CN116575184B - Preparation method of polytetrafluoroethylene nanofiber membrane - Google Patents
Preparation method of polytetrafluoroethylene nanofiber membrane Download PDFInfo
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- CN116575184B CN116575184B CN202310845582.2A CN202310845582A CN116575184B CN 116575184 B CN116575184 B CN 116575184B CN 202310845582 A CN202310845582 A CN 202310845582A CN 116575184 B CN116575184 B CN 116575184B
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 127
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 127
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 90
- 239000012528 membrane Substances 0.000 title claims abstract description 57
- 239000002121 nanofiber Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000839 emulsion Substances 0.000 claims abstract description 44
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 38
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 33
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000009987 spinning Methods 0.000 claims abstract description 17
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000009396 hybridization Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4318—Fluorine series
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
- D06C7/04—Carbonising or oxidising
Abstract
The invention belongs to the technical field of polytetrafluoroethylene membrane preparation, and particularly relates to a preparation method of a polytetrafluoroethylene nanofiber membrane. The preparation method comprises the following steps: (1) Preparation of PTFE/SiO 2 A hybrid material; (2) preparing modified nano tungsten disulfide; (3) PTFE/SiO 2 Uniformly mixing the hybrid material, the modified nano tungsten disulfide, the ethylene-tetrafluoroethylene copolymer, the polytetrafluoroethylene emulsion and the polyethylene oxide to prepare spinning solution; (4) And (3) placing the spinning solution into electrostatic spinning equipment for electrostatic spinning, and then performing heat treatment to obtain the polytetrafluoroethylene nanofiber membrane. According to the preparation method, polytetrafluoroethylene emulsion is used as a film forming polymer, polyethylene oxide is used as a spinning carrier, an electrostatic spinning process is adopted to prepare the polytetrafluoroethylene nanofiber film, and the prepared polytetrafluoroethylene nanofiber film has the advantages of few defects, excellent mechanical properties and high heat resistance.
Description
Technical Field
The invention belongs to the technical field of polytetrafluoroethylene membrane preparation, and particularly relates to a preparation method of a polytetrafluoroethylene nanofiber membrane.
Background
Polytetrafluoroethylene, commonly known as "plastic king", has a molecular structure unit of- [ CF 2 -CF 2 ]The polymer is a highly symmetrical perfluoro linear polymer which is formed by taking C-C as a main chain and replacing hydrogen atoms in polyethylene by fluorine atoms. Because of the molecular structure of polytetrafluoroethylene, the polytetrafluoroethylene has the following characteristics: excellent thermal stability, excellent aging resistance and corrosion resistance, surface non-tackiness and self-lubricity, molding and secondary processing difficulties. The porous polytetrafluoroethylene membrane prepared by taking polytetrafluoroethylene as a raw material has excellent chemical stability, high heat resistance, strong hydrophobicity and high fracture toughness, and the characteristics make the porous polytetrafluoroethylene membrane suitable for application in the fields of waste gas treatment, membrane distillation, osmotic distillation, oil-water separation and the like.
The polytetrafluoroethylene film is prepared by various methods, mainly comprising mechanical stretching, pore-forming agent forming process, spinning and the like; wherein, the mechanical stretching and pore-forming agent forming process has the defects of large pore diameter difference and low porosity of the prepared polytetrafluoroethylene membrane. Unlike traditional spinning technology, electrostatic spinning mainly relies on high voltage power supply to generate electrostatic field, so that polymer solution or melt is charged and deformed, and suspension cone-shaped liquid drops are formed at the tail end of a spinning needle; when the repulsive force of the charges on the surface of the liquid drop reaches a certain degree (exceeding the surface tension), the polymer fluid is sprayed at a very high speed and is simply referred to as 'jet'; the jet flow is continuously elongated, cracked and pulled into nano fibers, and simultaneously, the solvent in the polymer solution is volatilized or melt is cooled, and finally solidified on a fiber collection device to obtain the fiber. The fibers obtained by the electrostatic spinning technology generally have the diameter distribution of a few nanometers to a few micrometers, and the collected nanofibers can be collected according to the jet flow direction, so that the fibers can be regularly arranged and then mutually built to form the nanofiber membrane.
The majority of the polytetrafluoroethylene nanofiber membranes prepared by the electrostatic spinning method are pure polytetrafluoroethylene nanofiber membranes, the mechanical properties are poor, the application range of the polytetrafluoroethylene nanofiber membranes is greatly limited, therefore, modification treatment is necessary to the polytetrafluoroethylene nanofiber membranes, the properties of the polytetrafluoroethylene nanofiber membranes are improved, and the application fields of the polytetrafluoroethylene nanofiber membranes are widened.
Disclosure of Invention
The purpose of the invention is that: provides a preparation method of a polytetrafluoroethylene nanofiber membrane. The polytetrafluoroethylene nanofiber membrane prepared by the method has the characteristics of excellent mechanical property, few defects and good thermal stability.
The preparation method of the polytetrafluoroethylene nanofiber membrane provided by the invention comprises the following steps:
(1) Mixing silica sol and PTFE emulsion in 50-55deg.C water bath to obtain hybrid sol, drying the hybrid sol, crushing, and pulverizing to obtain PTFE/SiO 2 A hybrid material;
(2) Adding nano tungsten disulfide into a mixed solution consisting of gamma-aminopropyl triethoxysilane, absolute ethyl alcohol and water, performing ultrasonic dispersion for 33-35min, then dropwise adding acetic acid, adjusting the pH value of a reaction system to 5, reacting for 6.5-7h at 65-68 ℃, cooling to room temperature after the reaction is finished, centrifuging by a centrifugal machine, and drying in a vacuum drying oven to obtain modified nano tungsten disulfide;
(3) PTFE/SiO prepared in the step (1) is treated 2 Uniformly mixing the hybrid material, the modified nano tungsten disulfide, the ethylene-tetrafluoroethylene copolymer and the polytetrafluoroethylene emulsion prepared in the step (2) with a polyethylene oxide solution to prepare spinning solution;
(4) And (3) placing the spinning solution prepared in the step (3) into electrostatic spinning equipment for electrostatic spinning, and then performing heat treatment to prepare the polytetrafluoroethylene nanofiber membrane.
Wherein:
the mass ratio of the silica sol to the PTFE emulsion in the step (1) is 4.5:5.5.
Stirring and mixing for 2.5-3h in the step (1); the drying temperature is 85-88 ℃, and the drying time is 8.5-9h.
PTFE/SiO in step (1) 2 The particle size of the hybrid material was 250nm.
In the step (2), the mass ratio of the gamma-aminopropyl triethoxysilane to the absolute ethyl alcohol to the water is 20:72:8.
The mass of the gamma-aminopropyl triethoxysilane in the step (2) accounts for 3.0-3.2% of the total mass of the nano tungsten disulfide.
In the step (2), the centrifugal rotating speed is 3000r/min, the centrifugal time is 6-8min, and the centrifugal times are 3 times.
The drying time in the step (2) is 24-26h, and the drying temperature is 70-75 ℃.
PTFE/SiO in step (3) 2 The mass of the hybridization material accounts for 2.9-3.2% of the mass of the polytetrafluoroethylene emulsion; the mass of the modified nano tungsten disulfide accounts for 0.8-1.0% of the mass of the polytetrafluoroethylene emulsion; the mass of the ethylene-tetrafluoroethylene copolymer accounts for 1.8-2.2% of the mass of the polytetrafluoroethylene emulsion.
The mass concentration of the polyethylene oxide solution in the step (3) is 9%, and the solid content of the polytetrafluoroethylene emulsion is 60%.
In the step (3), polyethylene oxide solution is prepared by dissolving polyethylene oxide with the molecular weight of 300000g/mol in deionized water and stirring for 6.5h in a water bath environment at 50 ℃ to dissolve the polyethylene oxide.
The mass ratio of the polytetrafluoroethylene emulsion to the mass ratio of the polyethylene oxide solution is 1:0.90.
In the step (4), the electrostatic spinning voltage is 18-20KV, the advancing speed of the electrostatic spinning equipment is 0.55-0.60mL/h, and the distance between a spray head of the electrostatic spinning equipment and a collector of a roller of a counter electrode is 15-17cm.
And (3) the heat treatment in the step (4) is to dry the composite fiber membrane prepared by electrostatic spinning at 85-88 ℃ for 1.5-2h, and then sinter at 385-390 ℃ for 15-20min.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the polytetrafluoroethylene nanofiber membrane uses polytetrafluoroethylene emulsion as a film-forming polymer and polyethylene oxide as a spinning carrier, PTFE/SiO 2 The mixture of the hybrid material, the modified nano tungsten disulfide and ethylene-tetrafluoroethylene copolymer (ETFE) resin particles is used as a modifier, and the electrostatic spinning technology is adopted to prepare the polytetrafluoroethylene nanofiber membrane.
(2) The preparation method of the polytetrafluoroethylene nanofiber membrane prepares PTFE/SiO 2 The hybrid material is mixed in liquid state, so that the nano particles in the silica sol are wrapped by PTFE macromolecules in the stirring process, the surface characteristics of the nano particles are fully exerted, and the SiO is 2 The dispersion of the nano particles in PTFE is more uniform, and the prepared polytetrafluoroethylene nanofiber membrane is easier to uniformly disperse the load after heat treatment through electrostatic spinning; the wear resistance of the prepared polytetrafluoroethylene nanofiber membrane is improved by compounding the modified nano tungsten disulfide; the addition of ethylene-tetrafluoroethylene copolymer (ETFE) resin particles improves the tensile strength and weather resistance of the prepared polytetrafluoroethylene nanofiber membrane.
Detailed Description
The invention is further described below with reference to examples.
The PTFE emulsion used in the following examples and comparative examples had a solids content of 60% and a pH of 9 and was manufactured by Teflon PTFE TE3893 manufactured by DuPont, U.S.A.; siO in silica sol 2 The mass content of (2) is 30%, the pH value is 10, and the manufacturer is SS3015 produced by Yi Zhi Xuan New Material Co.
Example 1
The preparation method of the polytetrafluoroethylene nanofiber membrane of the embodiment 1 comprises the following steps:
(1) Mixing silica sol and PTFE emulsion in water bath at 53 deg.c to obtain hybridized sol, drying the hybridized sol, crushing, and final crushing to obtain PTFE/SiO 2 A hybrid material;
(2) Adding nano tungsten disulfide into a mixed solution consisting of gamma-aminopropyl triethoxysilane, absolute ethyl alcohol and water, performing ultrasonic dispersion for 34min, then dropwise adding acetic acid, adjusting the pH value of a reaction system to 5, reacting at 67 ℃ for 6.7h, cooling to room temperature after the reaction is finished, centrifuging by a centrifuge, and drying in a vacuum drying oven to obtain modified nano tungsten disulfide;
(3) PTFE/SiO prepared in the step (1) is treated 2 Uniformly mixing the hybrid material, the modified nano tungsten disulfide, the ethylene-tetrafluoroethylene copolymer and the polytetrafluoroethylene emulsion prepared in the step (2) with a polyethylene oxide solution to prepare spinning solution;
(4) And (3) placing the spinning solution prepared in the step (3) into electrostatic spinning equipment for electrostatic spinning, and then performing heat treatment to prepare the polytetrafluoroethylene nanofiber membrane.
Wherein:
the mass ratio of the silica sol to the PTFE emulsion in the step (1) is 4.5:5.5.
Stirring and mixing for 2.7 hours in the step (1); the drying temperature was 86℃and the drying time was 8.7h.
PTFE/SiO in step (1) 2 The particle size of the hybrid material was 250nm.
In the step (2), the mass ratio of the gamma-aminopropyl triethoxysilane to the absolute ethyl alcohol to the water is 20:72:8.
The mass of the gamma-aminopropyl triethoxysilane in the step (2) accounts for 3.1 percent of the total mass of the nano tungsten disulfide.
In the step (2), the centrifugal speed is 3000r/min, the centrifugal time is 7min, and the centrifugal times are 3 times.
The drying time in the step (2) was 25 hours and the drying temperature was 73 ℃.
PTFE/SiO in step (3) 2 The mass of the hybridization material accounts for 3.0% of the mass of the polytetrafluoroethylene emulsion; the mass of the modified nano tungsten disulfide accounts for 0.9% of the mass of the polytetrafluoroethylene emulsion; the mass of the ethylene-tetrafluoroethylene copolymer accounts for 2.0% of the mass of the polytetrafluoroethylene emulsion.
The mass concentration of the polyethylene oxide solution in the step (3) is 9%, and the solid content of the polytetrafluoroethylene emulsion is 60%.
In the step (3), polyethylene oxide solution is prepared by dissolving polyethylene oxide with the molecular weight of 300000g/mol in deionized water and stirring for 6.5h in a water bath environment at 50 ℃ to dissolve the polyethylene oxide.
The mass ratio of the polytetrafluoroethylene emulsion to the mass ratio of the polyethylene oxide solution is 1:0.90.
In the step (4), the electrostatic spinning voltage is 20KV, the advancing speed of the electrostatic spinning equipment is 0.60mL/h, and the distance between a spray head of the electrostatic spinning equipment and a collector of a roller of a counter electrode is 17cm.
The heat treatment in the step (4) is to dry the composite fiber membrane prepared by electrostatic spinning at 88 ℃ for 1.5 hours, and then sinter the composite fiber membrane at 390 ℃ for 20 minutes.
Example 2
The preparation method of the polytetrafluoroethylene nanofiber membrane of the embodiment 2 comprises the following steps:
(1) Mixing silica sol and PTFE emulsion in water bath at 50deg.C to obtain hybrid sol, drying the hybrid sol, crushing, and pulverizing to obtain PTFE/SiO 2 A hybrid material;
(2) Adding nano tungsten disulfide into a mixed solution consisting of gamma-aminopropyl triethoxysilane, absolute ethyl alcohol and water, performing ultrasonic dispersion for 33min, then dropwise adding acetic acid, adjusting the pH value of a reaction system to 5, reacting at 68 ℃ for 6.5h, cooling to room temperature after the reaction is finished, centrifuging by a centrifuge, and drying in a vacuum drying oven to obtain modified nano tungsten disulfide;
(3) PTFE/SiO prepared in the step (1) is treated 2 Uniformly mixing the hybrid material, the modified nano tungsten disulfide, the ethylene-tetrafluoroethylene copolymer and the polytetrafluoroethylene emulsion prepared in the step (2) with a polyethylene oxide solution to prepare spinning solution;
(4) And (3) placing the spinning solution prepared in the step (3) into electrostatic spinning equipment for electrostatic spinning, and then performing heat treatment to prepare the polytetrafluoroethylene nanofiber membrane.
Wherein:
the mass ratio of the silica sol to the PTFE emulsion in the step (1) is 4.5:5.5.
Stirring and mixing for 3 hours in the step (1); the drying temperature was 88℃and the drying time was 8.5h.
PTFE/SiO in step (1) 2 The particle size of the hybrid material was 250nm.
In the step (2), the mass ratio of the gamma-aminopropyl triethoxysilane to the absolute ethyl alcohol to the water is 20:72:8.
The mass of the gamma-aminopropyl triethoxysilane in the step (2) accounts for 3.0 percent of the total mass of the nano tungsten disulfide.
In the step (2), the centrifugal speed is 3000r/min, the centrifugal time is 6min, and the centrifugal times are 3 times.
The drying time in the step (2) is 24 hours, and the drying temperature is 75 ℃.
PTFE/SiO in step (3) 2 The mass of the hybridization material accounts for 3.2 percent of the mass of the polytetrafluoroethylene emulsion; the mass of the modified nano tungsten disulfide accounts for 0.8% of the mass of the polytetrafluoroethylene emulsion; the mass of the ethylene-tetrafluoroethylene copolymer accounts for 1.8% of the mass of the polytetrafluoroethylene emulsion.
The mass concentration of the polyethylene oxide solution in the step (3) is 9%, and the solid content of the polytetrafluoroethylene emulsion is 60%.
In the step (3), polyethylene oxide solution is prepared by dissolving polyethylene oxide with the molecular weight of 300000g/mol in deionized water and stirring for 6.5h in a water bath environment at 50 ℃ to dissolve the polyethylene oxide.
The mass ratio of the polytetrafluoroethylene emulsion to the mass ratio of the polyethylene oxide solution is 1:0.90.
In the step (4), the electrostatic spinning voltage is 18KV, the advancing speed of the electrostatic spinning equipment is 0.55mL/h, and the distance between a spray head of the electrostatic spinning equipment and a collector of a roller of a counter electrode is 15cm.
The heat treatment in the step (4) is to dry the composite fiber membrane prepared by electrostatic spinning at 86 ℃ for 1.7h, and then sinter at 388 ℃ for 15min.
Example 3
The preparation method of the polytetrafluoroethylene nanofiber membrane of the embodiment 3 comprises the following steps:
(1) Mixing silica sol and PTFE emulsion in a water bath environment at 55 ℃ to obtain hybrid sol, drying the hybrid sol, crushing, and finally crushing to obtain PTFE/SiO 2 A hybrid material;
(2) Adding nano tungsten disulfide into a mixed solution consisting of gamma-aminopropyl triethoxysilane, absolute ethyl alcohol and water, performing ultrasonic dispersion for 35min, then dropwise adding acetic acid, adjusting the pH value of a reaction system to 5, reacting for 7h at 65 ℃, cooling to room temperature after the reaction is finished, centrifuging by a centrifuge, and drying in a vacuum drying oven to obtain modified nano tungsten disulfide;
(3) PTFE/SiO prepared in the step (1) is treated 2 Uniformly mixing the hybrid material, the modified nano tungsten disulfide, the ethylene-tetrafluoroethylene copolymer and the polytetrafluoroethylene emulsion prepared in the step (2) with a polyethylene oxide solution to prepare spinning solution;
(4) And (3) placing the spinning solution prepared in the step (3) into electrostatic spinning equipment for electrostatic spinning, and then performing heat treatment to prepare the polytetrafluoroethylene nanofiber membrane.
Wherein:
the mass ratio of the silica sol to the PTFE emulsion in the step (1) is 4.5:5.5.
Stirring and mixing for 2.5 hours in the step (1); the drying temperature was 85℃and the drying time was 9 hours.
PTFE/SiO in step (1) 2 The particle size of the hybrid material was 250nm.
In the step (2), the mass ratio of the gamma-aminopropyl triethoxysilane to the absolute ethyl alcohol to the water is 20:72:8.
The mass of the gamma-aminopropyl triethoxysilane in the step (2) accounts for 3.2 percent of the total mass of the nano tungsten disulfide.
In the step (2), the centrifugal speed is 3000r/min, the centrifugal time is 8min, and the centrifugal times are 3 times.
The drying time in the step (2) is 26 hours, and the drying temperature is 70 ℃.
PTFE/SiO in step (3) 2 The mass of the hybridization material accounts for 2.9 percent of the mass of the polytetrafluoroethylene emulsion; the mass of the modified nano tungsten disulfide accounts for 1.0% of the mass of the polytetrafluoroethylene emulsion; the mass of the ethylene-tetrafluoroethylene copolymer is 2.2% of the mass of the polytetrafluoroethylene emulsion.
The mass concentration of the polyethylene oxide solution in the step (3) is 9%, and the solid content of the polytetrafluoroethylene emulsion is 60%.
In the step (3), polyethylene oxide solution is prepared by dissolving polyethylene oxide with the molecular weight of 300000g/mol in deionized water and stirring for 6.5h in a water bath environment at 50 ℃ to dissolve the polyethylene oxide.
The mass ratio of the polytetrafluoroethylene emulsion to the mass ratio of the polyethylene oxide solution is 1:0.90.
In the step (4), the electrostatic spinning voltage is 19KV, the advancing speed of the electrostatic spinning equipment is 0.57mL/h, and the distance between a spray head of the electrostatic spinning equipment and a collector of a roller of a counter electrode is 16cm.
The heat treatment in the step (4) is to dry the composite fiber membrane prepared by electrostatic spinning at 85 ℃ for 2 hours, and then sinter the composite fiber membrane at 385 ℃ for 17 minutes.
Comparative example 1
The preparation method of the polytetrafluoroethylene nanofiber membrane described in this comparative example 1 is the same as that of example 1, except that,PTFE/SiO is not added in the step (3) 2 A hybrid material.
Comparative example 2
The preparation method of the polytetrafluoroethylene nanofiber membrane according to the comparative example 2 is the same as that of example 1, except that modified nano tungsten disulfide is not added in the step (3).
Comparative example 3
The preparation method of the polytetrafluoroethylene nanofiber membrane according to this comparative example 3 is the same as that of example 1, except that the ethylene-tetrafluoroethylene copolymer is not added in step (3).
The polytetrafluoroethylene nanofiber membranes prepared in examples 1-3 and comparative examples 1-3 were subjected to performance testing, and the results are shown below:
TABLE 1 results of Performance test of Polytetrafluoroethylene nanofiber membranes of examples 1-3 and comparative examples 1-3
Claims (10)
1. A preparation method of a polytetrafluoroethylene nanofiber membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) Mixing silica sol and PTFE emulsion in 50-55deg.C water bath to obtain hybrid sol, drying the hybrid sol, crushing, and pulverizing to obtain PTFE/SiO 2 A hybrid material;
(2) Adding nano tungsten disulfide into a mixed solution consisting of gamma-aminopropyl triethoxysilane, absolute ethyl alcohol and water, performing ultrasonic dispersion for 33-35min, then dropwise adding acetic acid, adjusting the pH value of a reaction system to 5, reacting for 6.5-7h at 65-68 ℃, cooling to room temperature after the reaction is finished, centrifuging by a centrifugal machine, and drying in a vacuum drying oven to obtain modified nano tungsten disulfide;
(3) PTFE/SiO prepared in the step (1) is treated 2 Hybrid material, modified nano tungsten disulfide, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene emulsion and modified nano tungsten disulfide prepared in step (2)Uniformly mixing polyethylene oxide solution to prepare spinning solution;
(4) And (3) placing the spinning solution prepared in the step (3) into electrostatic spinning equipment for electrostatic spinning, and then performing heat treatment to prepare the polytetrafluoroethylene nanofiber membrane.
2. The method for preparing a polytetrafluoroethylene nanofiber membrane according to claim 1, wherein: stirring and mixing for 2.5-3h in the step (1); the drying temperature is 85-88 ℃, and the drying time is 8.5-9h.
3. The method for preparing a polytetrafluoroethylene nanofiber membrane according to claim 1, wherein: PTFE/SiO in step (1) 2 The particle size of the hybrid material is 250nm; the mass ratio of the silica sol to the PTFE emulsion in the step (1) is 4.5:5.5.
4. The method for preparing a polytetrafluoroethylene nanofiber membrane according to claim 1, wherein: in the step (2), the mass ratio of the gamma-aminopropyl triethoxysilane to the absolute ethyl alcohol to the water is 20:72:8;
the mass of the gamma-aminopropyl triethoxysilane in the step (2) accounts for 3.0-3.2% of the total mass of the nano tungsten disulfide;
in the step (2), the centrifugal rotating speed is 3000r/min, the centrifugal time is 6-8min, and the centrifugal times are 3 times;
the drying time in the step (2) is 24-26h, and the drying temperature is 70-75 ℃.
5. The method for preparing a polytetrafluoroethylene nanofiber membrane according to claim 1, wherein: PTFE/SiO in step (3) 2 The mass of the hybridization material accounts for 2.9-3.2% of the mass of the polytetrafluoroethylene emulsion; the mass of the modified nano tungsten disulfide accounts for 0.8-1.0% of the mass of the polytetrafluoroethylene emulsion; the mass of the ethylene-tetrafluoroethylene copolymer accounts for 1.8-2.2% of the mass of the polytetrafluoroethylene emulsion.
6. The method for preparing a polytetrafluoroethylene nanofiber membrane according to claim 1, wherein: the mass concentration of the polyethylene oxide solution in the step (3) is 9%, and the solid content of the polytetrafluoroethylene emulsion is 60%.
7. The method for preparing a polytetrafluoroethylene nanofiber membrane according to claim 1, wherein: in the step (3), polyethylene oxide solution is prepared by dissolving polyethylene oxide with the molecular weight of 300000g/mol in deionized water and stirring for 6.5h in a water bath environment at 50 ℃ to dissolve the polyethylene oxide.
8. The method for preparing a polytetrafluoroethylene nanofiber membrane according to claim 1, wherein: the mass ratio of the polytetrafluoroethylene emulsion to the mass of the polyethylene oxide solution in the step (3) is 1:0.90.
9. The method for preparing a polytetrafluoroethylene nanofiber membrane according to claim 1, wherein: in the step (4), the electrostatic spinning voltage is 18-20KV, the advancing speed of the electrostatic spinning equipment is 0.55-0.60mL/h, and the distance between a spray head of the electrostatic spinning equipment and a collector of a roller of a counter electrode is 15-17cm.
10. The method for preparing a polytetrafluoroethylene nanofiber membrane according to claim 1, wherein: and (3) the heat treatment in the step (4) is to dry the composite fiber membrane prepared by electrostatic spinning at 85-88 ℃ for 1.5-2h, and then sinter at 385-390 ℃ for 15-20min.
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