CN106492660B - Temperature response PVDF semi-interpenetrating network polymer film and preparation method thereof - Google Patents
Temperature response PVDF semi-interpenetrating network polymer film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a temperature response PVDF semi-interpenetrating network polymer film and a preparation method thereof, comprising the following processes: (1) polymerizing a temperature-responsive monomer and PVDF in a DMF organic solvent to obtain a semi-interpenetrating network polymer; (2) uniformly dispersing the obtained semi-interpenetrating network polymer and pore-forming agent in an organic solvent to obtain a membrane casting solution; (3) the obtained casting solution is scraped into a liquid film on a clean and flat glass plate by a glass rod, and then the liquid film is converted into a film in a coagulating bath. The temperature response PVDF semi-interpenetrating network polymer membrane prepared by the invention has good hydrophilicity and high membrane porosity; has obvious dependence on temperature, and the flux variation range with the temperature at 0.1MP is 200-2h, the bovine serum albumin retention rate can reach more than 85%, and the bovine serum albumin has excellent performances of large flux and high retention.
Description
Technical Field
The invention belongs to the field of temperature response polymer films, and particularly relates to a preparation method of a semi-interpenetrating network temperature response polymer film.
Background
The polymer separation membrane has the advantages of high separation efficiency, low energy consumption, simple operation and the like, and becomes one of the main means of separation and purification. However, the rapidly developed membrane separation process puts more new requirements on the physical and chemical properties, functionalization and the like of membrane materials, so that the preparation of novel membrane separation materials by using new technologies and new methods becomes a latest research hotspot.
Polyvinylidene fluoride (PVDF) is a crystalline polymer, has excellent aging resistance and ultraviolet resistance, is not corroded by acid, alkali, strong oxidants and the like at room temperature, has good chemical stability, thermal stability and mechanical properties, is a separation membrane material with good comprehensiveness, and is widely applied to the fields of medical treatment, water treatment, petrochemical industry, food industry and the like. However, pure PVDF membranes do not have intelligent separation characteristics, and their intelligent modification and sensitive characteristics such as pH, temperature, and ionic strength have attracted great interest.
From the current literature reports, two modification methods of blending and grafting are mainly used for preparing the responsive PVDF membrane. Functional components in the membrane material prepared by blending modification are easy to lose in the separation process, and the performance of the membrane is reduced. The grafting modification mainly comprises methods of surface chemical modification, irradiation grafting modification, plasma modification and the like. The surface chemical modification and irradiation grafting processes are complex, the conditions are harsh, and large-scale production is not easy to realize; the plasma modified surface treatment efficiency is low, the equipment is complex, and the modification effect is gradually reduced along with time. Therefore, it is a new need to find a simple, convenient, reliable and low-cost modification method.
The semi-interpenetrating network polymerization technology has simple preparation and is easy to realize continuous industrial production, and the obtained semi-interpenetrating network polymer is a network structure polymer formed by interpenetrating one non-crosslinked linear polymer into another crosslinked polymer. Unlike blends, the two polymers still exist in their respective phases in the semi-interpenetrating network polymer structure; unlike graft copolymers, no chemical bonding occurs between the two polymers in the semi-interpenetrating network polymer structure. The polymer with the structure has uniform composition, is not easy to damage in the using process and has stable performance. The invention adopts the technology to modify PVDF and prepares the temperature response PVDF semi-interpenetrating network polymer film. The membrane has good hydrophilicity, temperature sensitivity and stability, and has high water flux and high protein retention capacity.
Disclosure of Invention
The invention aims to prepare a temperature response PVDF membrane by adopting a novel modification method. The invention provides a temperature response PVDF semi-interpenetrating network polymer film and a preparation method thereof. The temperature response macromolecule cross-linked polymer in the membrane and linear polyvinylidene fluoride (PVDF) form a semi-interpenetrating network structure, so that the membrane has lasting stability in the using process. The membrane has the advantages of high flux, high rejection rate and temperature responsiveness; meanwhile, the membrane has good hydrophilicity and can obviously improve the pollution resistance.
The technical scheme for solving the technical problem of the preparation method of the product is as follows: a preparation method of a temperature response PVDF semi-interpenetrating network polymer membrane is designed, which comprises the synthesis of semi-interpenetrating network polymer and the preparation of the membrane, and comprises the following steps:
(1) preparation of temperature response PVDF semi-interpenetrating network polymer: dissolving vinylidene fluoride (PVDF), a temperature response monomer, N-Methylene Bisacrylamide (MBA) and Azobisisobutyronitrile (AIBN) in an organic solvent DMF, carrying out polymerization crosslinking under the condition of nitrogen protection, and obtaining a temperature response PVDF semi-interpenetrating network polymer through centrifugation, cleaning and drying; the temperature-responsive monomer is one of N-isopropylacrylamide (NIPAM) or N, N-dimethylacrylamide (PDMAAm).
(2) Preparing a casting solution: uniformly dispersing the temperature response PVDF semi-interpenetrating network polymer obtained in the step (1) and a pore-forming agent in an organic solvent, and defoaming in vacuum to obtain a membrane casting solution; the organic solvent is one of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC) and N-methylpyrrolidone (NMP).
(3) Preparing a temperature response PVDF semi-interpenetrating network polymer film: and (3) scraping the casting solution obtained in the step (2) on a clean and flat glass plate by using a glass rod to form a liquid film, and performing phase conversion to form a film in a coagulating bath, wherein the coagulating bath is distilled water or 90-95% ethanol water solution.
The invention relates to a preparation method of a temperature response PVDF semi-interpenetrating network polymer film, which is prepared by scraping polyvinylidene fluoride (PVDF) modified by a cross-linked polymer with temperature responsiveness. The method has the advantages that the temperature-responsive monomer is subjected to cross-linking polymerization in the presence of PVDF so as to form a semi-interpenetrating network structure, and compared with grafting modification, the method is simple to operate and easy to realize continuous production; compared with blending modification, the temperature response component is not easy to lose in the using process of the membrane, and has lasting stability. The membrane pores can be reversibly swelled and shrunk, and the flux and interception can be effectively controlled. And the advantages are good hydrophilicity and pollution resistance. The membrane has the advantages of high flux and high interception performance, and is a novel membrane separation material.
The preparation process and the preparation method are simple, can be carried out under normal pressure, all the used reagents are conventional reagents, and the equipment is simple and easy for continuous industrial production.
Detailed Description
The invention relates to a temperature response PVDF semi-interpenetrating network polymer film and a preparation method thereof. The film is prepared by selecting polyvinylidene fluoride (PVDF) as a main material for film formation, physically blending a temperature response monomer and the PVDF, then carrying out polymerization crosslinking to prepare a temperature response PVDF semi-interpenetrating network polymer, and finally adopting a solution phase conversion method for film formation. The design principle is that PVDF powder and temperature response monomer are dispersed in organic solvent DMF at the same time, initiator and cross-linking agent are added to promote the monomer to carry out polymerization and cross-linking in the presence of PVDF to form semi-interpenetrating network polymer, and then the semi-interpenetrating network polymer is scraped into a film. The preparation method of the invention ensures that the polymer with temperature responsiveness and PVDF are not easy to lose in the use process of the membrane and the stability of the membrane is good.
The method of the invention is applied to the preparation of flat membrane, but is also applicable to other forms of membrane, including hollow fiber membrane, tubular membrane, etc.
The preparation of the temperature responsive PVDF semi-interpenetrating network polymer membrane of the present invention is further described by the following examples.
Example 1
(1) Uniformly dispersing 5g of PVDF in 80ml DMF (saturated solution of propylene) in a three-neck flask at 70 ℃, adding 5g of N-isopropylacrylamide (NIPAM) and 0.13g of crosslinking agent MBA (the mass ratio of the MBA to the monomer is 1: 62.5 and 1: 40) respectively, stirring to form uniform mixed solution, and introducing nitrogen for 30 min; 0.08g of initiator AIBN was rapidly added to the three-necked flask and the reaction was stirred under a nitrogen atmosphere for 6 hours. The reaction was centrifuged to precipitate, the precipitate was dried in vacuo at 50 ℃ for 48h and ground to a powder.
(2) And (2) adding the product obtained in the step (1) into a certain amount of N, N-Dimethylformamide (DMF), keeping the solid contents of the casting solution at 16%, 17%, 18%, 19% and 20%, respectively, stirring for 2 hours at 60 ℃ to form a uniform casting solution, and defoaming for 30 minutes in vacuum.
(3) And (3) pouring the casting solution obtained in the step (2) onto a clean glass plate, scraping the casting solution into a film by using a glass rod, immersing the film into distilled water at 25 ℃ to solidify the film, and washing the residual solvent by using the distilled water to obtain the temperature response film.
Example 2
(1) Uniformly dispersing 5g of PVDF in 100ml of mixed solution in a three-neck flask at 70 ℃, adding 7.5g N-isopropyl acrylamide (NIPAM) and 0.19g of cross-linking agent MBA (the mass ratio of the MBA to the monomer is 1: 62.5 and 1: 40) respectively, stirring to form uniform mixed solution, and introducing nitrogen for 30 min; 0.12g of AIBN initiator was quickly added to the three-necked flask and the reaction was stirred under a nitrogen atmosphere for 6 hours. The reaction was centrifuged to precipitate, the precipitate was dried in vacuo at 50 ℃ for 48h and ground to a powder.
(2) Adding the product obtained in the step (1) into a certain amount of N, N-Dimethylacetamide (DMAC), keeping the solid contents of the casting solution at 16%, 17%, 18%, 19% and 20%, respectively, stirring for 2 hours at 60 ℃ to form a uniform casting solution, and defoaming for 40min in vacuum.
(3) Pouring the casting solution obtained in the step (2) on a clean glass plate, scraping the casting solution by using a glass rod to form a film, immersing the film in a 95% ethanol water solution at 28 ℃ to solidify the film, and washing the residual solvent by using distilled water to obtain the temperature response film
Example 3
(1) Uniformly dispersing 5g of PVDF in 140ml DMF (dimethyl formamide) in a three-neck flask at 70 ℃, adding 11.7g N-isopropyl acrylamide (NIPAM) and 0.3g of cross-linking agent MBA (the mass ratio of the MBA to the monomer is 1: 62.5 and 1: 40) respectively, stirring to form uniform mixed liquid, and introducing nitrogen for 30 min; 0.19g of AIBN initiator was quickly added to the three-necked flask and the reaction was stirred under a nitrogen atmosphere for 6 hours. The reaction was centrifuged to precipitate, the precipitate was dried in vacuo at 50 ℃ for 48h and ground to a powder.
(2) Adding the product obtained in the step (1) into a certain amount of N-methylpyrrolidone (NMP), keeping the solid contents of the casting solution at 16%, 17%, 18%, 19% and 20%, respectively, stirring for 2 hours at 60 ℃ to form a uniform casting solution, and defoaming for 50min in vacuum.
(3) Pouring the casting solution obtained in the step (2) onto a clean glass plate, scraping the casting solution by using a glass rod to form a film, immersing the film in a 90% ethanol water solution at the temperature of 30 ℃ to solidify the film, and washing the residual solvent by using distilled water to obtain the temperature response film.
Example 4
(1) Uniformly dispersing 5g of PVDF in 200ml of mixed solution of sodium fluoride and sodium fluoride in a three-neck flask at 75 ℃, adding 20g N-isopropyl acrylamide (NIPAM) and 0.5g of crosslinking agent MBA (the mass ratio of the MBA to the monomer is 1: 62.5 and 1: 40) respectively, and introducing nitrogen for 30 min; 0.32g of AIBN initiator was quickly added to the three-necked flask and the reaction was stirred under a nitrogen atmosphere for 6 hours. The reaction was centrifuged to precipitate, the precipitate was dried in vacuo at 50 ℃ for 48h and ground to a powder.
(2) Same as example 1
(3) Same as example 3
Example 5
(1) Uniformly dispersing 5g of PVDF in 80ml DMF (dimethyl formamide) in a three-neck flask at 75 ℃, adding 5g N, wherein the mass ratio of N-dimethylacrylamide (PDMAAm) to a cross-linking agent MBA is 0.08g and 0.13g respectively (the mass ratio of MBA to a monomer is 1: 62.5 and 1: 40), stirring to form uniform mixed solution, and introducing nitrogen for 30 min; 0.08g of initiator AIBN was rapidly added to the three-necked flask and the reaction was stirred under a nitrogen atmosphere for 6 hours. The reaction was centrifuged to precipitate, the precipitate was dried in vacuo at 50 ℃ for 48h and ground to a powder.
(2) Same as example 1
(3) Same as example 1
Example 6
(1) Uniformly dispersing 5g of PVDF in 100ml of mixed solution in a three-neck flask at 75 ℃, adding 7.5g of N, N-dimethylacrylamide (PDMAAm) and 0.19g of cross-linking agent MBA (the mass ratio of the MBA to the monomer is 1: 62.5 and 1: 40) respectively, stirring to form uniform mixed solution, and introducing nitrogen for 30 min; 0.12g of AIBN initiator was quickly added to the three-necked flask and the reaction was stirred under a nitrogen atmosphere for 6 hours. The reaction was centrifuged to precipitate, the precipitate was dried in vacuo at 50 ℃ for 48h and ground to a powder.
(2) Same as example 1
(3) Same as example 3
Example 7
(1) Uniformly dispersing 5g of PVDF in 140ml DMF (dimethyl formamide) in a three-neck flask at 80 ℃, adding 11.7g N, respectively 0.19g and 0.3g of N-dimethylacrylamide (PDMAAm) and a cross-linking agent MBA (the mass ratio of the MBA to the monomer is 1: 62.5 and 1: 40), stirring to form uniform mixed solution, and introducing nitrogen for 30 min; 0.19g of AIBN initiator was quickly added to the three-necked flask and the reaction was stirred under a nitrogen atmosphere for 6 hours. The reaction was centrifuged to precipitate, the precipitate was dried in vacuo at 50 ℃ for 48h and ground to a powder.
(2) Same as example 2
(3) Same as example 3
Example 8
(1) Uniformly dispersing 5g of PVDF in 200ml of mixed solution in a three-neck flask at 80 ℃, adding 20g N, wherein the mass ratio of N-dimethylacrylamide (PDMAAm) to a cross-linking agent MBA is 0.32g and 0.5g respectively (the mass ratio of MBA to a monomer is 1: 62.5 and 1: 40), stirring to form a uniform mixed solution, and introducing nitrogen for 30 min; 0.32g of AIBN initiator was quickly added to the three-necked flask and the reaction was stirred under a nitrogen atmosphere for 6 hours. The reaction was centrifuged to precipitate, the precipitate was dried in vacuo at 50 ℃ for 48h and ground to a powder.
(2) Same as example 2
(3) Same as example 3
Example 9
(1) Same as example 1
(2) Adding the product obtained in the step (1) and pore-forming agent F127 with mass percentages (F127/(F127+ IPN)) of 8%, 15% and 22% into a certain amount of N, N-Dimethylformamide (DMF), keeping the solid contents of the casting solution at 16% -20%, stirring for 2h at 60 ℃ to form a clear and transparent uniform casting solution, and defoaming for 30min in vacuum.
(3) Same as example 1
Example 10
(1) Same as example 2
(2) Adding the product obtained in the step (1) and a pore-forming agent F127 with the mass percentages (F127/(F127+ IPN)) of 8%, 15% and 22% into a certain amount of N, N-Dimethylacetamide (DMAC), wherein the solid content of the casting solution is 16% -20%, stirring for 3h at 60 ℃ to form a clear and transparent uniform casting solution, and defoaming for 30min in vacuum.
(3) Same as example 2
Example 11
(1) Same as example 5
(2) Adding the product obtained in the step (1) and a pore-forming agent F127 with the mass percentages (F127/(F127+ IPN)) of 8%, 15% and 22% into a certain amount of N-methylpyrrolidone (NMP), wherein the solid content of the casting solution is 16% -20%, stirring for 3h at 60 ℃ to form a clear and transparent uniform casting solution, and defoaming for 30min in vacuum.
(3) Same as example 3
Example 12
(1) Same as example 6
(2) Same as example 9
(3) Same as example 1
Example 13
(1) Same as example 3
(2) Adding the product obtained in the step (1) and pore-forming agent F127 with mass percentages (PEG/(PEG + IPN)) of 8%, 15% and 22% into a certain amount of N, N-Dimethylformamide (DMF), keeping the solid contents of the casting solution at 16-20%, stirring for 2h at 60 ℃ to form a clear and transparent uniform casting solution, and defoaming for 30min in vacuum. The molecular weight of PEG is 6000, 10000, 20000 respectively.
(3) Same as example 1
Example 14
(1) Same as example 4
(2) Adding the product obtained in the step (1) and a pore-forming agent F127 with the mass percentages (PEG/(PEG + IPN)) of 8%, 15% and 22% into a certain amount of N, N-Dimethylacetamide (DMAC), wherein the solid content of the casting solution is 16% -20%, stirring for 3h at 60 ℃ to form a clear and transparent uniform casting solution, and defoaming for 30min in vacuum. The molecular weight of PEG is 6000, 10000, 20000 respectively.
(3) Same as example 2
Example 15
(1) Same as example 7
(2) Adding the product obtained in the step (1) and a pore-forming agent F127 with the mass percentages (PEG/(PEG + IPN)) of 8%, 15% and 22% into a certain amount of N-methylpyrrolidone (NMP), wherein the solid content of the casting solution is 16% -20%, stirring for 3h at 60 ℃ to form a clear and transparent uniform casting solution, and defoaming for 30min in vacuum. The molecular weight of PEG is 6000, 10000, 20000 respectively.
(3) Same as example 3
Example 16
(1) Same as example 8
(2) Adding the product obtained in the step (1) and a pore-forming agent F127 with the mass percentages (PEG/(PEG + IPN)) of 8%, 15% and 22% into a certain amount of N, N-Dimethylformamide (DMF)), wherein the solid content of the casting solution is 16% -20%, stirring for 4h at 60 ℃ to form a clear and transparent uniform casting solution, and defoaming for 30min in vacuum. The molecular weight of PEG is 6000, 10000, 20000 respectively.
(3) Same as example 3
Through detection, the mass ratio of the temperature-responsive polymer to the PVDF of the prepared temperature-responsive PVDF semi-interpenetrating network polymer film is 1: 1-1: 4; with the increase of the amount of the temperature response monomer, the number of the membrane pores is increased, the flux is increased, and the hydrophilicity is obviously improved; along with the increase of the pore-forming amount, the number of the membrane pores is increased, the pore diameter is increased, the contact angle can be reduced to 0 degree from 80 degrees, and the pore diameter of the membrane can be adjusted between 100 and 1000 nm. The temperature response PVDF semi-interpenetrating network polymer membrane has obvious dependence on temperature, and the flux variation range is 200-2000L/m under 0.1MP2h, and the retention rate of bovine serum albumin can reach more than 85%.
The preparation method of the temperature response PVDF semi-interpenetrating network polymer membrane provided by the invention has been described by way of example, and the invention can be realized by modifying or properly changing and combining the contents described in the invention without departing from the contents, spirit and scope of the invention. It is specifically noted that all such substitutions and modifications will be apparent to those skilled in the art. They are deemed to be within the spirit, scope and content of the invention.
Claims (7)
1. A temperature response PVDF semi-interpenetrating network polymer membrane is characterized in that the membrane is formed by semi-interpenetrating a temperature response polymer and polyvinylidene fluoride (PVDF), the mass ratio of the PVDF to the temperature response polymer is 1: 1-1: 4, and the membrane is prepared by the following method steps:
(1) preparation of temperature response PVDF semi-interpenetrating network polymer: dissolving a certain amount of PVDF in a solvent DMF, adding a temperature response monomer, a crosslinking agent N, N-methylene bisacrylamide and an initiator azobisisobutyronitrile, and carrying out free radical polymerization to obtain a temperature response PVDF semi-interpenetrating network polymer;
(2) preparing a casting solution: uniformly dispersing the temperature response PVDF semi-interpenetrating network polymer obtained in the step (1) and a pore-forming agent in an organic solvent, and defoaming in vacuum for 30-50min to obtain a membrane casting solution;
(3) preparing a temperature response PVDF semi-interpenetrating network polymer film: and (3) scraping the casting solution obtained in the step (2) on a clean and flat glass plate by using a glass rod to form a liquid film, and converting the liquid film into a film in a coagulating bath.
2. The PVDF semi-interpenetrating network polymer membrane with temperature response as defined in claim 1, wherein the membrane pore size can be changed by adjusting the ambient temperature, and the flux size is 200-2h is adjustable, and the retention rate of bovine serum albumin is more than 85%.
3. The PVDF semi-ipn polymer film as claimed in claim 1, wherein the temperature responsive polymer is poly N-isopropylacrylamide or poly N, N-dimethylacrylamide.
4. The temperature-responsive PVDF semi-interpenetrating network polymer membrane according to claim 1, wherein the temperature-responsive monomer is N-isopropylacrylamide or N, N-dimethylacrylamide.
5. The temperature-responsive PVDF semi-interpenetrating network polymer membrane according to claim 1, wherein said organic solvent is one of N, N-Dimethylformamide (DMF) or N, N-Dimethylacetamide (DMAC) or N-methylpyrrolidone (NMP).
6. The PVDF semi-interpenetrating network polymer membrane with temperature response of claim 1, wherein the pore-forming agent is oxyethylene-oxypropylene-oxyethylene triblock copolymer (F127) or polyethylene glycol (PEG).
7. The temperature-responsive PVDF semi-interpenetrating network polymer membrane as defined in claim 1, wherein said coagulating bath is distilled water or 90-95% aqueous ethanol.
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| JPS60188411A (en) * | 1984-03-09 | 1985-09-25 | Agency Of Ind Science & Technol | Temperature-sensitive film material and its production |
| CN102061049A (en) * | 2010-11-30 | 2011-05-18 | 天津工业大学 | Temperature sensitive polyvinylidene fluoride gel film and preparation method thereof |
| CN103182257A (en) * | 2013-04-07 | 2013-07-03 | 福州大学 | Temperature-sensitive self-cleaning polyvinylidene fluoride film and preparation method thereof |
| CN103418255A (en) * | 2012-05-22 | 2013-12-04 | 宁波大学 | Thermo-sensitive type ultrafiltration membrane and preparation method thereof |
| CN104248918A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Method for preparing hydrophilic pollution-resistant composite ultrafiltration membrane by semi-interpenetrating network method |
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| JPS60188411A (en) * | 1984-03-09 | 1985-09-25 | Agency Of Ind Science & Technol | Temperature-sensitive film material and its production |
| CN102061049A (en) * | 2010-11-30 | 2011-05-18 | 天津工业大学 | Temperature sensitive polyvinylidene fluoride gel film and preparation method thereof |
| CN103418255A (en) * | 2012-05-22 | 2013-12-04 | 宁波大学 | Thermo-sensitive type ultrafiltration membrane and preparation method thereof |
| CN103182257A (en) * | 2013-04-07 | 2013-07-03 | 福州大学 | Temperature-sensitive self-cleaning polyvinylidene fluoride film and preparation method thereof |
| CN104248918A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Method for preparing hydrophilic pollution-resistant composite ultrafiltration membrane by semi-interpenetrating network method |
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