CN114160213A - Polystyrene sodium sulfonate/polyvinyl alcohol cation exchange membrane and preparation method thereof - Google Patents
Polystyrene sodium sulfonate/polyvinyl alcohol cation exchange membrane and preparation method thereof Download PDFInfo
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- CN114160213A CN114160213A CN202111440979.0A CN202111440979A CN114160213A CN 114160213 A CN114160213 A CN 114160213A CN 202111440979 A CN202111440979 A CN 202111440979A CN 114160213 A CN114160213 A CN 114160213A
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- polyvinyl alcohol
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention belongs to the technical field of cation exchange membranes, and particularly relates to a sodium polystyrene sulfonate/polyvinyl alcohol cation exchange membrane and a preparation method thereof. The preparation method of the sodium polystyrene sulfonate polyvinyl alcohol cation exchange membrane comprises the following steps: mixing a polyvinyl alcohol solution and a sodium polystyrene sulfonate solution to prepare a membrane casting solution; mixing methanol, acetic acid, sulfuric acid and a cross-linking agent to prepare cross-linking liquid; and mixing the membrane casting solution and the crosslinking solution, scraping the membrane, and heating for crosslinking to obtain the crosslinked cation exchange membrane. The invention takes polyvinyl alcohol and sodium polystyrene sulfonate as membrane materials, takes water as solvent, and meets the environmental protection requirement in process; the cross-linked sodium polystyrene sulfonate/polyvinyl alcohol cation exchange membrane prepared by the invention has better water resistance, and keeps higher water absorption and dimensional stability while improving the water resistance.
Description
Technical Field
The invention belongs to the technical field of cation exchange membranes, and particularly relates to a sodium polystyrene sulfonate/polyvinyl alcohol cation exchange membrane and a preparation method thereof.
Background
The ion exchange membrane is a polymer membrane which contains ionic groups and has selective permeability to ions in a solution. Since its ion permselectivity is generally mainly utilized in application, it is also referred to as an ion permselective membrane.
Ion exchange membrane separation technology has occupied an indispensable position in the fields of environmental protection, chemical synthesis, food processing and the like. The best-known cation exchange membrane with the best performance is a perfluorosulfonic acid membrane produced by DuPont company, which has important application in the fields of dye batteries, chlor-alkali industry and the like, but the price is high, so that the development of new cation exchange membrane materials is paid attention by researchers in various countries.
Disclosure of Invention
The invention provides a sodium polystyrene sulfonate/polyvinyl alcohol cation exchange membrane and a preparation method thereof.
In order to solve the technical problems, the invention provides a preparation method of a sodium polystyrene sulfonate polyvinyl alcohol cation exchange membrane, which comprises the following steps: mixing a polyvinyl alcohol solution and a sodium polystyrene sulfonate solution to prepare a membrane casting solution; mixing methanol, acetic acid, sulfuric acid and a cross-linking agent to prepare cross-linking liquid; and mixing the membrane casting solution and the crosslinking solution, scraping the membrane, and heating for crosslinking to obtain the crosslinked cation exchange membrane.
In another aspect, the invention also provides the sodium polystyrene sulfonate polyvinyl alcohol cation exchange membrane prepared by the preparation method, wherein the water absorption rate of the sodium polystyrene sulfonate polyvinyl alcohol cation exchange membrane is 70-500%, and the swelling degree is 0.5-0.8.
The invention has the beneficial effects that polyvinyl alcohol and sodium polystyrene sulfonate are used as membrane materials, and the solvent is water, so that the invention meets the environmental protection requirement in the process; the cross-linked sodium polystyrene sulfonate/polyvinyl alcohol cation exchange membrane prepared by the invention has good water resistance, and keeps high water absorption and dimensional stability while improving the water resistance; the cross-linked sodium polystyrene sulfonate/polyvinyl alcohol cation exchange membrane prepared by the invention can be sulfonated by a sulfonation reagent to residual polyvinyl alcohol hydroxyl in the membrane, so that the ion exchange performance is further improved.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description.
In order to make the aforementioned and other objects, features and advantages of the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Currently, the base materials for cation exchange membranes are mainly sulfonated resins, such as perfluorosulfonic acid resin, sulfonated polystyrene, and sulfonated polysulfone. The sulfonic acid group is a functional group which plays a role in ion exchange, can form ion clusters to transfer ions, and can improve the hydrophilicity of the membrane. Therefore, a high density of sulfonic acid groups is an important factor for securing excellent hydrophilicity and ion exchange performance. Lower degrees of sulfonation result in poor film-forming properties and low ion exchange properties of the material.
The preparation method of the sulfonated membrane material mainly comprises two methods of front sulfonation and rear sulfonation, and can be divided into main chain sulfonation and side chain sulfonation according to the position of a sulfonic acid group, and the side chain sulfonation is mainly adopted at present. The membrane material with high sulfonation degree is mainly prepared by a pre-sulfonation method, namely, sulfonated monomers are adopted for polymerization, and the membrane material prepared by homopolymerization of the sulfonated monomers has very high hydrophilicity and very high swelling degree in water, and even is dissolved in a large amount. Thus, the pre-sulfonation method generally employs copolymerization of a sulfonated monomer with other monomers to form a cross-linked structure to improve the water resistance of the membrane. The post-sulfonation method is to graft a sulfonic acid group on a polymer chain, and the sulfonation degree is generally low due to the steric hindrance effect.
The invention provides a preparation method of a sodium polystyrene sulfonate polyvinyl alcohol cation exchange membrane, which comprises the following steps: mixing a polyvinyl alcohol solution and a sodium polystyrene sulfonate solution to prepare a membrane casting solution; mixing methanol, acetic acid, sulfuric acid and a cross-linking agent to prepare cross-linking liquid; and mixing the membrane casting solution and the crosslinking solution, scraping the membrane, and heating for crosslinking to obtain the crosslinked cation exchange membrane.
Specifically, the sodium polystyrene sulfonate is a gel-type strong-acid ion exchange resin, is prepared by taking polystyrene crosslinked by divinylbenzene as a framework material and then performing post sulfonation, and the prior industrial resin has more impurities, complicated pretreatment and poor film-forming property of the crosslinked resin. The sodium styrene sulfonate monomer is polymerized in a simple free radical solution to prepare sodium polystyrene sulfonate solution, wherein the purity of the polymer is high, and the purity of the film forming material can be further improved after simple treatment. On the other hand, the polyvinyl alcohol has the characteristics of low toxicity, good biocompatibility, excellent water solubility and film-forming performance, the water resistance of the polyvinyl alcohol can be obviously improved through proper crosslinking, and the polyvinyl alcohol can be widely applied to the fields of soilless culture, fuel cell film materials and the like. The preparation method adopted by the invention is simpler and more convenient in process and is beneficial to industrial production.
Optionally, the mass ratio of the polyvinyl alcohol to the sodium polystyrene sulfonate in the casting solution may be, but is not limited to, (2: 1) to (1: 2).
Optionally, the concentration of the polymer in the casting solution may be, but is not limited to, 8-20%.
Optionally, the polymerization degree of the polyvinyl alcohol can be but is not limited to 1300-2600, and the alcoholysis degree can be but is not limited to 88-99, so as to improve the mechanical property of the cation exchange membrane.
Optionally, the molecular weight of the sodium polystyrene sulfonate can be, but is not limited to, 50000-70000 g/mol.
Optionally, the cross-linking agent is one or more of formaldehyde, glyoxal and glutaraldehyde. Among them, methanol acts as a crosslinking stabilizer to prevent the film from being deformed by too fast crosslinking.
Optionally, the content of each component in the crosslinking solution is as follows: 4-6 mL of 50 vol% methanol; 2-4 mL of 10 vol% acetic acid; 1-2 mL of 10 vol% sulfuric acid; and 2-4 mL of a cross-linking agent; wherein the concentration of the cross-linking agent is 2-10%.
Optionally, the volume ratio of the casting solution to the crosslinking solution may be, but is not limited to, (10: 3) to (10: 1).
Optionally, the crosslinking temperature of the heating crosslinking can be but is not limited to 50-80 ℃, and the crosslinking reaction time can be but is not limited to 2-5 hours.
Furthermore, the polystyrene sodium sulfonate polyvinyl alcohol cation exchange membrane prepared by the preparation method has the water content of 15-50% and the swelling degree of 10-40%.
Example 1
(1) Preparation of the casting solution
Adding a polyvinyl alcohol solid with the polymerization degree of 2000 and the alcoholysis degree of 88 into distilled water, mechanically stirring at 90 ℃ until the polyvinyl alcohol solid is completely dissolved, and cooling for later use; dissolving sodium polystyrene sulfonate solid with the molecular weight of 70000g/mol in distilled water at normal temperature to prepare a solution for later use, and uniformly mixing polyvinyl alcohol and the sodium polystyrene sulfonate solution to prepare a membrane casting solution, wherein the mass ratio of the polyvinyl alcohol to the sodium polystyrene sulfonate is 2:1, and the concentration of the whole membrane casting solution is controlled to be 8%.
(2) Preparation of the Cross-linking solution
6mL of 50 vol% methanol, 4mL of 10 vol% acetic acid, 2mL of 10 vol% sulfuric acid, and 2mL of 5 vol% glutaraldehyde were mixed uniformly to prepare a crosslinked solution.
(3) Preparation of cation exchange membranes
And (3) quickly and uniformly mixing 15mL of membrane casting solution and 3mL of crosslinking solution, scraping the membrane on a clean glass plate, and carrying out crosslinking reaction for 4 hours in a forced air drying oven at 50 ℃ to obtain the crosslinked cation exchange membrane.
Example 2
(1) Preparation of the casting solution
Adding polyvinyl alcohol solid with the polymerization degree of 1700 and the alcoholysis degree of 99 into distilled water, mechanically stirring at 90 ℃ until the polyvinyl alcohol solid is completely dissolved, and cooling for later use; dissolving sodium polystyrene sulfonate solid with the molecular weight of 60000g/mol in distilled water at normal temperature to prepare a solution for later use, and uniformly mixing polyvinyl alcohol and a sodium polystyrene sulfonate solution according to a certain proportion to prepare a membrane casting solution, wherein the mass ratio of the polyvinyl alcohol to the sodium polystyrene sulfonate is 1:1, and the concentration of the whole membrane casting solution is controlled to be 12%.
(2) Preparation of the Cross-linking solution
5mL of 50 vol% methanol, 3mL of 10 vol% acetic acid, 1mL of 10 vol% sulfuric acid, and 3mL of 8 vol% glutaraldehyde were mixed uniformly to prepare a crosslinking solution.
(3) Preparation of cation exchange membranes
And (3) quickly and uniformly mixing 10mL of membrane casting solution and 2mL of crosslinking solution, scraping the membrane on a clean glass plate, and carrying out crosslinking reaction for 2h in a forced air drying oven at the temperature of 80 ℃ to obtain the crosslinked cation exchange membrane.
Example 3
(1) Preparation of the casting solution
Adding a polyvinyl alcohol solid with the polymerization degree of 2600 and the alcoholysis degree of 99 into distilled water, mechanically stirring at 90 ℃ until the polyvinyl alcohol solid is completely dissolved, and cooling for later use; dissolving sodium polystyrene sulfonate solid with the molecular weight of 50000g/mol in distilled water at normal temperature to prepare a solution for later use, and uniformly mixing polyvinyl alcohol and a sodium polystyrene sulfonate solution according to a certain proportion to prepare a membrane casting solution, wherein the mass ratio of the polyvinyl alcohol to the sodium polystyrene sulfonate is 1:2, and the concentration of the whole membrane casting solution is controlled to be 10%.
(2) Preparation of the Cross-linking solution
4mL of 50 vol% methanol, 2mL of 10 vol% acetic acid, 1mL of 10 vol% sulfuric acid, and 2mL of 10 vol% glutaraldehyde were mixed uniformly to prepare a crosslinked solution.
(3) Preparation of cation exchange membranes
And (3) quickly and uniformly mixing 10mL of membrane casting solution and 1mL of crosslinking solution, scraping the membrane on a clean glass plate, and carrying out crosslinking reaction for 4.5 hours in a forced air drying oven at 60 ℃ to obtain the crosslinked cation exchange membrane.
Example 4
(1) Preparation of the casting solution
Adding a polyvinyl alcohol solid with the polymerization degree of 1400 and the alcoholysis degree of 99 into distilled water, mechanically stirring at 90 ℃ until the polyvinyl alcohol solid is completely dissolved, and cooling for later use; dissolving sodium polystyrene sulfonate solid with the molecular weight of 70000g/mol in distilled water at normal temperature to prepare a solution for later use, and uniformly mixing polyvinyl alcohol and sodium polystyrene sulfonate solution according to a certain proportion to prepare a membrane casting solution, wherein the mass ratio of the polyvinyl alcohol to the sodium polystyrene sulfonate is 1:2, and the concentration of the whole membrane casting solution is controlled to be 15%.
(2) Preparation of the Cross-linking solution
6mL of 50 vol% methanol, 3mL of 10 vol% acetic acid, 1mL of 10 vol% sulfuric acid, and 2mL of 6 vol% glutaraldehyde were mixed uniformly to prepare a crosslinked solution.
(3) Preparation of cation exchange membranes
And (3) quickly and uniformly mixing 15mL of membrane casting solution and 2mL of crosslinking solution, scraping the membrane on a clean glass plate, and carrying out crosslinking reaction for 4.5 hours in a forced air drying oven at 70 ℃ to obtain the crosslinked cation exchange membrane.
Example 5
(1) Preparation of the casting solution
Adding a polyvinyl alcohol solid with the polymerization degree of 2600 and the alcoholysis degree of 88 into distilled water, mechanically stirring at 90 ℃ until the polyvinyl alcohol solid is completely dissolved, and cooling for later use; dissolving sodium polystyrene sulfonate solid with the molecular weight of 60000g/mol in distilled water at normal temperature to prepare a solution for later use, and uniformly mixing polyvinyl alcohol and a sodium polystyrene sulfonate solution according to a certain proportion to prepare a membrane casting solution, wherein the mass ratio of the polyvinyl alcohol to the sodium polystyrene sulfonate is 1:2, and the concentration of the whole membrane casting solution is controlled to be 20%.
(2) Preparation of the Cross-linking solution
5mL of 50 vol% methanol, 3mL of 10 vol% acetic acid, 2mL of 10 vol% sulfuric acid, and 4mL of 10 vol% glutaraldehyde were mixed uniformly to prepare a crosslinking solution.
(3) Preparation of cation exchange membranes
And (3) quickly and uniformly mixing 15mL of membrane casting solution and 2mL of crosslinking solution, scraping the membrane on a clean glass plate, and carrying out crosslinking reaction for 4 hours in a forced air drying oven at 60 ℃ to obtain the crosslinked cation exchange membrane.
Example 6
(1) Preparation of the casting solution
Adding a polyvinyl alcohol solid with the polymerization degree of 1300 and the alcoholysis degree of 88 into distilled water, mechanically stirring at 90 ℃ until the polyvinyl alcohol solid is completely dissolved, and cooling for later use; dissolving sodium polystyrene sulfonate solid with the molecular weight of 70000g/mol in distilled water at normal temperature to prepare a solution for later use, and uniformly mixing polyvinyl alcohol and sodium polystyrene sulfonate solution according to a certain proportion to prepare a membrane casting solution, wherein the mass ratio of the polyvinyl alcohol to the sodium polystyrene sulfonate is 1:2, and the concentration of the whole membrane casting solution is controlled to be 16%.
(2) Preparation of the Cross-linking solution
5mL of 50 vol% methanol, 3mL of 10 vol% acetic acid, 2mL of 10 vol% sulfuric acid, and 4mL of 8 vol% glutaraldehyde were mixed uniformly to prepare a crosslinking solution.
(3) Preparation of cation exchange membranes
And (3) quickly and uniformly mixing 10mL of membrane casting solution and 3mL of crosslinking solution, scraping the membrane on a clean glass plate, and carrying out crosslinking reaction for 2h in a forced air drying oven at the temperature of 80 ℃ to obtain the crosslinked cation exchange membrane.
The cation exchange membranes prepared in the examples were subjected to performance tests, and the data results are summarized in table 1.
TABLE 1 Performance data for cation exchange membranes prepared in the examples
As can be seen from the data in Table 1, according to the data in example 2, the cation exchange membrane prepared by crosslinking the polyvinyl alcohol aqueous solution with the polymerization degree of 1700 and the alcoholysis degree of 99 and the sodium polystyrene sulfonate aqueous solution with the molecular weight of 60000g/mol has the best ion exchange capacity performance of 1.33 mmol/g.
In summary, the invention uses polyvinyl alcohol and sodium polystyrene sulfonate with good film forming performance as film forming base materials to prepare a blend casting solution, then the blend casting solution is mixed with a crosslinking solution, and the self-crosslinking of the polyvinyl alcohol and the crosslinking reaction between the sodium polystyrene sulfonate and the polyvinyl alcohol are realized under an acidic condition to further prepare the cation exchange membrane. The invention takes polyvinyl alcohol and sodium polystyrene sulfonate as membrane materials, and takes water as solvent, thus meeting the environmental protection requirement in process; the cross-linked sodium polystyrene sulfonate/polyvinyl alcohol cation exchange membrane prepared by the invention has good water resistance, and keeps high water absorption and dimensional stability while improving the water resistance; the cross-linked sodium polystyrene sulfonate/polyvinyl alcohol cation exchange membrane prepared by the invention can be sulfonated by a sulfonation reagent to residual polyvinyl alcohol hydroxyl in the membrane, so that the ion exchange performance is further improved.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The preparation method of the sodium polystyrene sulfonate polyvinyl alcohol cation exchange membrane is characterized by comprising the following steps:
mixing a polyvinyl alcohol solution and a sodium polystyrene sulfonate solution to prepare a membrane casting solution;
mixing methanol, acetic acid, sulfuric acid and a cross-linking agent to prepare cross-linking liquid;
and mixing the membrane casting solution and the crosslinking solution, scraping the membrane, and heating for crosslinking to obtain the crosslinked cation exchange membrane.
2. The method according to claim 1, wherein the reaction mixture,
the mass ratio of the polyvinyl alcohol to the sodium polystyrene sulfonate in the casting solution is (2: 1) - (1: 2).
3. The method according to claim 1, wherein the reaction mixture,
the concentration of the polymer in the casting solution is 8-20%.
4. The method according to claim 1, wherein the reaction mixture,
the polymerization degree of the polyvinyl alcohol is 1300-2600, and the alcoholysis degree is 88-99.
5. The method according to claim 1, wherein the reaction mixture,
the molecular weight of the sodium polystyrene sulfonate is 50000-70000 g/mol.
6. The method according to claim 1, wherein the reaction mixture,
the cross-linking agent is one or more of formaldehyde, glyoxal and glutaraldehyde.
7. The method according to claim 1, wherein the reaction mixture,
the content of each component in the crosslinking liquid is respectively as follows:
4-6 mL of 50 vol% methanol;
2-4 mL of 10 vol% acetic acid;
1-2 mL of 10 vol% sulfuric acid; and
2-4 mL of a cross-linking agent; wherein
The concentration of the cross-linking agent is 2-10%.
8. The method according to claim 1, wherein the reaction mixture,
the volume ratio of the casting solution to the cross-linking solution is (10: 3) - (10: 1).
9. The method according to claim 1, wherein the reaction mixture,
the crosslinking temperature of the heating crosslinking is 50-80 ℃, and the crosslinking reaction time is 2-5 h.
10. A sodium polystyrene sulfonate polyvinyl alcohol cation exchange membrane prepared by the preparation method as claimed in claim 1,
the polystyrene sodium sulfonate/polyvinyl alcohol cation exchange membrane has the water content of 15-50% and the swelling degree of 10-40%.
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Cited By (1)
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