CN114085402A - A kind of base-crosslinked sulfonated polyetheretherketone ion exchange membrane and preparation method thereof - Google Patents
A kind of base-crosslinked sulfonated polyetheretherketone ion exchange membrane and preparation method thereof Download PDFInfo
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- CN114085402A CN114085402A CN202111198148.7A CN202111198148A CN114085402A CN 114085402 A CN114085402 A CN 114085402A CN 202111198148 A CN202111198148 A CN 202111198148A CN 114085402 A CN114085402 A CN 114085402A
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- base
- ether ketone
- polyether ether
- exchange membrane
- sulfonated polyether
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 100
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 100
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 18
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 238000005266 casting Methods 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 230000004913 activation Effects 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims abstract description 7
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract 7
- 238000005406 washing Methods 0.000 claims description 38
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- OPTASPLRGRRNAP-UHFFFAOYSA-N cytosine Chemical compound NC=1C=CNC(=O)N=1 OPTASPLRGRRNAP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 15
- 229930024421 Adenine Natural products 0.000 claims description 13
- 229960000643 adenine Drugs 0.000 claims description 13
- 230000001376 precipitating effect Effects 0.000 claims description 13
- 150000001408 amides Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 150000003462 sulfoxides Chemical group 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229940113082 thymine Drugs 0.000 claims description 9
- 229940104302 cytosine Drugs 0.000 claims description 7
- 239000013557 residual solvent Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000006277 sulfonation reaction Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- -1 ether ketone Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000003993 interaction Effects 0.000 claims description 2
- DRTQHJPVMGBUCF-XVFCMESISA-N Uridine Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1N1C(=O)NC(=O)C=C1 DRTQHJPVMGBUCF-XVFCMESISA-N 0.000 claims 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- DRTQHJPVMGBUCF-PSQAKQOGSA-N beta-L-uridine Natural products O[C@H]1[C@@H](O)[C@H](CO)O[C@@H]1N1C(=O)NC(=O)C=C1 DRTQHJPVMGBUCF-PSQAKQOGSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- DRTQHJPVMGBUCF-UHFFFAOYSA-N uracil arabinoside Natural products OC1C(O)C(CO)OC1N1C(=O)NC(=O)C=C1 DRTQHJPVMGBUCF-UHFFFAOYSA-N 0.000 claims 1
- 229940045145 uridine Drugs 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 32
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 25
- 229940035893 uracil Drugs 0.000 description 12
- 230000009471 action Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HZOYZGXLSVYLNF-UHFFFAOYSA-N 2-amino-3,7-dihydropurin-6-one;1h-pyrimidine-2,4-dione Chemical compound O=C1C=CNC(=O)N1.O=C1NC(N)=NC2=C1NC=N2 HZOYZGXLSVYLNF-UHFFFAOYSA-N 0.000 description 1
- FFKUHGONCHRHPE-UHFFFAOYSA-N 5-methyl-1h-pyrimidine-2,4-dione;7h-purin-6-amine Chemical compound CC1=CNC(=O)NC1=O.NC1=NC=NC2=C1NC=N2 FFKUHGONCHRHPE-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明公开了一种碱基交联的磺化聚醚醚酮离子交换膜的制备方法，包括以下步骤：(1)将聚醚醚酮用浓硫酸磺化得到磺化聚醚醚酮；(2)将磺化聚醚醚酮溶解在有机溶剂中，加入N,N′‑羰基二咪唑活化后，分别加入一种嘧啶和一种嘌呤碱基单体，反应得到两种不同碱基作用的磺化聚醚醚酮聚合物；(3)将两种不同碱基作用的磺化聚醚醚酮聚合物混合后，用有机溶剂溶解得到铸膜液，过滤后涂布在干净的玻璃板上，烘干得到最终产物。本发明还公开了一种碱基交联的磺化聚醚醚酮离子交换膜。本发明在磺化聚醚醚酮上引入不同的碱基基团，并形成碱基交联网络，在提高薄膜的机械性能和热稳定性的同时对薄膜的质子通量没有影响，甚至有所提升。The invention discloses a method for preparing a base-crosslinked sulfonated polyether ether ketone ion exchange membrane, comprising the following steps: (1) sulfonating polyether ether ketone with concentrated sulfuric acid to obtain sulfonated polyether ether ketone; ( 2) Dissolving the sulfonated polyether ether ketone in an organic solvent, adding N,N'-carbonyldiimidazole for activation, adding a pyrimidine and a purine base monomer respectively, and reacting to obtain two kinds of different bases. Sulfonated polyether ether ketone polymer; (3) after mixing two sulfonated polyether ether ketone polymers with different bases, dissolve with organic solvent to obtain casting liquid, filter and spread on a clean glass plate , drying to obtain the final product. The invention also discloses a base-crosslinked sulfonated polyether ether ketone ion exchange membrane. The present invention introduces different base groups on the sulfonated polyether ether ketone, and forms a base cross-linking network, which has no influence on the proton flux of the film while improving the mechanical properties and thermal stability of the film, and even has some effect on the proton flux of the film. promote.
Description
Technical Field
The invention belongs to the technical field of ion exchange membrane preparation, and particularly relates to a base-crosslinked sulfonated polyether ether ketone ion exchange membrane and a preparation method thereof.
Background
In recent years, people pay more and more attention to the protection of ecological environment, and the pickling waste liquid in the steel industry contains pollutants such as hydrochloric acid, sulfuric acid and metal waste residues, and can cause irrecoverable pollution of water, soil and the like when being directly discharged into the natural environment, so that the development of a green, efficient and sustainable-circulation waste acid recovery treatment technology is imperative. The membrane separation technology has the advantages of simple operation, low energy consumption, environmental friendliness and the like, and is widely applied to the fields of salt water desalination, drinking water purification, industrial wastewater treatment, environmental engineering, petrochemical industry and the like. The ion exchange membrane is used as a key part of the membrane separation technology, and the preparation of the ion exchange membrane material which has good mechanical property and thermal stability and is separated efficiently becomes a research hotspot of researchers.
The ion exchange membrane is combined with an electrodialysis technology to effectively separate protons from metal ions, and has huge developable potential in the application fields of waste acid recovery, water treatment and the like, so that researchers successfully research and prepare a series of cation exchange membranes which aim at improving the separation of metal cations and protons. The sulfonated polyether ether ketone (SPEEK) membrane is concerned with a lot of attention because the preparation process is simple, the structural performance is stable, and the cost is low, and the SPEEK has high water absorption rate, can effectively promote the dissociation of-SO 3H groups and push protons to move, and therefore, the sulfonated polyether ether ketone (SPEEK) membrane has excellent proton conductivity. However, the basic performance of the membrane is influenced by the sulfonation Degree (DS), the sulfonation degree is high, the proton flux is large, but high water absorption is caused, the mechanical performance is reduced, and the prepared membrane is easy to disperse; if the sulfonation degree is too low, the water absorption rate decreases, and the proton transport ability decreases.
Disclosure of Invention
Aiming at the defects or the improvement requirements of the prior art, the invention aims to prepare the base-crosslinked sulfonated polyether ether ketone ion exchange membrane, which improves the mechanical property of the membrane and does not influence the proton flux of the membrane.
In order to achieve the aim, the invention provides a preparation method of a base-crosslinked sulfonated polyether ether ketone ion exchange membrane, which comprises the following steps:
(1) sulfonating polyether-ether-ketone by concentrated sulfuric acid, precipitating in ice water, washing to neutrality, and drying in an oven to obtain sulfonated polyether-ether-ketone;
(2) dissolving sulfonated polyether ether ketone in an organic solvent, adding N, N' -carbonyl diimidazole after complete dissolution, heating and stirring to fully activate the sulfonated polyether ether ketone, dividing a product of an activation reaction into two parts, adding a pyrimidine base monomer into one part, adding a purine base monomer into the other part, continuously heating and stirring, respectively precipitating the obtained products in ice water after the reaction, fully washing the products with deionized water, removing residual solvent, and drying the products in an oven to obtain sulfonated polyether ether ketone polymers with two different base effects;
(3) mixing two sulfonated polyether ether ketone polymers with different basic groups, dissolving the sulfonated polyether ether ketone polymers by using an organic solvent, reacting under a heating condition to obtain a membrane casting solution, filtering the membrane casting solution, coating the membrane casting solution on a clean glass plate, putting the glass plate into an oven for drying, and removing the solvent to obtain the basic group crosslinked sulfonated polyether ether ketone ion exchange membrane.
Further, the sulfonation temperature in the step (1) is 40-60 ℃, and the sulfonation reaction time is 4-6 h.
Further, the drying temperature in the step (1) is 60 ℃.
Further, in the step (2), the pyrimidine base monomer is one of cytosine, thymine and uracil, and the purine base monomer is one of adenine and guanine.
Further, in the step (2), the amount of the basic monomer is 0.5 to 2.0 times of the amount of the sulfonated polyether ether ketone substance, and the amount of the N, N' -carbonyldiimidazole substance is 0.8 to 1.5 times of the amount of the basic monomer substance.
Further, the heating and stirring temperature in the step (2) is 50-80 ℃, and the time for the activation reaction and the reaction of the activation product and the base monomer are both 2-4 h.
Further, the mixture of the sulfonated polyether ether ketone polymer with base interaction in the step (3) is dissolved by an organic solvent, and the solid content is 6-12%.
Further, the heating temperature of the casting solution obtained by the reaction under the heating condition in the step (3) is 50-80 ℃, and the reaction time is 2-4 h.
Further, the organic solvent is a sulfoxide or amide solvent.
The invention also provides a base-crosslinked sulfonated polyether ether ketone ion exchange membrane prepared by the preparation method.
Compared with the prior art, the invention can obtain the following beneficial effects: (1) the sulfonated polyether ether ketone is adopted as a matrix, and the sulfonated polyether ether ketone has excellent heat resistance, solvent resistance and hydrolysis resistance, good mechanical properties and proton transmission capacity equivalent to that of a Nafion membrane. (2) The base group introduced by the invention is combined with proton and positively charged, and the ion exchange membrane is ensured to have excellent selectivity in application due to Donnan exclusion effect and pore size sieving effect. (3) The base group introduced by the invention can provide a transmission site required by the hydrogen ions to permeate the membrane, and the hydrogen ions can freely migrate in the membrane, so that the flux of the hydrogen ions is kept unchanged or improved, and the high-efficiency selectivity of the membrane to the hydrogen ions is improved. (4) A hydrogen bond cross-linking network is formed among the base pairs, so that the swelling degree of the film is obviously reduced, the mechanical property and the thermal stability of the film are improved, and the proton flux of the film is not influenced or even improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A preparation method of a base-crosslinked sulfonated polyether ether ketone ion exchange membrane comprises the following steps:
(1) sulfonating polyether-ether-ketone by concentrated sulfuric acid at 40-60 ℃ for 4-6h, precipitating and washing in ice deionized water, measuring the washing liquid by using pH test paper in the washing process until the washing liquid is washed clean and neutral, putting the washing liquid into an oven to be dried at 60 ℃, and turning over the washing liquid frequently in the drying process to prevent bonding to obtain the sulfonated polyether-ether-ketone.
(2) Dissolving sulfonated polyether ether ketone in sulfoxide or amide solvent, adding N, N '-carbonyl diimidazole after complete dissolution, heating and stirring at 50-80 ℃ for 2-4h to fully activate the sulfonated polyether ether ketone, dividing the product of the activation reaction into two parts, adding one pyrimidine base monomer of cytosine, thymine and uracil in one part, and adding one purine base monomer of adenine and guanine in the other part, wherein the amount of the added base monomer is 0.5-2.0 times of that of the sulfonated polyether ether ketone substance, and the amount of the N, N' -carbonyl diimidazole substance is 0.8-1.5 times of that of the base monomer substance. Heating and stirring two parts of activated reaction products added with base monomers at 50-80 ℃ for 2-4h, respectively precipitating the obtained products in ice water, fully washing with deionized water, removing residual solvent, and drying in an oven to obtain sulfonated polyether ether ketone polymers with two different base functions.
(3) Mixing two sulfonated polyether ether ketone polymers with different basic groups, dissolving the sulfonated polyether ether ketone polymers with sulfoxide or amide solvents to ensure that the solid content is 6-12%, reacting the mixture for 2-4h under the heating condition of 50-80 ℃ to obtain a membrane casting solution, filtering the membrane casting solution, coating the membrane casting solution on a clean glass plate, putting the glass plate into an oven to dry the membrane at 60 ℃, and removing the solvents to obtain the basic group crosslinked sulfonated polyether ether ketone ion exchange membrane.
A base-crosslinked sulfonated polyether ether ketone ion exchange membrane prepared by the preparation method.
Example 1
A preparation method of a base-crosslinked sulfonated polyether ether ketone ion exchange membrane comprises the following steps:
(1) sulfonating polyether-ether-ketone by concentrated sulfuric acid at 40-60 ℃ for 4-6h, precipitating and washing in ice deionized water, measuring the washing liquid by using pH test paper in the washing process until the washing liquid is washed clean and neutral, putting the washing liquid into an oven to be dried at 60 ℃, and turning over the washing liquid frequently in the drying process to prevent bonding to obtain the sulfonated polyether-ether-ketone.
(2) Dissolving sulfonated polyether ether ketone in sulfoxide or amide solvent, adding N, N '-carbonyl diimidazole after complete dissolution, heating and stirring at 50-80 ℃ for 2-4h to fully activate the sulfonated polyether ether ketone, dividing the product of the activation reaction into two parts, adding adenine into one part and thymine into the other part, wherein the amount of the added adenine and thymine is 0.5-2.0 times of the amount of the sulfonated polyether ether ketone substance, and the amount of the N, N' -carbonyl diimidazole substance is 0.8-1.5 times of the amount of the adenine and thymine substances. Heating and stirring the activation reaction product added with adenine or thymine at 50-80 ℃ for 2-4h, respectively precipitating the obtained products in ice water, fully washing with deionized water, removing residual solvent, and drying in an oven to obtain the sulfonated polyether ether ketone polymer with the action of adenine and the sulfonated polyether ether ketone polymer with the action of thymine.
(3) Mixing the sulfonated polyether ether ketone polymer with the action of adenine and the sulfonated polyether ether ketone polymer with the action of thymine, dissolving the mixture by using a sulfoxide or amide solvent to ensure that the solid content is 6-12%, reacting the mixture for 2-4h under the heating condition of 50-80 ℃ to obtain a membrane casting solution, filtering the membrane casting solution, coating the membrane casting solution on a clean glass plate, putting the glass plate into an oven to dry the membrane casting solution at 60 ℃, and removing the solvent to obtain the adenine-thymine base pair crosslinked sulfonated polyether ether ketone ion exchange membrane.
Example 2
A preparation method of a base-crosslinked sulfonated polyether ether ketone ion exchange membrane comprises the following steps:
(1) sulfonating polyether-ether-ketone by concentrated sulfuric acid at 40-60 ℃ for 4-6h, precipitating and washing in ice deionized water, measuring the washing liquid by using pH test paper in the washing process until the washing liquid is washed clean and neutral, putting the washing liquid into an oven to be dried at 60 ℃, and turning over the washing liquid frequently in the drying process to prevent bonding to obtain the sulfonated polyether-ether-ketone.
(2) Dissolving sulfonated polyether ether ketone in sulfoxide or amide solvent, adding N, N '-carbonyl diimidazole after complete dissolution, heating and stirring at 50-80 ℃ for 2-4h to fully activate the sulfonated polyether ether ketone, dividing the product of the activation reaction into two parts, adding cytosine in one part and guanine in the other part, wherein the amount of the added cytosine and guanine is 0.5-2.0 times of the amount of the sulfonated polyether ether ketone substance, and the amount of the N, N' -carbonyl diimidazole substance is 0.8-1.5 times of the amount of the cytosine and guanine substances. Heating and stirring the activation reaction product added with cytosine or guanine at 50-80 ℃ for 2-4h, respectively precipitating the obtained products in ice water, fully washing with deionized water, removing residual solvent, and drying in an oven to obtain the sulfonated polyether ether ketone polymer with cytosine function and the sulfonated polyether ether ketone polymer with guanine function.
(3) Mixing sulfonated polyether ether ketone polymer with cytosine function and sulfonated polyether ether ketone polymer with guanine function, dissolving with sulfoxide or amide solvent to make solid content be 6% -12%, reacting for 2-4h under the heating condition of 50-80 ℃ to obtain casting solution, then filtering the casting solution, coating on a clean glass plate, putting into an oven to dry at 60 ℃, removing the solvent to obtain the sulfonated polyether ether ketone ion exchange membrane with cytosine-guanine base pair crosslinking.
Example 3
A preparation method of a base-crosslinked sulfonated polyether ether ketone ion exchange membrane comprises the following steps:
(1) sulfonating polyether-ether-ketone by concentrated sulfuric acid at 40-60 ℃ for 4-6h, precipitating and washing in ice deionized water, measuring the washing liquid by using pH test paper in the washing process until the washing liquid is washed clean and neutral, putting the washing liquid into an oven to be dried at 60 ℃, and turning over the washing liquid frequently in the drying process to prevent bonding to obtain the sulfonated polyether-ether-ketone.
(2) Dissolving sulfonated polyether ether ketone in sulfoxide or amide solvent, adding N, N '-carbonyl diimidazole after complete dissolution, heating and stirring at 50-80 ℃ for 2-4h to fully activate the sulfonated polyether ether ketone, dividing the product of the activation reaction into two parts, adding uracil into one part, and adding guanine into the other part, wherein the amount of the added uracil and guanine is 0.5-2.0 times of the amount of the sulfonated polyether ether ketone substance, and the amount of the N, N' -carbonyl diimidazole substance is 0.8-1.5 times of the amount of the uracil and guanine. Heating and stirring the activation reaction product added with uracil or guanine at 50-80 ℃ for 2-4h, respectively precipitating the obtained products in ice water, fully washing with deionized water, removing residual solvent, and drying in an oven to obtain the sulfonated polyether ether ketone polymer with the action of uracil and the sulfonated polyether ether ketone polymer with the action of guanine.
(3) Mixing a sulfonated polyether ether ketone polymer with uracil function and a sulfonated polyether ether ketone polymer with guanine function, dissolving the mixture by using a sulfoxide or amide solvent to ensure that the solid content is 6-12%, reacting the mixture for 2-4h under the heating condition of 50-80 ℃ to obtain a membrane casting solution, filtering the membrane casting solution, coating the membrane casting solution on a clean glass plate, putting the glass plate into an oven to dry the membrane casting solution at 60 ℃, and removing the solvent to obtain the uracil-guanine base pair crosslinked sulfonated polyether ether ketone ion exchange membrane.
Example 4
A preparation method of a base-crosslinked sulfonated polyether ether ketone ion exchange membrane comprises the following steps:
(1) sulfonating polyether-ether-ketone by concentrated sulfuric acid at 40-60 ℃ for 4-6h, precipitating and washing in ice deionized water, measuring the washing liquid by using pH test paper in the washing process until the washing liquid is washed clean and neutral, putting the washing liquid into an oven to be dried at 60 ℃, and turning over the washing liquid frequently in the drying process to prevent bonding to obtain the sulfonated polyether-ether-ketone.
(2) Dissolving sulfonated polyether ether ketone in sulfoxide or amide solvent, adding N, N '-carbonyl diimidazole after complete dissolution, heating and stirring at 50-80 ℃ for 2-4h to fully activate the sulfonated polyether ether ketone, dividing the product of the activation reaction into two parts, adding adenine into one part and adding uracil into the other part, wherein the amount of the added adenine and uracil is 0.5-2.0 times of the amount of the sulfonated polyether ether ketone substance, and the amount of the N, N' -carbonyl diimidazole substance is 0.8-1.5 times of the amount of the adenine and uracil substances. Heating and stirring the activation reaction product added with adenine or uracil at 50-80 ℃ for 2-4h, respectively precipitating the obtained products in ice water, fully washing with deionized water, removing residual solvent, and drying in an oven to obtain sulfonated polyether ether ketone polymer with adenine function and sulfonated polyether ether ketone polymer with uracil function.
(3) Mixing the sulfonated polyether ether ketone polymer with adenine function and the sulfonated polyether ether ketone polymer with uracil function, dissolving the mixture by using a sulfoxide or amide solvent to ensure that the solid content is 6-12%, reacting the mixture for 2-4h under the heating condition of 50-80 ℃ to obtain a membrane casting solution, filtering the membrane casting solution, coating the membrane casting solution on a clean glass plate, putting the glass plate into an oven to dry the membrane casting solution at 60 ℃, and removing the solvent to obtain the adenine-uracil base pair crosslinked sulfonated polyether ether ketone ion exchange membrane.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
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