℃ for 24 hours to obtain an uncrosslinked anion exchange membrane;
(4) Putting the anion exchange membrane prepared in the step (3) into a vacuum oven, performing heat treatment for 48 hours at 100 ℃, and then slowly cooling to room temperature to obtain a cross-linked anion exchange membrane;
(5) Immersing the cross-linked anion exchange membrane prepared in the step (4) into 1M sodium chloride solution for 24 hours to replace the cross-linked anion exchange membrane with chloride ions; immersing in 1M sodium hydroxide solution for 24h to replace hydroxide ions, washing with deionized water to neutrality, and making into anion exchange membrane.
As shown in fig. 2, according to SEM images of the cross-section of the anion exchange membrane of comparative example 2, examples 1, 2, and 3, the blended membrane (examples 1, 2, and 3) shows a bicontinuous phase-separated morphology structure compared to the non-blended membrane (comparative example 2), and combined with the membrane process and the existing theory, it can be considered that the structure of the blended membrane is caused by spinodal phase separation of two polymer components. The phase separation size is between 40 and 120nm, and the method belongs to the nanometer scale.
The membranes after thermal crosslinking (comparative example 1, examples 1, 2, 3) were not completely soluble in the casting solution n.n dimethylpyrrolidone, indicating the presence of a crosslinked structure. FIG. 2 is the nuclear magnetic hydrogen spectrum of the extract of high chloromethylated polyetheretherketone in deuterated chloroform after thermal crosslinking treatment, and the appearance of a new signal peak can be observed, which is the benzyl hydrogen generated after crosslinking and connecting two benzene rings, and shows that the crosslinking of the membrane is formed by Friedel-crafts alkylation of residual chloromethyl in the membrane.
FIG. 3 is a graph showing the ion conductivity of anion exchange membranes (chloride ion) according to temperature, which are prepared in comparative examples. It can be seen that the membranes with the blended structure (examples 1, 2, 3) have significantly higher ionic conductivities than the non-blended membranes (comparative examples 1, 2). This indicates that the blended structure can significantly improve the ionic conductivity of the membrane.
FIG. 4 is a graph of swelling capacity versus temperature for anion exchange membranes prepared in comparative examples and comparative examples. The degree of swelling is the change in length of the film in the wet and dry state. It can be seen that the swelling degree of the film having a crosslinked structure (comparative example 2, example 1, 2, 3) is significantly lower than that of the non-crosslinked film (comparative example 1). This indicates that the crosslinked structure can significantly improve the physical stability of the membrane.
In summary, the method for preparing the anion exchange membrane provided by the invention is to blend two polyether-ether-ketone polymers to form a spinodal bi-continuous phase separation structure; the ion conductivity and physical stability of the anion exchange membrane can be improved by enabling chloromethyl remained in the membrane to form a self-crosslinking structure through heat treatment. The method is simple and efficient, and has practical value.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and those skilled in the art can make various changes and modifications within the spirit and scope of the present invention without departing from the spirit and scope of the appended claims.
Claims (6)
1. A preparation method of a polymer anion exchange membrane is characterized in that after two polyether-ether-ketone high molecular parts with different chloromethylation degrees are imidazolium-treated, blending is carried out to prepare the anion exchange membrane with a bicontinuous phase separation structure, and the anion exchange membrane with the bicontinuous phase separation structure is subjected to self-crosslinking through heat treatment to prepare the polymer anion exchange membrane; the method comprises the following steps:
(1) Slowly adding polyether-ether-ketone into concentrated sulfuric acid at-10 ℃ to prepare a solution with the concentration of 16.67g/L, and then adding chloromethyl octyl ether, wherein the volume ratio of the chloromethyl octyl ether to the concentrated sulfuric acid is 1:12, raising the temperature by 10 ℃, and reacting for 50min to obtain low chloromethylated polyether-ether-ketone;
slowly adding polyether-ether-ketone into concentrated sulfuric acid at-10 ℃ to prepare a solution with the concentration of 16.67g/L, and then adding chloromethyl octyl ether, wherein the volume ratio of the chloromethyl octyl ether to the concentrated sulfuric acid is 1:12, raising the temperature by 10 ℃, and reacting for 18 hours to obtain high chloromethylation polyetheretherketone;
(2) Dissolving low chloromethylation polyether-ether-ketone in N, N-dimethyl pyrrolidone to prepare a low chloromethylation polyether-ether-ketone solution; dissolving high chloromethylation polyether-ether-ketone in N, N-dimethyl pyrrolidone to prepare a high chloromethylation polyether-ether-ketone solution; adding 1-methylimidazole into the high chloromethylated polyether-ether-ketone solution for reaction, and then adding the low chloromethylated polyether-ether-ketone solution into a reaction solution for reaction to obtain a membrane casting solution;
(3) Preparing the membrane casting solution prepared in the step (2) into an uncrosslinked anion exchange membrane by adopting a flow extension method;
(4) Carrying out heat treatment on the uncrosslinked anion exchange membrane prepared in the step (3) to obtain a crosslinked anion exchange membrane;
(5) And (4) immersing the crosslinked anion-exchange membrane prepared in the step (4) into a sodium salt solution containing corresponding anions for ion replacement, and washing away excessive ions by using deionized water to obtain the polymer anion-exchange membrane with the corresponding anions.
2. The method for preparing a polymer anion exchange membrane according to claim 1, wherein the mass ratio of the 1-methylimidazole to the sum of the dry weights of the low chloromethylated polyetheretherketone and the high chloromethylated polyetheretherketone in step (2) is 1.
3. The method for preparing a polymer anion exchange membrane according to claim 1, wherein the reaction conditions of the 1-methylimidazole and the high chloromethylated polyetheretherketone solution in the step (2) are 1-3h at room temperature.
4. The method for preparing a polymer anion exchange membrane according to claim 1, wherein the reaction temperature of the 1-methylimidazole and the low chloromethylated polyetheretherketone solution in the step (2) is 40-60 ℃ and the reaction time is 9-12h.
5. The method for preparing a polymer anion exchange membrane according to claim 1, wherein the temperature of the heat treatment in the step (4) is 100-120 ℃ and the time is 24-48h.
6. The method for preparing a polymer anion exchange membrane according to claim 1, wherein the sodium salt solution in the step (4) is a sodium chloride solution or a sodium hydroxide solution.
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