CN114272768A - Preparation process and application of functionalized montmorillonite-polyimide composite membrane material - Google Patents
Preparation process and application of functionalized montmorillonite-polyimide composite membrane material Download PDFInfo
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Abstract
The invention relates to the technical field of membrane separation, and discloses a functionalized montmorillonite-polyimide composite membrane material, wherein sulfonic acid groups and phthalimide are chemically grafted to the surface of montmorillonite to realize organic functionalized modification of montmorillonite, the montmorillonite and polyimide are prepared into a membrane by a coagulation bath phase conversion method, so that the functionalized montmorillonite-polyimide composite membrane material is obtained, a three-dimensional space network structure is formed between the functionalized montmorillonite and the polyimide, the porosity is rich, the specific surface area is large, the adsorption rate and the water flux of the composite membrane can be improved, the hydrophilicity and the water absorption of the composite membrane are further improved, the adsorption performance and the water flux of the membrane material are further improved, sulfonic acid groups are easy to ionize to form sulfonic acid negative ions, and the functionalized montmorillonite-polyimide-montmorillonite composite membrane material has strong electrostatic adsorption effect on cationic dye methylene blue and the like, and has wide development and application prospects in the fields of separation membranes and pollutant adsorption .
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a preparation process and application of a functionalized montmorillonite-polyimide composite membrane material.
Background
At present, the water pollution problem in China is very serious, and pollution treatment on water environment mainly comprises an adsorption method, a membrane separation method, a photodegradation method and the like, wherein the membrane separation method is a new subject in the high-tech field and has wide application in the aspects of protein separation, pollutant adsorption, medicine molecule purification and the like, and for example, polysulfone, polyamide and cellulose acetate membrane materials have good adsorption and separation performances.
Polyimide contains imide ring structure, good chemical stability, high mechanical strength and wide application prospect in the field of membrane separation and pollutant adsorption, and patent 201510792250.8 'polyimide/silicon dioxide nanometer heavy metal adsorption material and preparation and regeneration method thereof' discloses that after polyimide containing benzimidazole unit is compounded with silicon dioxide, the polyimide has good adsorption performance on heavy metal ions, montmorillonite is natural silicate mineral, has large specific surface area and good adsorption performance, is cheap and easy to obtain, so that the polyimide and montmorillonite composite membrane can be used in the field of separation membrane and pollutant adsorption.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation process and application of a functionalized montmorillonite-polyimide composite membrane material, wherein the montmorillonite nano modified sulfonic phthalimide structure and polyimide are compounded to form a membrane, and the membrane has excellent adsorption performance on methylene blue and the like.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a functionalized montmorillonite-polyimide composite membrane material is prepared by the following steps:
(1) adding polyimide into N, N-dimethylformamide or N, N-dimethylacetamide, uniformly stirring to form a casting solution, then adding functionalized montmorillonite, uniformly dispersing by ultrasonic wave, defoaming the mixed solution in vacuum, pouring the mixed solution into a glass mold for natural casting to form a film, then placing the film into a coagulating bath for curing to form a film, and placing the film into deionized water for dipping to remove residual solvent to obtain the functionalized montmorillonite-polyimide composite film material which is applied to the fields of separation films and pollutant adsorption separation.
Preferably, the dosage of the functionalized montmorillonite is 4-15%, and the dosage of the polyimide is 85-96%.
Preferably, the coagulating bath is a mixed solution of 5-35% by volume of N, N-dimethylacetamide and deionized water, or a mixed solution of 5-35% by volume of N, N-dimethylacetamide and deionized water.
Preferably, the preparation process of the functionalized montmorillonite comprises the following steps:
(1) carrying out surface modification on nano montmorillonite by toluene diisocyanate, then ultrasonically dispersing the modified montmorillonite into a reaction solvent, adding 4-hydroxyphthalic anhydride and a catalyst stannous octoate, heating to 60-85 ℃, reacting for 4-10h, cooling after reaction, carrying out centrifugal separation, and washing sequentially by dichloromethane and ethanol to obtain the phthalic anhydride modified montmorillonite.
(2) Ultrasonically dispersing the functionalized montmorillonite into a reaction solvent, adding sulfanilic acid, performing an anhydride ring-opening reaction, then adding a dehydrating agent acetic anhydride, dropwise adding a catalyst triethylamine, performing imide ring-closing reaction, cooling after the reaction, performing centrifugal separation, and washing by using acetone, dichloromethane and ethanol in sequence to obtain the sulfonic phthalimide modified functionalized montmorillonite.
Preferably, the reaction solvent in step (1) is dichloromethane or chloroform or toluene or tetrahydrofuran or ethyl acetate.
Preferably, the reaction solvent in step (2) is acetone or tetrahydrofuran or methanol or 1, 4-dioxane.
Preferably, the acid anhydride ring-opening reaction is carried out at 15-30 ℃ for 3-6h, and the imide ring-closing reaction is carried out at 60-100 ℃ for 12-36 h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the functionalized montmorillonite-polyimide composite membrane material, toluene diisocyanate and 4-hydroxyphthalic anhydride are sequentially used for carrying out surface modification on nano montmorillonite, rich phthalic anhydride structures are introduced into the surface of the montmorillonite, then, anhydride ring-opening and imide ring-closing reaction is carried out on the nano montmorillonite and the phthalic anhydride structures, so that sulfonic acid phthalimide modified functionalized montmorillonite is obtained, a sulfonic acid group and phthalimide are chemically grafted to the surface of the montmorillonite, and organic functionalized modification on the montmorillonite is achieved.
The functionalized montmorillonite and polyimide are prepared into a membrane by a coagulation bath phase inversion method to obtain a functionalized montmorillonite-polyimide composite membrane material, the phthalimide structure decorated on the surface of the nano montmorillonite has good compatibility with the phthalimide structure in the main chain of the polyimide, and pi-pi bond action and intermolecular action can be generated, so that the functionalized montmorillonite and the polyimide have good interfacial compatibility, the dispersity of the nano montmorillonite in the polyimide is improved, the agglomeration of the nano montmorillonite is overcome, a three-dimensional space network structure is formed between the functionalized montmorillonite and the polyimide, the porosity is rich, the specific surface area is large, the adsorption rate and the water flux of the composite membrane can be improved, and the surface of the montmorillonite contains rich hydrophilic sulfonic acid groups, so that the hydrophilicity and the water absorption of the composite membrane are further improved, the adsorption performance and water flux of the membrane material are further improved, sulfonic acid groups are easy to ionize to form sulfonic acid negative ions, a strong electrostatic adsorption effect is achieved on cationic dye methylene blue and the like, and the functionalized montmorillonite and polyimide composite membrane material has wide development and application prospects in the fields of separation membranes and pollutant adsorption.
Drawings
FIG. 1 is a reaction diagram for the preparation of phthalic anhydride modified montmorillonite;
FIG. 2 is a reaction diagram of sulfonic acid phthalimide modified functionalized montmorillonite.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a functionalized montmorillonite-polyimide composite membrane material is prepared by the following steps:
(1) carrying out surface modification on nano montmorillonite by toluene diisocyanate, then ultrasonically dispersing the modified montmorillonite into a dichloromethane or trichloromethane or toluene or tetrahydrofuran or ethyl acetate reaction solvent, adding 4-hydroxyphthalic anhydride and a catalyst stannous octoate, heating to 60-85 ℃, reacting for 4-10h, cooling after reaction, carrying out centrifugal separation, and sequentially washing by dichloromethane and ethanol to obtain the phthalic anhydride modified montmorillonite.
(2) Ultrasonically dispersing the functionalized montmorillonite into acetone, tetrahydrofuran, methanol or 1, 4-dioxane reaction solvent, adding sulfanilic acid, performing anhydride ring-opening reaction for 3-6h at 15-30 ℃, then adding a dehydrating agent acetic anhydride, dropwise adding a catalyst triethylamine, performing imide ring-closing reaction for 12-36h at 60-100 ℃, cooling after the reaction, performing centrifugal separation, and washing by using acetone, dichloromethane and ethanol in sequence to obtain the sulfonic phthalimide modified functionalized montmorillonite.
(3) Adding 0.85-0.96g of polyimide into 20-50mL of N, N-dimethylformamide or N, N-dimethylacetamide, uniformly stirring to form a casting solution, then adding 0.04-0.15g of functionalized montmorillonite, uniformly dispersing by ultrasonic, defoaming the mixed solution in vacuum, pouring the solution into a glass mold for natural casting to form a film, then placing the film into a coagulating bath for curing to form a film, wherein the coagulating bath is a mixed solution of 5-35% by volume of N, N-dimethylacetamide and deionized water or a mixed solution of 5-35% by volume of N, N-dimethylacetamide and deionized water, and placing the film into deionized water for dipping to remove residual solvent to obtain the functionalized montmorillonite-polyimide composite film material which is applied to the fields of separation films and pollutant adsorption separation.
Example 1
(1) Carrying out surface modification on nano montmorillonite by toluene diisocyanate, then ultrasonically dispersing 0.5g of modified montmorillonite into 15mL of dichloromethane reaction solvent, adding 0.2g of 4-hydroxyphthalic anhydride and 0.01g of catalyst stannous octoate, heating to 60 ℃, reacting for 40h, cooling after reaction, carrying out centrifugal separation, and sequentially washing by dichloromethane and ethanol to obtain phthalic anhydride modified montmorillonite.
(2) Ultrasonically dispersing 0.5g of functionalized montmorillonite into 15mL of acetone reaction solvent, adding 0.25g of sulfanilic acid, performing anhydride ring-opening reaction for 3h at 15 ℃, then adding 0.18g of dehydrating agent acetic anhydride, dropwise adding 0.15g of catalyst triethylamine, performing imide ring-closing reaction for 12h at 60 ℃, cooling after reaction, performing centrifugal separation, and washing by using acetone, dichloromethane and ethanol in sequence to obtain the sulfonic phthalimide modified functionalized montmorillonite.
(3) Adding 0.85g of polyimide into 20mL of N, N-dimethylformamide, uniformly stirring to form a membrane casting solution, then adding 0.04g of functionalized montmorillonite, uniformly dispersing by ultrasonic waves, defoaming the mixed solution in vacuum, pouring the mixed solution into a glass mold, naturally casting to form a membrane, then placing the membrane into a coagulating bath to be solidified to form a membrane, wherein the coagulating bath is a mixed solution of N, N-dimethylacetamide and deionized water with the volume ratio of 5%, and placing the membrane into deionized water to dip and remove residual solvent to obtain the functionalized montmorillonite-polyimide composite membrane material.
Example 2
(1) Carrying out surface modification on nano montmorillonite by toluene diisocyanate, then ultrasonically dispersing 0.5g of modified montmorillonite into 25mL of trichloromethane reaction solvent, adding 0.3g of 4-hydroxyphthalic anhydride and 0.015g of catalyst stannous octoate, heating to 60 ℃, reacting for 8h, cooling after reaction, carrying out centrifugal separation, and sequentially washing by dichloromethane and ethanol to obtain phthalic anhydride modified montmorillonite.
(2) Ultrasonically dispersing 0.5g of functionalized montmorillonite into 20mL of tetrahydrofuran reaction solvent, adding 0.45g of sulfanilic acid, performing anhydride ring-opening reaction for 4h at 20 ℃, then adding 0.3g of dehydrating agent acetic anhydride, dropwise adding 0.25g of catalyst triethylamine, performing imide ring-closing reaction for 12h at 80 ℃, cooling after reaction, performing centrifugal separation, and washing by using acetone, dichloromethane and ethanol in sequence to obtain the sulfonic phthalimide modified functionalized montmorillonite.
(3) Adding 0.92g of polyimide into 30mL of N, N-dimethylacetamide, uniformly stirring to form a membrane casting solution, then adding 0.08g of functionalized montmorillonite, uniformly dispersing by ultrasonic waves, defoaming the mixed solution in vacuum, pouring the mixed solution into a glass mold, naturally casting to form a membrane, then placing the membrane into a coagulating bath to be solidified to form a membrane, wherein the coagulating bath is a mixed solution of N, N-dimethylacetamide and deionized water with the volume ratio of 15%, and placing the membrane into deionized water to dip and remove residual solvent to obtain the functionalized montmorillonite-polyimide composite membrane material.
Example 3
(1) Carrying out surface modification on nano montmorillonite by toluene diisocyanate, then ultrasonically dispersing 0.5g of modified montmorillonite into 35mL of toluene reaction solvent, adding 0.45g of 4-hydroxyphthalic anhydride and 0.02g of catalyst stannous octoate, heating to 80 ℃, reacting for 6h, cooling after reaction, carrying out centrifugal separation, and sequentially washing by dichloromethane and ethanol to obtain phthalic anhydride modified montmorillonite.
(2) Ultrasonically dispersing 0.5g of functionalized montmorillonite into 30mL of methanol, adding 0.6g of sulfanilic acid, performing an anhydride ring-opening reaction for 4h at 25 ℃, then adding 0.4g of dehydrating agent acetic anhydride, dropwise adding 0.35g of catalyst triethylamine, performing an imide ring-closing reaction for 24h at 80 ℃, cooling after the reaction, performing centrifugal separation, and washing by using acetone, dichloromethane and ethanol in sequence to obtain the sulfonic phthalimide modified functionalized montmorillonite.
(3) Adding 0.88g of polyimide into 40mL of N, N-dimethylacetamide, uniformly stirring to form a membrane casting solution, then adding 0.12g of functionalized montmorillonite, uniformly dispersing by ultrasonic waves, defoaming the mixed solution in vacuum, pouring the mixed solution into a glass mold, naturally casting to form a membrane, then placing the membrane into a coagulating bath to be solidified to form a membrane, wherein the coagulating bath is a mixed solution of 25% by volume of N, N-dimethylacetamide and deionized water, and placing the membrane into deionized water to dip and remove residual solvent to obtain the functionalized montmorillonite-polyimide composite membrane material.
Example 4
(1) Carrying out surface modification on nano montmorillonite by toluene diisocyanate, then ultrasonically dispersing 0.5g of modified montmorillonite into 50mL of ethyl acetate reaction solvent, adding 0.6g of 4-hydroxyphthalic anhydride and 0.025g of catalyst stannous octoate, heating to 85 ℃, reacting for 10h, cooling after reaction, carrying out centrifugal separation, and sequentially washing by dichloromethane and ethanol to obtain phthalic anhydride modified montmorillonite.
(2) Ultrasonically dispersing 0.5g of functionalized montmorillonite into 40mL of 1, 4-dioxane reaction solvent, adding 0.8g of sulfanilic acid, performing anhydride ring-opening reaction for 6h at 30 ℃, then adding 0.5g of dehydrating agent acetic anhydride, dropwise adding 0.45g of catalyst triethylamine, performing imide ring-closing reaction for 36h at 100 ℃, cooling after reaction, performing centrifugal separation, and washing by using acetone, dichloromethane and ethanol in sequence to obtain the sulfonic phthalimide modified functionalized montmorillonite.
(3) Adding 0.96g of polyimide into 50mL of N, N-dimethylacetamide, uniformly stirring to form a membrane casting solution, then adding 0.15g of functionalized montmorillonite, uniformly dispersing by ultrasonic waves, defoaming the mixed solution in vacuum, pouring the mixed solution into a glass mold, naturally casting to form a membrane, then placing the membrane into a coagulating bath to be solidified to form a membrane, wherein the coagulating bath is a mixed solution of 35% by volume of N, N-dimethylacetamide and deionized water, and placing the membrane into deionized water to dip and remove residual solvent to obtain the functionalized montmorillonite-polyimide composite membrane material.
Comparative example 1
(1) Carrying out surface modification on nano montmorillonite by toluene diisocyanate, then ultrasonically dispersing 0.5g of modified montmorillonite into 20mL of tetrahydrofuran reaction solvent, adding 0.2g of 4-hydroxyphthalic anhydride and 0.01g of catalyst stannous octoate, heating to 75 ℃, reacting for 4h, cooling after reaction, carrying out centrifugal separation, and sequentially washing by dichloromethane and ethanol to obtain phthalic anhydride modified montmorillonite.
(2) Adding 0.96g of polyimide into 30mL of N, N-dimethylformamide, uniformly stirring to form a membrane casting solution, then adding 0.04g of phthalic anhydride modified montmorillonite, uniformly dispersing by ultrasonic, defoaming the mixed solution in vacuum, pouring the solution into a glass mold, naturally casting to form a membrane, then placing the membrane into a coagulating bath to be solidified to form a membrane, wherein the coagulating bath is a mixed solution of N, N-dimethylacetamide and deionized water with the volume ratio of 10%, and placing the membrane into deionized water to dip and remove the residual solvent to obtain the montmorillonite-polyimide composite membrane material.
Comparative example 2
(1) Adding 0.95g of polyimide into 30mL of N, N-dimethylacetamide, uniformly stirring to form a membrane casting solution, then adding 0.05g of montmorillonite, uniformly dispersing by ultrasonic, defoaming the mixed solution in vacuum, pouring the solution into a glass mold, naturally casting to form a membrane, then placing the membrane into a coagulating bath to be solidified to form a membrane, wherein the coagulating bath is a mixed solution of N, N-dimethylacetamide and deionized water with the volume ratio of 15%, and placing the membrane into deionized water to dip and remove the residual solvent to obtain the montmorillonite-polyimide composite membrane material.
V with a concentration of 200mL0Adding 0.2g of functionalized montmorillonite-polyimide composite membrane material into 50mg/L methylene blue standard solution, adjusting the pH value of the solution to 4, stirring and adsorbing for 4 hours, centrifuging to obtain supernatant, and testing the concentration V of the methylene blue by an ultraviolet visible spectrophotometry method1Test the adsorption Rate W1Adsorption ratio W1＝(V0-V1)/V0。
V with a concentration of 200mL0Adding 0.2g of functionalized montmorillonite-polyimide composite membrane material into 50mg/L methylene blue standard solution, adjusting the pH value of the solution to 7, stirring and adsorbing for 4 hours, centrifuging to obtain supernatant, and testing the concentration V of the methylene blue by an ultraviolet visible spectrophotometry method2Test the adsorption Rate W2Adsorption ratio W2＝(V0-V2)/V0。
V with a concentration of 200mL0Adding 0.2g of functionalized montmorillonite-polyimide composite membrane material into 50mg/L methylene blue standard solution, adjusting the pH value of the solution to 10, stirring and adsorbing for 4h, centrifuging to obtain supernatant, and testing the concentration V of the methylene blue by an ultraviolet-visible spectrophotometry method3Test the adsorption Rate W3Adsorption ratio W3＝(V0-V3)/V0。
Claims (8)
1. A preparation process of a functionalized montmorillonite-polyimide composite membrane material is characterized by comprising the following steps: the preparation process comprises the following steps:
(1) adding polyimide into N, N-dimethylformamide or N, N-dimethylacetamide, uniformly stirring to form a casting solution, then adding functionalized montmorillonite, uniformly dispersing by ultrasonic waves, defoaming the mixed solution in vacuum, pouring the mixed solution into a glass mold for natural casting to form a film, then placing the film into a coagulating bath for curing to form a film, and placing the film into deionized water for dipping to remove residual solvent to obtain the functionalized montmorillonite-polyimide composite film material.
2. The preparation process of the functionalized montmorillonite-polyimide composite membrane material as claimed in claim 1, wherein the preparation process comprises the following steps: the dosage of the functionalized montmorillonite is 4-15%, and the dosage of the polyimide is 85-96%.
3. The preparation process of the functionalized montmorillonite-polyimide composite membrane material as claimed in claim 1, wherein the preparation process comprises the following steps: the coagulating bath is a mixed solution of N, N-dimethylacetamide and deionized water with the volume ratio of 5-35%, or a mixed solution of N, N-dimethylacetamide and deionized water with the volume ratio of 5-35%.
4. The preparation process of the functionalized montmorillonite-polyimide composite membrane material as claimed in claim 1, wherein the preparation process comprises the following steps: the preparation process of the functionalized montmorillonite comprises the following steps:
(1) carrying out surface modification on nano montmorillonite by toluene diisocyanate, then ultrasonically dispersing the modified montmorillonite into a reaction solvent, adding 4-hydroxyphthalic anhydride and a catalyst stannous octoate, heating to 60-85 ℃, and reacting for 4-10h to obtain phthalic anhydride modified montmorillonite;
(2) ultrasonically dispersing the functionalized montmorillonite into a reaction solvent, adding sulfanilic acid, performing an anhydride ring-opening reaction, then adding a dehydrating agent acetic anhydride, dropwise adding a catalyst triethylamine, and performing an imide ring-closing reaction to obtain the sulfonic phthalimide modified functionalized montmorillonite.
5. The preparation process of the functionalized montmorillonite-polyimide composite membrane material as claimed in claim 4, wherein the preparation process comprises the following steps: the reaction solvent in the step (1) is dichloromethane or trichloromethane or toluene or tetrahydrofuran or ethyl acetate.
6. The preparation process of the functionalized montmorillonite-polyimide composite membrane material as claimed in claim 4, wherein the preparation process comprises the following steps: in the step (2), the reaction solvent is acetone or tetrahydrofuran or methanol or 1, 4-dioxane.
7. The preparation process of the functionalized montmorillonite-polyimide composite membrane material as claimed in claim 4, wherein the preparation process comprises the following steps: the ring-opening reaction of the anhydride is carried out for 3-6h at 15-30 ℃, and the ring-closing reaction of the imide is carried out for 12-36h at 60-100 ℃.
8. Use of a functionalized montmorillonite-polyimide composite membrane material as described in claims 1-7 in separation membranes and contaminant adsorption separation.
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| CN115207424A (en) * | 2022-08-22 | 2022-10-18 | 湖北工程学院 | A kind of preparation method of double functionalized montmorillonite sulfonated polyether ether ketone composite membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115207424A (en) * | 2022-08-22 | 2022-10-18 | 湖北工程学院 | A kind of preparation method of double functionalized montmorillonite sulfonated polyether ether ketone composite membrane |
| CN118325152A (en) * | 2024-06-13 | 2024-07-12 | 芜湖新航薄膜科技有限公司 | High-barrier-property film material and preparation method thereof |
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