CN113583290A - Preparation method of polyimide porous membrane containing amidoxime group - Google Patents
Preparation method of polyimide porous membrane containing amidoxime group Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 59
- 239000004642 Polyimide Substances 0.000 title claims abstract description 54
- 239000012528 membrane Substances 0.000 title claims abstract description 26
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical group C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000004985 diamines Chemical class 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 18
- 229910052770 Uranium Inorganic materials 0.000 abstract description 16
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002904 solvent Substances 0.000 abstract description 8
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000000614 phase inversion technique Methods 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000009719 polyimide resin Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 125000003544 oxime group Chemical group 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a preparation method of a polyimide porous membrane containing amidoxime groups, belonging to the field of special high polymer materials. The porous membrane can be used as a high-strength adsorbing material in the fields of uranium adsorption, enrichment, separation and the like. The preparation method of the polyimide porous membrane containing the amidoxime group comprises the steps of introducing a diamine monomer containing a cyano group into the monomer during polyimide preparation, copolymerizing the diamine monomer with other diamine monomers, preparing the polyimide porous membrane by a phase inversion method after the polyimide is prepared, and hydrolyzing the cyano group on a polyimide side chain into the amidoxime group to obtain the polyimide porous membrane containing the amidoxime group. The adsorption capacity of the porous membrane prepared by the method on uranium is more than 110 mg/g. The method for preparing the uranium-adsorbing polymer porous membrane is simple, practical and environment-friendly, the selected solvent and the non-solvent have low cost and are easy to recycle, and the comprehensive yield is higher than 90%.
Description
Technical Field
The invention relates to a preparation method of a polyimide porous membrane containing amidoxime groups, belonging to the field of special high polymer materials. The porous membrane can be used as a high-strength adsorbing material in the fields of uranium adsorption, enrichment, separation and the like.
Background
The radioactive waste liquid generated in the nuclear fuel circulation process has the obvious characteristics of low concentration and large volume, so that the method has important practical significance for effectively separating uranium in a water body. The uranium separation and enrichment methods mainly comprise a solvent extraction method, a foam flotation method, a liquid film enrichment method, an evaporation and concentration method, a precipitation method, an adsorption method and the like. Currently, the adsorption method is widely adopted due to its advantages of low cost, simple process, wide applicability, etc. Gem-aminesThe oxime functional group is named because it contains both an oxime group and an amino group. Wherein the oximino oxygen atom and the amino nitrogen atom both contain lone pair electrons which are not bonded and can be reacted with UO2 2+Coordination occurs to form a five-membered ring chelate. Therefore, amidoxime functional groups are widely used for modifying inorganic nano materials and high molecular polymers to improve the adsorption amount and adsorption selectivity of the modified materials to uranium. The key point of the research of the adsorption method is to develop a high-efficiency adsorbent which has the advantages of high adsorption capacity, high adsorption rate, good adsorption selectivity, stable mechanical and chemical properties and the like.
Polyimide (PI) is a high polymer material with excellent comprehensive performance obtained by performing a polycondensation reaction between a dicarboxylic anhydride and diamine, and can be classified into three main classes according to the difference of molecular structures in the structure: aromatic polyimide, semi-aromatic polyimide and aliphatic polyimide. Polyimide is a high molecular material with a rigid imide ring molecular skeleton, and has good thermal property, solvent resistance, radiation resistance, excellent mechanical property and the like. The polyimide resin has extremely high radiation resistance, and the polyimide film can bear 5 multiplied by 109After rad fast electron irradiation, the retention rate of mechanical properties reaches over 86 percent. Common polyimide resins are generally insoluble in common organic solvents, and common soluble polyimide resins are also only soluble in aprotic polar solvents such as amide solvents and phenol solvents. The polyimide resin can maintain high stability in dilute acid, oxidant and reductant, and even at high temperature, the stability is outstanding. According to the invention, the amidoxime functional group can be grafted to the polyimide substrate, and the porous membrane is prepared by a processing means, so that the polyimide porous membrane containing the amidoxime group, which has radiation resistance and high uranium adsorption, can be obtained.
Disclosure of Invention
The invention aims to overcome the current situation that the prior polyimide cannot specifically adsorb uranium as an adsorbing material and the prior adsorbing material for adsorbing uranium has poor radiation resistance, and provides a preparation method of a polyimide porous membrane containing an amidoxime group. Specifically, when polyimide is prepared, a diamine monomer containing a cyano group is introduced into the monomer, the monomer and other diamine monomers are copolymerized together, after the polyimide is prepared, a polyimide porous membrane is prepared through a phase inversion method, and then the cyano group on a side chain of the polyimide is hydrolyzed into an amidoxime group, so that the amidoxime group-containing polyimide porous membrane is obtained.
The preparation method of the polyimide porous membrane containing amidoxime groups is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) under the protection of nitrogen atmosphere, adding diamine monomer and N, N-dimethylacetamide into a reaction bottle to prepare a diamine solution with the concentration of 1-10 wt%, then adding tetracarboxylic dianhydride within 0.5-2 h, and stirring and reacting for 8-16 h at room temperature to obtain a polyamide acid solution, wherein the diamine contains 5-40 mol% of diamine with the structure shown in the attached drawing 1, other diamines are more than one of p-phenylenediamine, 4,4 '-diaminodiphenyl ether, 4, 4' -diaminophenylsulfone and 4,4 '-diaminodiphenylmethane, the tetracarboxylic dianhydride is more than one of pyromellitic dianhydride, 4, 4' -biphenyltetracarboxylic dianhydride and 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, and the molar ratio of the diamine to the tetracarboxylic dianhydride is 1: 1;
(2) heating the reaction solution obtained in the step (1) to 160-200 ℃ in a nitrogen environment, simultaneously heating and stirring for reaction for 10-20 hours to perform imidization reaction and remove moisture generated by the moisture reaction, then pouring the reaction solution into water with a volume 3-10 times that of the N, N-dimethylacetamide obtained in the step (1), and precipitating, filtering and drying to obtain polyimide powder;
(3) adding the polyimide obtained in the step (2) into N-methyl pyrrolidone, adding hydroxylamine hydrochloride and potassium carbonate, reacting for 5-15 h at 60-100 ℃, then pouring the mixture into water with the volume 5-10 times that of the N-methyl pyrrolidone for precipitation, collecting the precipitate, and drying for 5-10 h at 50-80 ℃ to obtain the polyimide containing amidoxime groups, wherein the polyimide: and (3) hydroxylamine hydrochloride: potassium carbonate: the proportion of N-methyl pyrrolidone is 1 g: 10-20 g: 10-20 g: 10-50 mL;
(4) dissolving the polyimide containing amidoxime groups obtained in the step (3) in N-methyl pyrrolidone to prepare a 1-10 wt% solution, pouring the solution onto a glass plate, scraping a liquid film with the thickness of 100-1000 microns by using a wet film preparation device, standing for 5-30 min, soaking the glass plate and the liquid film on the surface of the glass plate in water with the volume 50-200 times that of the N-methyl pyrrolidone for 0.5-3 h, stripping the obtained film from the glass plate, and drying to obtain the polyimide porous membrane.
The invention has the beneficial effects that: the polymer main chain of the polymer porous membrane is polyimide, so that the polymer porous membrane has excellent mechanical capacity and tensile strength of more than 15 MPa; the side chain has an amidoxime functional group, so that uranium can be specifically adsorbed and separated; the prepared porous membrane further improves the specific surface area and has the adsorption capacity to uranium of more than 110 mg/g. The method for preparing the uranium-adsorbing polymer porous membrane is simple, practical and environment-friendly, the selected solvent and the non-solvent have low cost and are easy to recycle, and the comprehensive yield is higher than 90%. The preparation method disclosed by the invention is simple to produce and operate, low in equipment requirement, green and environment-friendly, and capable of realizing large-scale production, and the solvent in the production process can be recycled.
Drawings
FIG. 1 is a structural formula of diamine containing cyano group
FIG. 2 is a structural formula of a cyano group-containing polyimide prepared in example 1 of the present invention
FIG. 3 is an SEM photograph of a porous polyimide membrane containing an amidoxime group prepared in example 1 of the present invention
Detailed Description
The following examples of the preparation process of the present invention are presented, but the following examples are illustrative of the present invention and do not constitute any limitation to the claims of the present invention.
Example 1
(1) Under the protection of nitrogen atmosphere, 2.42g of diamine monomer and 100g of N, N-dimethylacetamide are added into a reaction bottle to prepare a diamine solution with the concentration of 2 wt%, then 3.2g of 3,3 ', 4,4 ' -benzophenonetetracarboxylic dianhydride is added within 1h, and the mixture is stirred and reacted for 12h at room temperature to obtain a polyamic acid solution, wherein the diamine contains 0.82g (20 mol%) of diamine with the structure shown in the figure 1, and other diamines are 1.6g (80 mol%) of 4,4 ' -diaminodiphenyl ether;
(2) heating the reaction solution obtained in the step (1) to 180 ℃ in a nitrogen environment, simultaneously heating and stirring for reaction for 12 hours to perform imidization reaction and remove moisture generated by the moisture reaction, then pouring the reaction solution into 550mL of water, precipitating, filtering and drying to obtain polyimide powder, wherein the structural formula of the polyimide powder is shown in the attached figure 2;
(3) adding 1g of polyimide obtained in the step (2) into 50mL of N-methylpyrrolidone, adding 10g of hydroxylamine hydrochloride and 15g of potassium carbonate, reacting at 80 ℃ for 8h, then pouring the mixture into 500mL of water for precipitation, collecting the precipitate, and drying at 60 ℃ for 10h to obtain polyimide containing amidoxime groups;
(4) and (3) dissolving 1g of the polyimide containing the amidoxime group obtained in the step (3) in 100g of N-methylpyrrolidone to prepare a 1 wt% solution, pouring the solution onto a glass plate, scraping a liquid film with the thickness of 200 microns by using a wet film preparation device, standing for 10min, soaking the glass plate and the liquid film on the surface of the glass plate in 10L of water for 2h, stripping the obtained film from the glass plate, and drying to obtain a polyimide porous film, wherein the SEM picture of the polyimide porous film is shown in figure 3, and the adsorption capacity of the polyimide porous film on uranium reaches 125 mg/g.
Example 2
(1) Under the protection of nitrogen atmosphere, 4.84g of diamine monomer and 100g of N, N-dimethylacetamide are added into a reaction bottle to prepare a diamine solution with the concentration of 4 wt%, then 6.4g of 3,3 ', 4,4 ' -benzophenonetetracarboxylic dianhydride is added within 1h, and the mixture is stirred and reacted for 12h at room temperature to obtain a polyamic acid solution, wherein the diamine contains 1.64g (20 mol%) of diamine with the structure shown in the figure 1, and the other diamines are 3.2g (80 mol%) of 4,4 ' -diaminodiphenyl ether;
(2) in accordance with example 1, step (2);
(3) in accordance with example 1, step (3);
(4) consistent with the step (4) of the example 1, the adsorption capacity of the catalyst on uranium reaches 135 mg/g.
Example 3
(1) Under the protection of nitrogen atmosphere, 2.42g of diamine monomer and 100g of N, N-dimethylacetamide are added into a reaction bottle to prepare a diamine solution with the concentration of 2 wt%, 2.2g of pyromellitic anhydride is added within 1h, and the mixture is stirred and reacted for 12h at room temperature to obtain a polyamide acid solution, wherein the diamine contains 0.82g (20 mol%) of diamine with the structure shown in the figure 1, and the other diamines are 1.6g (80 mol%) of 4, 4' -diaminodiphenyl ether;
(2) in accordance with example 1, step (2);
(3) in accordance with example 1, step (3);
(4) consistent with the step (4) of the example 1, the adsorption capacity of the catalyst on uranium reaches 142 mg/g.
Example 4
(1) In accordance with example 1, step (1);
(2) in accordance with example 1, step (2);
(3) adding 1g of polyimide obtained in the step (2) into 50mL of N-methylpyrrolidone, adding 20g of hydroxylamine hydrochloride and 20g of potassium carbonate, reacting at 80 ℃ for 8h, then pouring the mixture into 500mL of water for precipitation, collecting the precipitate, and drying at 60 ℃ for 10h to obtain polyimide containing amidoxime groups;
(4) consistent with the step (4) of the example 1, the adsorption capacity of the catalyst on uranium reaches 121 mg/g.
Example 5
(1) In accordance with example 1, step (1);
(2) in accordance with example 1, step (2);
(3) in accordance with example 1, step (3);
(4) and (3) dissolving 1g of the polyimide containing the amidoxime group obtained in the step (3) in 50g of N-methylpyrrolidone to prepare a 2 wt% solution, pouring the solution onto a glass plate, scraping a liquid film with the thickness of 300 microns by using a wet film preparation device, standing for 10min, soaking the glass plate and the liquid film on the surface of the glass plate in 10L of water for 2h, stripping the obtained film from the glass plate, and drying to obtain a polyimide porous membrane with the uranium adsorption capacity of 132 mg/g.
Claims (1)
1. A method for preparing polyimide porous membrane containing amidoxime group is characterized in that: the preparation method comprises the following steps:
(1) under the protection of nitrogen atmosphere, adding diamine monomer and N, N-dimethylacetamide into a reaction bottle to prepare a diamine solution with the concentration of 1-10 wt%, then adding tetracarboxylic dianhydride within 0.5-2 h, and stirring and reacting for 8-16 h at room temperature to obtain a polyamide acid solution, wherein the diamine contains 5-40 mol% of diamine with the structure shown in the attached drawing 1, other diamines are more than one of p-phenylenediamine, 4,4 '-diaminodiphenyl ether, 4, 4' -diaminophenylsulfone and 4,4 '-diaminodiphenylmethane, the tetracarboxylic dianhydride is more than one of pyromellitic dianhydride, 4, 4' -biphenyltetracarboxylic dianhydride and 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, and the molar ratio of the diamine to the tetracarboxylic dianhydride is 1: 1;
(2) heating the reaction solution obtained in the step (1) to 160-200 ℃ in a nitrogen environment, simultaneously heating and stirring for reaction for 10-20 hours to perform imidization reaction and remove moisture generated by the moisture reaction, then pouring the reaction solution into water with a volume 3-10 times that of the N, N-dimethylacetamide obtained in the step (1), and precipitating, filtering and drying to obtain polyimide powder;
(3) adding the polyimide obtained in the step (2) into N-methyl pyrrolidone, adding hydroxylamine hydrochloride and potassium carbonate, reacting for 5-15 h at 60-100 ℃, then pouring the mixture into water with the volume 5-10 times that of the N-methyl pyrrolidone for precipitation, collecting the precipitate, and drying for 5-10 h at 50-80 ℃ to obtain polyimide containing amidoxime groups; wherein the polyimide: and (3) hydroxylamine hydrochloride: potassium carbonate: the proportion of N-methyl pyrrolidone is 1 g: 10-20 g: 10-20 g: 10-50 mL;
(4) dissolving the polyimide containing amidoxime groups obtained in the step (3) in N-methyl pyrrolidone to prepare a 1-10 wt% solution, pouring the solution onto a glass plate, scraping a liquid film with the thickness of 100-1000 microns by using a wet film preparation device, standing for 5-30 min, soaking the glass plate and the liquid film on the surface of the glass plate in water with the volume 50-200 times that of the N-methyl pyrrolidone for 0.5-3 h, stripping the obtained film from the glass plate, and drying to obtain the polyimide porous membrane.
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| CN202111022644.7A CN113583290A (en) | 2021-09-01 | 2021-09-01 | Preparation method of polyimide porous membrane containing amidoxime group |
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| CN116284983A (en) * | 2022-11-22 | 2023-06-23 | 中山大学 | Polyimide porous membrane and preparation method and application thereof |
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