CN114797512A - Star-poly (dimethylaminoethyl acrylate) polymer modified PVDF (polyvinylidene fluoride) membrane and application thereof - Google Patents
Star-poly (dimethylaminoethyl acrylate) polymer modified PVDF (polyvinylidene fluoride) membrane and application thereof Download PDFInfo
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Abstract
The invention discloses a PVDF membrane modified by star-poly (dimethylaminoethyl acrylate) polymer and application thereof. The PVDF membrane is formed by PVDF modified by star-poly (dimethylaminoethyl acrylate) polymer, wherein the star-poly (dimethylaminoethyl acrylate) polymer has a structure shown in a formula I,
wherein R is
Description
Technical Field
The invention relates to the field of material science, in particular to PVDF modified by star-poly (dimethylaminoethyl acrylate) polymer and application thereof; in particular, the present invention relates to PVDF membranes, star-polydimethylaminoethyl acrylate polymers, methods of making star-polydimethylaminoethyl acrylate polymers, casting solutions for forming modified PVDF membranes, and methods of making cellular thin films.
Background
In the past two decades, with the rapid development of the fields of polymer chemistry and material science, membrane separation technology has grown mature and is gradually applied to a variety of fields including water treatment, food and drug, petrochemical, and medicine. Membrane separation techniques have a number of advantages, including: simple use, low separation energy consumption, high separation efficiency, environmental protection and the like, and can bring huge social, economic and environmental benefits. Nowadays, membrane materials in membrane separation technology are various, such as polyvinylidene fluoride, conductive polymer materials, molecular sieve polymer materials, and the like.
Although developments in the field of material science have driven the use of membrane separation technology in a variety of areas, in certain complex applications, the development of membrane separation technology is still limited by key technical issues such as susceptibility of membrane materials to contamination, susceptibility of membrane materials to failure, short service life, etc.
Polyvinylidene fluoride (PVDF) is one of the most commonly used membrane materials, and has been widely used in various fields due to its high mechanical strength, good thermal stability, and excellent chemical resistance. But some characteristics of the existing PVDF membrane also limit the further application of the PVDF membrane, such as the surface free energy of the PVDF polymer is very low and is extremely hydrophobic, so that the driving force required by the PVDF membrane in the membrane separation process is increased, and the energy consumption is increased; meanwhile, the PVDF membrane is easy to be polluted by organic matters such as protein, grease and the like when certain samples such as wastewater are treated by the PVDF membrane due to higher hydrophobicity, so that the service life of the PVDF membrane is shortened. It can be seen that existing PVDF membranes remain to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to propose a PVDF membrane modified based on a star-polydimethylaminoethyl acrylate polymer and its use.
In a first aspect of the invention, the invention provides a PVDF membrane. According to an embodiment of the invention, the PVDF membrane is formed from PVDF modified with a star-polydimethylaminoethyl acrylate polymer having the structure shown in formula I,
wherein R is
n is a positive integer of 15 to 105.
According to the embodiment of the invention, the inventor finds that the long alkyl chain in the star-poly (dimethylaminoethyl acrylate) polymer has hydrophobicity and good compatibility with PVDF; the dimethylaminoethyl acrylate chain segment has high hydrophilicity, the star structure also helps the star-polydimethylaminoethyl acrylate polymer to be firmly fixed on the matrix membrane, and the stability of the combination of the polymer and the PVDF membrane is improved while the hydrophilicity is improved. Therefore, the star-poly (dimethylaminoethyl acrylate) polymer hydrophilic modified PVDF membrane has higher hydrophilicity, permeability and stain resistance, and still has higher recovery performance after being used for a plurality of times and for a long time. Furthermore, the PVDF membrane is not easy to be polluted by organic matters such as protein, grease and the like when being used for treating certain samples such as waste water, the service life is longer, and the required energy consumption is lower.
According to an embodiment of the invention, the PVDF film may have at least one of the following additional features:
according to an embodiment of the invention, the PDVF membrane comprises hollow areas.
According to an embodiment of the invention, the PVDF membrane is circular.
In a second aspect of the invention, the invention provides a star-poly (dimethylaminoethyl acrylate) polymer. According to an embodiment of the present invention, the star-poly (dimethylaminoethyl acrylate) polymer has a structure shown in formula I,
wherein R is
n is a positive integer of 15 to 105.
According to the embodiment of the invention, the long alkyl chain in the star-poly (dimethylaminoethyl acrylate) polymer has hydrophobicity and good compatibility with PVDF; the dimethylaminoethyl acrylate chain segment has high hydrophilicity, the star structure also helps the star-polydimethylaminoethyl acrylate polymer to be more firmly fixed on a matrix membrane, and the hydrophilicity is improved while the stability of the combination of the polymer and the PVDF membrane is increased. The star-poly (dimethylaminoethyl acrylate) polymer is used for modifying the PVDF membrane, so that the hydrophilicity, permeability and stain resistance of the PVDF membrane can be effectively improved, and the PVDF membrane still has higher recovery performance after being used for a plurality of times and for a long time.
According to the embodiment of the invention, the polymerization degree of the star-poly (dimethylaminoethyl acrylate) polymer is between 100 and 400.
According to an embodiment of the invention, the star-poly (dimethylaminoethyl acrylate) polymer has a molecular weight of between 10,000 and 60,000 daltons.
In a third aspect of the invention, the invention provides a method of making the star-poly (dimethylaminoethyl acrylate) polymer of the above example. According to an embodiment of the invention, the method comprises: polymerizing dimethylaminoethyl acrylate and four-branched-chain 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid to obtain the star-poly (dimethylaminoethyl acrylate) polymer; wherein the four-branched-chain 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid has a structure shown in a formula II,
According to the embodiment of the invention, the method can prepare the star-shaped poly (dimethylaminoethyl acrylate) polymer simply, efficiently and structurally controllably.
According to an embodiment of the present invention, the above method for preparing star-polydimethylaminoethyl acrylate polymer may further have at least one of the following additional technical features:
according to the embodiment of the invention, the molar ratio of the dimethylaminoethyl acrylate to the four-branched 2- (dodecyl trithiocarbonate) -2-methylpropionic acid is (60-420): 1.
According to an embodiment of the invention, the polymerization is a reversible addition-fragmentation chain transfer polymerization and is carried out under the following conditions: an inert atmosphere; azodiisobutyronitrile is used as an initiator; dissolving the dimethylaminoethyl acrylate and the four-branched-chain 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid in 2-butanone; the reaction temperature is 70-120 ℃; and the reaction time is 4-20 h.
In a fourth aspect of the invention, a casting solution for forming a modified PVDF membrane is presented. According to an embodiment of the invention, the casting solution comprises: 10-20 v% PVDF; 0.1-5 v% of pore-foaming agent; 0.1-15 v% of the star-polydimethylaminoethyl acrylate polymer; and the balance solvent.
According to the embodiment of the invention, the casting solution contains the star-polydimethylaminoethyl acrylate polymer which is suitable for modifying PVDF, so that the modified PVDF membrane formed by the casting solution has higher hydrophilicity, permeability and dirt resistance and still has higher recovery performance after being used for a plurality of times and for a long time. Furthermore, the modified PVDF membrane is not easy to be polluted by organic matters such as protein, grease and the like when being used for treating certain samples such as waste water, the service life is longer, and the required energy consumption is lower.
According to an embodiment of the present invention, the casting solution for forming a modified PVDF film may further have at least one of the following additional technical features:
according to an embodiment of the present invention, the solvent is selected from at least one of dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide.
According to an embodiment of the present invention, the casting solution is obtained by the following steps: stirring the raw materials in a metal bath at the temperature of 60-80 ℃ for reaction for 10-15 h, and then placing the raw materials in a vacuum oven for degassing.
In a fifth aspect of the invention, the invention proposes the use of the PVDF membrane of the above example in the preparation of a thin cell film. As described above, the PVDF membrane has excellent hydrophilicity, permeability, and stain resistance. For the monolayer cell membrane obtained by adherent culture, the monolayer cell membrane can be easily collected from the culture dish by using the PVDF membrane so as to be convenient for subsequent application.
In a sixth aspect of the invention, a method of preparing a thin film of cells is presented. According to an embodiment of the invention, the method comprises: carrying out adherent culture on the cells in a culture dish so as to form a monolayer cell film; the monolayer cell film is in stripping liquid so as to change the bonding force between the monolayer cell film and the culture dish and enable the monolayer cell film to be separated from the culture dish; and removing the monolayer cell membrane from the culture dish using the PVDF membrane of the above example.
According to the embodiment of the invention, by carrying out adherent culture on the cells, the cells can be attached to the bottom of the culture dish in the amplification process and carry out adherent proliferation, so that the monolayer cell film is obtained. Subsequently, the binding force between the monolayer cell film and the culture dish is changed by the stripping solution to enable the cell film to fall off, and the PVDF film of the embodiment is used for absorbing the fallen monolayer cell film to finish the collection of the cell film.
According to an embodiment of the present invention, the method for preparing a cell membrane may further have at least one of the following additional technical features:
according to an embodiment of the invention, the cell comprises at least one selected from the group consisting of stem cells, neuronal cells, astrocytes, oligodendrocytes, epithelial cells, endothelial cells, muscle cells, fibroblasts.
According to an embodiment of the present invention, the stem cell includes at least one of an induced pluripotent stem cell, an adult stem cell, a mesenchymal stem cell, a neural stem cell, a cardiac stem cell and a lung stem cell.
According to an embodiment of the present invention, the mesenchymal stem cell includes at least one of a bone marrow-derived mesenchymal stem cell, an adipose-derived mesenchymal stem cell, and an umbilical cord-derived mesenchymal stem cell.
According to an embodiment of the invention, the epithelial cells comprise at least one of corneal epithelial cells, prostate epithelial cells, renal tubular epithelial cells, coronary artery.
According to an embodiment of the invention, the endothelial cells comprise at least one of vascular endothelial cells, pulmonary arterial endothelial cells, aortic endothelial cells.
According to an embodiment of the invention, the muscle cells comprise at least one of aortic smooth muscle cells, pulmonary smooth muscle cells, coronary smooth muscle cells.
According to an embodiment of the invention, the fibroblasts comprise at least one of cardiac fibroblasts, skin fibroblasts, renal interstitial fibroblasts, preferably mesenchymal stem cells.
According to an embodiment of the present invention, the stripping solution is a buffer solution that does not contain calcium ions and magnesium ions.
According to the embodiment of the invention, the pH value of the buffer solution is 6.9-7.4, and preferably, the buffer solution is DPBS.
According to an embodiment of the invention, the method further comprises: and superposing a plurality of the monolayer cell films so as to obtain a composite cell film.
According to the embodiment of the invention, the composite cell film comprises 2-3 layers of cell films.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic structural view of a PVDF membrane according to one embodiment of the invention;
FIG. 2 is a schematic structural view of a PVDF membrane according to yet another embodiment of the invention;
FIG. 3 is a NMR spectrum of a star-polydimethylaminoethyl polyacrylate polymer according to one embodiment of the present invention;
FIG. 4 is an SEM image of a star-polydimethylaminoethyl polyacrylate polymer according to one embodiment of the present invention;
FIG. 5 is a water contact angle test chart of a hydrophilic modified PVDF membrane of star-polydimethylaminoethyl acrylate polymer, according to one embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, are not to be construed as limiting the present invention.
Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include at least one of the feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In a first aspect of the invention, the invention provides a PVDF membrane. According to an embodiment of the invention, the PVDF membrane is formed from PVDF modified with a star-polydimethylaminoethyl acrylate polymer having the structure shown in formula I,
wherein R is
n is a positive integer of 15 to 105.
According to an embodiment of the invention, with reference to fig. 1 and 2, the PVDF membrane described above comprises hollow regions. Therefore, the surface of the membrane has certain gaps, and the operation of adsorbing the monolayer cell membrane is more convenient. In some embodiments of the invention, the PVDF membrane is circular (as shown in fig. 2).
In a second aspect of the invention, the invention provides a star-poly (dimethylaminoethyl acrylate) polymer. According to an embodiment of the present invention, the star-poly (dimethylaminoethyl acrylate) polymer has a structure shown in formula I,
wherein R is
n is a positive integer of 15 to 105.
The polymerization degree of the star-poly (dimethylaminoethyl acrylate) polymer is between 100 and 400, and the molecular weight of the star-poly (dimethylaminoethyl acrylate) polymer is between 10,000 and 60,000 daltons. The inventor finds that the long alkyl chain in the star-poly (dimethylaminoethyl acrylate) polymer has hydrophobicity and good compatibility with PVDF; the dimethylaminoethyl acrylate chain segment has high hydrophilicity, the star structure also helps the star-polydimethylaminoethyl acrylate polymer to be firmly fixed on the matrix membrane, and the hydrophilicity is improved, and the stability of the combination of the modifier and the PVDF membrane is also improved. Therefore, the star-polydimethylaminoethyl acrylate polymer hydrophilic modified PVDF membrane has higher hydrophilicity, permeability and dirt resistance, and still has higher recovery performance after being used for a plurality of times and for a long time.
In a third aspect of the invention, the invention provides a method of making the star-poly (dimethylaminoethyl acrylate) polymer of the above example. According to an embodiment of the invention, the method comprises: polymerizing dimethylaminoethyl acrylate and four-branched-chain 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid to obtain the star-poly (dimethylaminoethyl acrylate) polymer; wherein the four-branched-chain 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid has a structure shown in a formula II,
According to the embodiment of the invention, the molar ratio of the dimethylaminoethyl acrylate to the four-branched 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid is (60-420): 1. By controlling the ratio of the two, the degree of polymerization of the polymer produced can be controlled.
According to an embodiment of the present invention, the above polymerization is a reversible addition-fragmentation chain transfer polymerization and is carried out under the following conditions: an inert atmosphere; azodiisobutyronitrile is used as an initiator; dissolving dimethylaminoethyl acrylate and four-branched-chain 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid in 2-butanone; the reaction temperature is 70-120 ℃; and the reaction time is 4-20 h. Specifically, the polymerization reaction can be carried out according to the following method: dissolving a certain amount of dimethylaminoethyl acrylate, four-branched-chain 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid and an initiator azobisisobutyronitrile into 2-butanone, removing oxygen in a reaction vessel by adopting a freezing-degassing-unfreezing method, and injecting nitrogen or argon as a protective gas; and (3) placing the reaction container in a metal bath at the temperature of 70-120 ℃, and stirring for reaction for 4-20 hours to obtain a polymer product. The reaction temperature may be, for example, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or the like, and the reaction time may be 4 hours, 8 hours, 12 hours, 16 hours, 20 hours or the like.
Further, according to an embodiment of the present invention, a solution containing a polymer product may be dropped into hexane, and the product may be collected by a precipitation-precipitation method. The obtained product is treated by rotary evaporation, vacuum drying and the like to remove impurities and is dried to constant weight.
In a fourth aspect of the invention, a casting solution for forming a modified PVDF membrane is presented. According to an embodiment of the invention, the casting solution comprises: 10-20 v% PVDF; 0.1-5 v% of pore-foaming agent; 0.1-15 v% of the star-polydimethylaminoethyl acrylate polymer; and the balance solvent.
Specifically, in the casting solution, the content of PVDF may be 10 v%, 11 v%, 12 v%, 13 v%, 14 v%, 15 v%, 16 v%, 17 v%, 18 v%, 19 v%, 20 v%, etc., the content of the porogen may be 0.1 v%, 0.5 v%, 1 v%, 2 v%, 3 v%, 5 v%, etc., and the content of the star-dimethylaminoethyl acrylate polymer may be 0.1 v%, 0.5 v%, 1 v%, 2 v%, 3 v%, 5 v%, 8 v%, 10 v%, 12 v%, 15 v%, etc. The inventor finds in research that if the content of PVDF in the casting solution is too low, the casting solution is difficult to form and fix in a solidification solution; if the content of PVDF is too high, the resulting modified PVDF membrane may be rendered less hydrophilic; if the content of the porogen is too low, the number of micropores on the final PVDF membrane is reduced, and the permeability is reduced; if the content of the pore-forming agent is too high, the pore diameter of finally formed micropores is too large, the distribution of the micropores is too dense, and the structural uniformity and the membrane surface structure of the modified PVDF membrane are influenced; if the content of the star-polydimethylaminoethyl acrylate polymer is too low, the proportion of hydrophilic polymers in the components can be changed, and finally the hydrophilicity of the modified PVDF membrane is reduced; if the content of the star-polydimethylaminoethyl acrylate polymer is too high, the casting solution may be difficult to fix and mold.
In addition, the specific kind of the solvent is not particularly limited, and those skilled in the art can select the solvent according to actual needs. According to some embodiments of the present invention, the solvent may be at least one selected from the group consisting of dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide.
According to the embodiment of the invention, the casting solution is obtained by the following steps: and stirring and reacting the raw materials of the casting solution in a metal bath at 60-80 ℃ (preferably 70 ℃) for 10-15 h, and then placing the mixture in a vacuum oven for degassing. The temperature of the vacuum oven is not particularly limited, and for example, 50 ℃, 60 ℃, 70 ℃ or the like can be used.
In a fifth aspect of the invention, the invention proposes the use of the PVDF membrane of the above example in the preparation of a thin cell film. As described above, the PVDF membrane has excellent hydrophilicity, permeability, and stain resistance. For the monolayer cell membrane obtained by adherent culture, the monolayer cell membrane can be easily collected from the culture dish by using the PVDF membrane so as to be convenient for subsequent application.
In a sixth aspect of the invention, a method of making a thin film of cells is presented. According to an embodiment of the invention, the method comprises: carrying out adherent culture on the cells in a culture dish so as to form a monolayer cell film; the monolayer cell film is positioned in the stripping solution so as to change the bonding force between the monolayer cell film and the culture dish and separate the monolayer cell film from the culture dish; and removing the monolayer cell membrane from the culture dish using the PVDF membrane of the above example.
The specific method of exposing the monolayer cell film to the stripping solution to change the binding force between the monolayer cell film and the culture dish is not particularly limited. For example, a monolayer cell membrane can be peeled off using a peeling solution having a lower concentration of calcium ions and/or magnesium ions than the liquid medium.
The method for producing a cell membrane according to the present invention is not particularly limited with respect to the specific type of cells, and may be, for example, at least one selected from stem cells, neuronal cells, astrocytes, oligodendrocytes, epithelial cells, endothelial cells, muscle cells, and fibroblasts. Specifically, the stem cell includes at least one of an induced pluripotent stem cell, an adult stem cell, a mesenchymal stem cell, a neural stem cell, a cardiac stem cell and a lung stem cell; the mesenchymal stem cells comprise at least one of bone marrow-derived mesenchymal stem cells, adipose-derived mesenchymal stem cells and umbilical cord-derived mesenchymal stem cells; the epithelial cells include at least one of corneal epithelial cells, prostate epithelial cells, renal tubular epithelial cells, and coronary artery cells; the endothelial cells comprise at least one of endothelial cells of arteries, pulmonary artery and aorta; the muscle cells comprise at least one of aortic smooth muscle cells, pulmonary smooth muscle cells, and coronary smooth muscle cells; the fibroblast includes at least one of myocardial fibroblast, skin fibroblast and renal interstitial fibroblast. Preferably, the above cells are mesenchymal stem cells.
According to an embodiment of the present invention, the stripping solution is preferably a buffer solution containing no calcium ion or magnesium ion. Therefore, the stripping solution has better effect of reducing the binding force between the cell membrane and the culture dish. More preferably, the buffer solution without calcium ions and magnesium ions has a pH of 6.9 to 7.4, and for example, a commercially available DPBS buffer solution can be used.
Further, according to an embodiment of the present invention, the method for preparing a cell membrane may further include: and (3) superposing a plurality of monolayer cell films so as to obtain a composite cell film. Specifically, for example, 2 single-layer cell films are stacked, 2 single-layer cell films may be collected by using 2 PVDF films, and then the 2 PVDF films are bonded in a direction in which the cell film surfaces are opposite to each other, so as to obtain the stacked 2 single-layer cell films.
According to the embodiment of the invention, the prepared composite cell film can comprise 2-3 layers of cell films. Thereby, a better therapeutic effect can be obtained.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
Dissolving 36mg of azobisisobutyronitrile, 4.0g of dimethylaminoethyl acrylate and 0.4g of four-branched-chain 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid in 16mL of 2-butanone, removing oxygen in a reaction container by adopting a freezing-degassing-unfreezing method, injecting nitrogen as a protective gas, and placing on a metal bath at 70 ℃ to stir for reaction for 4 hours; dropping the obtained polymer solution into hexane, collecting the product by precipitation-precipitation method, removing impurities from the obtained product by rotary evaporation, vacuum drying and other steps, and drying to constant weight to obtain star-shaped poly (dimethylaminoethyl acrylate) polymer, wherein the nuclear magnetic resonance hydrogen spectrum of the star-shaped poly (dimethylaminoethyl acrylate) polymer is shown in figure 3, and the SEM spectrum is shown in figure 4.
50g of PVDF, 2g of PVP, 2.7g of star-shaped-poly (dimethylaminoethyl acrylate) polymer and a proper amount of DMF are added into a reaction vessel, stirred and reacted for 12 hours in a metal bath at 70 ℃, and then placed into a vacuum oven at 60 ℃ for degassing for 8 hours to obtain a casting solution. The PVDF flat membrane is prepared by adopting a solvent induced phase separation method, water is used as a coagulating bath, the temperature is room temperature, the membrane casting solution is poured on a clean glass plate, an automatic membrane scraping machine is used for scraping the membrane, and the scraper thickness is 150 mu m. And (3) exposing the scraped membrane in air for 30s, putting the membrane into a coagulating bath until the membrane falls off on a glass plate, soaking the prepared membranes (M-0, M-1, M-2, M-3 and M-4) in distilled water, and changing water every 12h to remove residual solvent and pore-forming agent in the membrane to obtain a star-polydimethylaminoethyl acrylate polymer hydrophilic modified PVDF membrane product.
The prepared product was subjected to a water contact angle test, and the results are shown in fig. 5. It can be seen that compared to the control sample with 0% star-polydimethylaminoethyl acrylate, PVDF membranes prepared with 5% and 10% star-polydimethylaminoethyl acrylate significantly decreased water contact angle and increased hydrophilicity.
Example 2
Dissolving 18mg of azobisisobutyronitrile, 4.0g of dimethylaminoethyl acrylate and 0.22g of four-branched-chain 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid in 16mL of 2-butanone, removing oxygen in a reaction container by adopting a freezing-degassing-unfreezing method, injecting nitrogen as a protective gas, and placing on a metal bath at 70 ℃ to stir for 20 hours; and dripping the obtained polymer solution into hexane, collecting a product by a precipitation-precipitation method, removing impurities of the obtained product by the steps of rotary evaporation, vacuum drying and the like, and drying to constant weight to obtain the star-poly (dimethylaminoethyl acrylate) polymer.
50g of PVDF, 2g of PVP, 5.8g of star-shaped-poly (dimethylaminoethyl acrylate) polymer and a proper amount of DMF are taken and added into a reaction vessel, stirred and reacted for 12 hours in a metal bath at 70 ℃, and then placed into a vacuum oven at 60 ℃ for degassing for 8 hours to obtain a casting solution. The PVDF flat membrane is prepared by adopting a solvent induced phase separation method, water is used as a coagulating bath, the temperature is room temperature, the membrane casting solution is poured on a clean glass plate, an automatic membrane scraping machine is used for scraping the membrane, and the scraper thickness is 150 mu m. And (3) exposing the scraped membrane in air for 30s, putting the scraped membrane into a coagulating bath until the scraped membrane falls off on a glass plate, soaking the prepared membrane (M-0, M-1, M-2, M-3 and M-4) in distilled water, and changing water every 12h to remove residual solvent and pore-forming agent in the membrane to obtain a star-poly (dimethylaminoethyl acrylate) polymer hydrophilic modified PVDF membrane product.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (17)
1. A PVDF membrane, wherein the PVDF membrane is formed from a PVDF modified with a star-polydimethylaminoethyl acrylate polymer having the structure of formula I,
wherein R is
n is a positive integer of 15 to 105.
2. The PVDF membrane of claim 1, wherein the PDVF membrane comprises hollow regions.
3. The PVDF membrane of claim 2, wherein the PVDF membrane is circular.
4. A star-poly (dimethylaminoethyl acrylate) polymer is characterized in that the polymer has a structure shown in a formula I,
wherein R is
n is a positive integer of 15 to 105.
5. A method of making the star-poly (dimethylaminoethyl acrylate) polymer of claim 4, comprising:
polymerizing dimethylaminoethyl acrylate and four-branched-chain 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid to obtain the star-poly (dimethylaminoethyl acrylate) polymer; wherein the four-branched-chain 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid has a structure shown in a formula II,
6. The method of claim 5, wherein the molar ratio of dimethylaminoethyl acrylate to the tetra-branched 2- (dodecyltrithiocarbonate) -2-methylpropionic acid is (60-420): 1.
7. The method according to claim 5, wherein the polymerization is a reversible addition-fragmentation chain transfer polymerization and is carried out under the following conditions:
an inert atmosphere;
azodiisobutyronitrile is used as an initiator;
dissolving the dimethylaminoethyl acrylate and the four-branched-chain 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid in 2-butanone;
the reaction temperature is 70-120 ℃; and
the reaction time is 4-20 h.
8. The casting solution for forming the modified PVDF membrane is characterized by comprising the following raw materials:
10-20 v% PVDF;
0.1-5 v% of pore-foaming agent;
0.1 to 15% v/v of the star-polydimethylaminoethyl acrylate polymer of claim 4; and
the balance of solvent.
9. The casting solution according to claim 8, wherein the solvent is selected from at least one of dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide.
10. The casting solution according to claim 8, characterized in that it is obtained by the following steps: stirring the raw materials in a metal bath at the temperature of 60-80 ℃ for reaction for 10-15 h, and then placing the raw materials in a vacuum oven for degassing.
11. Use of the PVDF membrane as defined in any one of claims 1 to 3 for the preparation of a thin cell film.
12. A method of preparing a thin film of cells, comprising:
carrying out adherent culture on the cells in a culture dish so as to form a monolayer cell film;
the monolayer cell film is in stripping liquid so as to change the bonding force between the monolayer cell film and the culture dish and enable the monolayer cell film to be separated from the culture dish; and
removing the monolayer cell thin film from the culture dish using the PVDF membrane according to any one of claims 1 to 3.
13. The method of claim 12, wherein the cells comprise at least one selected from stem cells, neuronal cells, astrocytes, oligodendrocytes, epithelial cells, endothelial cells, muscle cells, fibroblasts;
optionally, the stem cells include at least one of induced pluripotent stem cells, adult stem cells, mesenchymal stem cells, neural stem cells, cardiac stem cells, and lung stem cells;
optionally, the mesenchymal stem cells comprise at least one of bone marrow-derived mesenchymal stem cells, adipose-derived mesenchymal stem cells, umbilical cord-derived mesenchymal stem cells;
optionally, the epithelial cells include at least one of corneal epithelial cells, prostate epithelial cells, renal tubular epithelial cells, coronary artery cells;
optionally, the endothelial cells comprise at least one of vascular endothelial cells, pulmonary artery endothelial cells, aortic endothelial cells;
optionally, the muscle cells comprise at least one of aortic smooth muscle cells, pulmonary smooth muscle cells, coronary smooth muscle cells;
optionally, the fibroblasts include at least one of cardiac fibroblasts, skin fibroblasts, renal interstitial fibroblasts.
14. The method according to claim 12, wherein the stripping solution is a buffer solution containing no calcium ions and no magnesium ions.
15. The method according to claim 14, wherein the buffer has a pH of 6.9 to 7.4, preferably wherein the buffer is DPBS.
16. The method of claim 12, further comprising: and superposing a plurality of the monolayer cell films so as to obtain a composite cell film.
17. The method of claim 16, wherein the composite cell membrane comprises 2-3 layers of cell membranes.
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