CN116041773B - Micro-nano-scale strong three-dimensional interpenetrating network polyvinylidene fluoride hydrophobic membrane and preparation method thereof - Google Patents
Micro-nano-scale strong three-dimensional interpenetrating network polyvinylidene fluoride hydrophobic membrane and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 46
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 43
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 43
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000005266 casting Methods 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007493 shaping process Methods 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000003607 modifier Substances 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 229920002959 polymer blend Polymers 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000013329 compounding Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000007790 scraping Methods 0.000 claims description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000005543 nano-size silicon particle Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 229910002011 hydrophilic fumed silica Inorganic materials 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- -1 polydimethylsiloxane Polymers 0.000 claims description 3
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 238000005345 coagulation Methods 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000230 xanthan gum Substances 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 235000010493 xanthan gum Nutrition 0.000 claims description 2
- 229940082509 xanthan gum Drugs 0.000 claims description 2
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims 1
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 24
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 238000002145 thermally induced phase separation Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001054 cortical effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 210000001595 mastoid Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- 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
- C08J9/0014—Use of organic additives
- C08J9/0033—Use of organic additives containing sulfur
-
- 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
- C08J9/0014—Use of organic additives
- C08J9/0042—Use of organic additives containing silicon
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- C08J9/009—Use of pretreated compounding ingredients
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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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0422—Elimination of an organic solid phase containing oxygen atoms, e.g. saccharose
-
- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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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
- C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a micro-nano scale strong three-dimensional interpenetrating network polyvinylidene fluoride hydrophobic membrane and a preparation method thereof, belonging to the field of film modification. The preparation method adopts the following formula and process in percentage by mass: the formula is as follows: polyvinylidene fluoride: 4% -8%; pore-forming agent: the total concentration is 5-10%, and the compounding ratio is 1:3-2:1; dispersion stabilizer: 0.5% -5%; blend polymer: 0.3 to 1.1 percent; pore-forming shaping agent: the total concentration is 0.04 to 0.06 percent, and the compounding ratio is 1:1 to 1:2; hydrophobic modifier: 0.3 to 0.9 percent. The preparation method of the invention is approximately as follows; PVDF, a pore-forming agent, a dispersion stabilizer, a polymer blend, a pore-forming regulator and a hydrophobic modifier are uniformly dispersed in an organic solvent by a solution blending method to form a casting solution, and a film is scraped on the section of a core and is subjected to aftertreatment to obtain the strong three-dimensional interpenetrating network polyvinylidene fluoride hydrophobic film with micro-nano scale, which has a multi-level pore structure and can be used in the field of gas-water separation.
Description
Technical Field
The invention relates to a micro-nano scale strong three-dimensional interpenetrating network polyvinylidene fluoride hydrophobic membrane and a preparation method thereof, belonging to the field of film modification.
Background
Polyvinylidene fluoride (PVDF) is a semi-crystalline polymer, with crystalline phases providing mechanical strength and impact resistance, while amorphous phases provide flexibility, high molecular chain regularity, and close inter-chain alignment. The prepared PVDF film has higher mechanical strength, good chemical stability and thermal stability, is very stable when encountering corrosive chemical substances and organic compounds (including acid and oxidant), and is widely applied to preparing porous film materials in industry.
At present, the PVDF membrane is mostly applied in the fields of water treatment, gas phase separation, medical engineering and the like, and the modification research is mostly conducted to enhance the hydrophilic direction of the PVDF membrane. However, for the gas-liquid (water) separation process, the liquid (water) phase is prevented from passing through the membrane, and the hydrophobicity thereof is necessarily required. In addition, porous membranes are a better choice in order to reduce gas mass transfer resistance.
Methods for preparing the PVDF porous membrane can be classified into a non-solvent induced phase separation method (NIPS) and a thermally induced phase separation method (TIPS). However, for the NIPS method solvent, although the processing temperature is low and the porosity is high, the pore size distribution of the prepared membrane is wider, and cavities are easy to generate in the membrane, so that the membrane is easy to break; the PVDF membrane obtained by the TIPS method has narrow pore size distribution, but needs to be heated to above the melting temperature of the polymer in the whole processing process, has high requirements on experimental equipment and devices, and increases energy consumption. Thus, the NIPS method was selected to prepare the PVDF porous membrane.
When the NIPS method is used for preparing the porous membrane, the residual of the common pore-forming agent in the phase conversion process can increase the hydrophilicity of the polyvinylidene fluoride membrane, and the pore-forming shaping agent is easy to agglomerate to cause unstable membrane casting liquid or sedimentation to cause uneven distribution in the membrane casting liquid, thereby influencing the morphology, microstructure and performance of the membrane. Thus, the membrane hydrophobicity is enhanced with a hydrophobic modifier; forming a three-dimensional interpenetrating network structure by using a pore-forming modifier; the dispersion stabilizer is used for improving the dispersibility and stability of the pore-forming shaping agent in the blending solution, preventing agglomeration and precipitation, and further being beneficial to forming a multistage pore structure. Meanwhile, the three-dimensional interpenetrating network structure connecting sites and connecting strength among the micro-nano scale holes are enhanced by utilizing the blending polymer.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: in the prior art, when the polyvinylidene fluoride porous membrane is prepared by using the NIPS method, the problems of large pore diameter, easiness in generating cavities, weak inter-pore connection and strong hydrophilicity of the prepared PVDF porous membrane exist.
In order to solve the technical problem, the invention discloses a micro-nano-scale strong three-dimensional interpenetrating network polyvinylidene fluoride hydrophobic membrane.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The invention provides a method for preparing the micro-nano-scale reticular strong three-dimensional interpenetrating hierarchical porous hydrophobic polyvinylidene fluoride membrane, which comprises the following steps of, by mass, 4% -8% of polyvinylidene fluoride, wherein the weight percentage of the polyvinylidene fluoride is taken as an organic solvent by each raw material; the pore-forming agent with the total concentration of 5-10 percent is compounded in a ratio of 1:3-2:1; 0.5% -5% of dispersion stabilizer; 0.3 to 1.1 percent of polymer blend; pore-forming shaping agent with total concentration of 0.04% -0.06% and compounding ratio of 1:1-1:2; 0.3 to 0.9 percent of hydrophobic modifier and the balance of organic solvent.
(1) Adding polyvinylidene fluoride and a pore-forming agent into an organic solvent, stirring and keeping the temperature of the system at 50-120 ℃;
Wherein the organic solvent is selected from N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetone, tetrahydrofuran, or a combination of any two of the foregoing solvents;
the pore-forming agent is polyvinylpyrrolidone and polyethylene glycol;
(2) Stirring and ultrasonically dispersing the pore-forming shaping agent into the solution obtained in the step (1), and keeping the temperature of the system at 50-120 ℃; the pore-forming shaping agent is selected from any two combinations of nano silicon dioxide, nano zinc oxide and polydimethyl siloxane modified HL-200 hydrophilic fumed silica;
(3) Sequentially adding the polymer blend, the dispersion stabilizer and the hydrophobic modifier into the solution obtained in the step (2), fully stirring, and maintaining the system temperature at 30-120 ℃ after dissolution to obtain uniform casting solution;
the polymer blend is selected from one of phenolic resin, N' -methylene bisacrylamide and xanthan gum; the dispersion stabilizer is one selected from polyacrylamide, polyvinylpyrrolidone, hydroxypropyl cellulose and cellulose acetate;
(4) Standing and defoaming the casting film liquid obtained in the step (3) in a laboratory environment;
(5) Scraping the membrane of the defoamed membrane casting solution at the temperature of 20-40 ℃;
(6) After scraping the membrane, immersing the membrane into deionized water coagulation bath to form the micro-nano-scale net-shaped strong three-dimensional interpenetrating hierarchical porous hydrophobic polyvinylidene fluoride membrane.
The invention provides a micro-nano scale strong three-dimensional interpenetrating network polyvinylidene fluoride hydrophobic membrane and a preparation method thereof, and has the advantages that: the pore-forming agent and the pore-forming shaping agent are matched with each other to obtain a porous membrane with the aperture of micro-nano scale; the blend polymer is utilized to enhance the bonding strength between holes and further reduce the generation of cavities in the film forming process; the dispersion stability of the pore-forming shaping agent in the blending solution is improved by using a dispersion stabilizer, and the agglomeration or sedimentation phenomenon is prevented; the hydrophobicity of the PVDF porous membrane is enhanced by a hydrophobic modifier. The research result not only can develop a novel modification technology of the polymer membrane and promote the development of a novel membrane separation material, but also can widen the application of the separation membrane in the field of gas-water separation and promote the reasonable and efficient development of natural gas.
Drawings
FIG. 1 is an SEM image of PVDF-1 of the comparative example.
FIG. 2 is an SEM image of PVDF-2 of the comparative example.
FIG. 3 is an SEM image of PVDF-3 of the comparative example.
FIG. 4 is an SEM image of PVDF-4 in the examples.
FIG. 5 is an SEM image of PVDF-5 in the examples.
FIG. 6 is an SEM image of PVDF-6 in the examples.
FIG. 7 is an SEM image of PVDF-7 of the examples
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
Comparative example 1
50G of N, N-dimethylacetamide (DMAc) organic solvent, heating the mixture to 80 ℃ in an oil bath, adding 2.5g of polyvinylidene fluoride and 2.5g of polyethylene glycol, fully stirring the mixture, keeping the temperature of the mixture at 80 ℃, and strongly stirring the mixture for 4 hours to form a uniform casting solution, standing the casting solution at normal temperature and normal pressure for 6 hours, defoamating the casting solution, scraping the casting solution, carrying out phase inversion in deionized water at 40 ℃ after scraping the casting solution, and balancing the casting solution for 48 hours to form the PVDF-1.
FIG. 1 is a plan view of PVDF-1.
Comparative example 2
50G of N, N-dimethylacetamide (DMAc) organic solvent, heating the mixture to 80 ℃ in an oil bath, adding 2.5g of polyvinylidene fluoride, 2.5g of polyethylene glycol and 0.01g of nano silicon dioxide, stirring the mixture fully after ultrasonic dispersion, keeping the temperature of the mixture at 80 ℃, stirring the mixture strongly for 4 hours to form a uniform casting solution, standing the casting solution at normal temperature and normal pressure for 6 hours, defoaming, scraping the film, carrying out phase inversion in deionized water at 40 ℃ after scraping the film, balancing the film, and recording the film as PVDF-2.
FIG. 2 is a PVDF-2 planar scanning electron microscope image.
Compared with PVDF-1 and PVDF-2 scanning electron microscope images, the addition of pore-forming plastic agent nano silicon dioxide enables the mastoid structure to be converted into a through three-dimensional interpenetrating structure when only pore-forming agent polyethylene glycol exists, but the bonding strength among pores is low, and more cavities are formed.
Comparative example 3
50G of N, N-dimethylacetamide (DMAc) organic solvent, heating the mixture to 80 ℃ in an oil bath, adding 2.5g of polyvinylidene fluoride, 2.5g of polyethylene glycol and 0.01g of nano silicon dioxide, fully stirring the mixture after ultrasonic dispersion, adding 1.25g of dispersion stabilizer polyvinylpyrrolidone, keeping the temperature of the mixture at 80 ℃, and strongly stirring the mixture for 4 hours to form uniform casting solution, standing the casting solution at normal temperature and normal pressure for 6 hours for deaeration, scraping the film, carrying out phase inversion in deionized water at 40 ℃ after scraping the film, balancing the film for 48 hours, and recording as PVDF-3.
FIG. 3 is a plan view of PVDF-3.
Comparing PVDF-2 and PVDF-3 scanning electron microscope images, the cavity is reduced after adding dispersion stabilizer, but the average pore diameter is increased (41.969 um can be reached), and the porosity is reduced.
Example 1
50G of N, N-dimethylacetamide (DMAc) organic solvent, heating the mixture to 80 ℃ in an oil bath, adding 2.5g of polyvinylidene fluoride, 2.5g of polyethylene glycol and 0.01g of nano silicon dioxide, fully stirring the mixture after ultrasonic dispersion, adding 0.25g of polymer N, N' -methylene bisacrylamide blend, keeping the temperature of the mixture at 80 ℃, and strongly stirring the mixture for 4 hours to form uniform casting solution, standing the uniform casting solution at normal temperature and normal pressure for 6 hours, scraping the film after deaeration, carrying out phase inversion in deionized water at 40 ℃ after scraping the film, and balancing the film to form the film, namely PVDF-4.
FIG. 4 is a plan view of PVDF-4.
And compared with PVDF-2 and PVDF-4 scanning electron microscope images, the addition of the polymer blend increases the connecting sites between the through three-dimensional interpenetrating structures, and the cavities under the same scale are obviously reduced.
Example 2
50G of N, N-dimethylacetamide (DMAc) organic solvent, heating to 80 ℃ in an oil bath, adding 2.5g of polyvinylidene fluoride, 2.5g of polyethylene glycol and 1g of polyvinylpyrrolidone, fully stirring, adding 0.01g of nano silicon dioxide and 0.01g of nano zinc oxide, uniformly dispersing by ultrasonic, adding 0.25g of polymer N, N' -methylene bisacrylamide and 0.25g of dispersion stabilizer polyvinylpyrrolidone, keeping the temperature of the mixed solution at 80 ℃, strongly stirring for 4 hours to form uniform casting solution, standing for 6 hours at normal temperature and normal pressure, scraping the film, carrying out phase inversion in deionized water at 40 ℃ after scraping the film, balancing for 48 hours, and obtaining PVDF-5.
FIG. 5 is a PVDF-5 planar scanning electron microscope image.
Compared with PVDF-3, the pore-forming shaping agent nano zinc oxide in PVDF-5 is added, so that the average pore diameter of the membrane is greatly reduced on the basis of improving the porosity, and the average pore diameter is reduced to 0.159um.
Example 3
50G of N, N-dimethylacetamide (DMAc) organic solvent, heating the mixture to 80 ℃ in an oil bath, adding 2.5g of polyvinylidene fluoride, 2.5g of polyethylene glycol and 1g of polyvinylpyrrolidone, fully stirring, adding 0.01g of nano silicon dioxide and 0.01g of polydimethylsiloxane modified HL-200 hydrophilic fumed silica, uniformly dispersing the mixture by ultrasonic, adding 0.25g of polymer N, N' -methylenebisacrylamide, 0.25g of dispersion stabilizer polyvinylpyrrolidone and 0.25g of potassium perfluorobutyl sulfonate, keeping the temperature of the mixture at 80 ℃, strongly stirring for 4 hours to form uniform casting film liquid, scraping the film after standing for 6 hours at normal temperature and normal pressure, carrying out phase inversion in deionized water at 40 ℃ after the film scraping, balancing for 48 hours, and recording as PVDF-6.
FIG. 6 is a PVDF-6 scanning electron microscope image.
Example 4
50G of N, N-dimethylacetamide (DMAc) organic solvent, heating the mixture to 80 ℃ in an oil bath, adding 2.5g of polyvinylidene fluoride, 2.5g of polyethylene glycol and 1g of polyvinylpyrrolidone, fully stirring, adding 0.01g of nano silicon dioxide and 0.02g of nano zinc oxide, uniformly dispersing by ultrasonic, adding 0.25g of polymer N, N' -methylene bisacrylamide, 0.25g of dispersion stabilizer polyvinylpyrrolidone and 0.45g of potassium perfluorobutyl sulfonate, keeping the temperature of the mixture at 80 ℃, strongly stirring for 4 hours to form uniform casting film liquid, standing for 6 hours at normal temperature and normal pressure, defoaming, scraping the film, carrying out phase conversion in deionized water at 40 ℃ after scraping the film, balancing for 48 hours, and recording as PVDF-7.
FIG. 7 is a view of a PVDF-7 scanning electron microscope, in which a hierarchical pore structure is formed in a plane, in which the cortical layer is not evident in a natural cross section, and a three-dimensional interpenetrating network structure is also formed.
The water-in-air contact angles of the film samples obtained in examples 2 to 4 were measured, and the measurement results obtained by taking the contact angles at three different positions and taking the average value are shown in Table 1.
Table 1 each set of membrane-like air water contact horns.
TABLE 1 Water in air contact angles for each group of film samples
Claims (5)
1. The utility model provides a strong three-dimensional interpenetrating network polyvinylidene fluoride hydrophobic membrane of micro-nano scale which characterized in that: the micro-nano scale strong three-dimensional interpenetrating network and multistage pore structure of the polyvinylidene fluoride separation membrane is obtained by the combined action of a pore-forming agent, a dispersion stabilizer, a blending polymer and a pore-forming regulator; the hydrophobicity of the polyvinylidene fluoride separation membrane is obtained by the action of a hydrophobic modifier; according to the mass percent of the organic solvent occupied by each raw material, 4% -8% of polyvinylidene fluoride; the pore-forming agent with the total concentration of 5-10 percent is selected from polyvinylpyrrolidone and polyethylene glycol according to the compounding ratio of 1:3-2:1; 0.5% -5% of dispersion stabilizer; 0.3 to 1.1 percent of polymer blend selected from one of phenolic resin, N' -methylene bisacrylamide and xanthan gum; pore-forming shaping agent with total concentration of 0.04% -0.06%, and compounding ratio of 1:1-1:2, wherein the pore-forming shaping agent is selected from nano silicon dioxide and nano zinc oxide or nano silicon dioxide and polydimethylsiloxane modified HL-200 hydrophilic fumed silica; the balance of organic solvent.
2. A strong three-dimensional interpenetrating network polyvinylidene fluoride hydrophobic membrane according to claim 1, characterized in that: the organic solvent is selected from N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetone, tetrahydrofuran, or a combination of any two of the above solvents.
3. A strong three-dimensional interpenetrating network polyvinylidene fluoride hydrophobic membrane according to claim 1, characterized in that: the dispersion stabilizer is one selected from polyacrylamide, polyvinylpyrrolidone, hydroxypropyl cellulose and cellulose acetate.
4. A strong three-dimensional interpenetrating network polyvinylidene fluoride hydrophobic membrane according to claim 1, characterized in that: the hydrophobic modifier is one of potassium perfluorobutyl sulfonate and perfluorooctyl triethoxysilane.
5. A method for preparing a strong three-dimensional interpenetrating network polyvinylidene fluoride hydrophobic film with micro-nano scale as set forth in claim 1, which comprises the following steps:
(1) Adding polyvinylidene fluoride and a pore-forming agent into an organic solvent, stirring and keeping the temperature of the system at 50-120 ℃;
(2) Stirring and ultrasonically dispersing the pore-forming shaping agent into the solution obtained in the step (1), and keeping the temperature of the system at 50-120 ℃;
(3) Sequentially adding the polymer blend, the dispersion stabilizer and the hydrophobic modifier into the solution obtained in the step (2), fully stirring, and maintaining the system temperature at 30-120 ℃ after dissolution to obtain uniform casting solution;
(4) Standing and defoaming the casting film liquid obtained in the step (3) in a laboratory environment; scraping the membrane of the defoamed membrane casting solution at the temperature of 20-40 ℃; after scraping the membrane, immersing the membrane into deionized water coagulation bath to form a netlike multi-level porous polyvinylidene fluoride hydrophobic membrane with strong micro-nano scale three-dimensional interpenetrating.
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