CN111996811A - PTFE double-component waterproof moisture-permeable film and preparation method thereof - Google Patents
PTFE double-component waterproof moisture-permeable film and preparation method thereof Download PDFInfo
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- CN111996811A CN111996811A CN202010871408.1A CN202010871408A CN111996811A CN 111996811 A CN111996811 A CN 111996811A CN 202010871408 A CN202010871408 A CN 202010871408A CN 111996811 A CN111996811 A CN 111996811A
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- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 114
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 90
- 239000012528 membrane Substances 0.000 claims abstract description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- 239000000835 fiber Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 17
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 48
- 239000000839 emulsion Substances 0.000 claims description 41
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 36
- 239000004814 polyurethane Substances 0.000 claims description 34
- 229920002635 polyurethane Polymers 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 150000002009 diols Chemical class 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 27
- 239000004417 polycarbonate Substances 0.000 claims description 27
- 229920000515 polycarbonate Polymers 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 20
- 238000001291 vacuum drying Methods 0.000 claims description 20
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 18
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004327 boric acid Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 7
- 238000009987 spinning Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010041 electrostatic spinning Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 13
- 238000001354 calcination Methods 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 5
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 3
- 229920006264 polyurethane film Polymers 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- 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
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- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- 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
- D04H1/40—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
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- 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
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- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2201/00—Chemical constitution of the fibres, threads or yarns
- D06N2201/02—Synthetic macromolecular fibres
- D06N2201/029—Fluoropolymer fibres
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06N2209/00—Properties of the materials
- D06N2209/12—Permeability or impermeability properties
- D06N2209/126—Permeability to liquids, absorption
- D06N2209/128—Non-permeable
Abstract
The invention discloses a PTFE double-component waterproof moisture-permeable film, which comprises a modified PTFE film and a modified polyurethane film layer coated on the surface of the modified PTFE film; adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring in an ice bath for 15min, adding potassium chlorate, continuing to stir for 30min, then heating in a water bath at 40 ℃ for 3h, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, continuing to react for 10min, and preparing a graphene oxide solution; the invention also discloses a preparation method of the PTFE double-component waterproof moisture-permeable film; the modified PTFE membrane is prepared by calcination, PVA is decomposed in the calcination process, the purity of the modified PTFE membrane can be guaranteed, the modified PTFE membrane is of a hollow structure, and the roughness and the pores of the surface of the prepared fiber can be increased by adding nano silicon dioxide particles, so that the fiber is endowed with excellent air permeability and moisture permeability.
Description
Technical Field
The invention belongs to the technical field of waterproof moisture-permeable films, and particularly relates to a PTFE (polytetrafluoroethylene) double-component waterproof moisture-permeable film and a preparation method thereof.
Background
The PTFE membrane is a microporous membrane prepared from polytetrafluoroethylene by adopting a special process and adopting methods such as calendering, extruding, biaxial stretching and the like. PTFE membranes can be classified into clothing membranes, air filtration membranes and air purification membranes according to purposes. The PTFE membrane has a fibril-like microporous structure, the porosity is more than 85%, 14 hundred million micropores are formed in each square centimeter, and the pore diameter ranges from 0.02 mu m to 15 mu m.
The waterproof moisture-permeable film on the market is various and various, and comprises acrylic resin, polyurethane, polyvinyl chloride, rubber-based resin, polytetrafluoroethylene and the like. With the progress of science and technology, the waterproof moisture permeability of various films has been developed greatly, and polyurethane resin has a large space for waterproof moisture permeability, good wearability and moderate price, so that the polyurethane resin occupies the largest share in the market.
Chinese patent CN111187440A discloses a method for producing a two-component modified TPU waterproof breathable film, which comprises the following steps: (1) stirring the PU resin stock solution and the matting powder until the matting powder is completely dissolved in the resin stock solution, and stopping stirring after the temperature is reduced to 10-15 ℃; (2) adding color paste and organic silicon, and stirring until the color paste is completely dissolved in the resin; (3) then uniformly stirring the solvent mixed solution; (4) and (3) coating the surface layer of the TPU film with the resin mixed solution, and then placing the TPU film in an oven. The invention relates to a production method of a two-component modified TPU waterproof breathable film, which is a two-component modified TPU film prepared by modifying PU resin stock solution with matting powder, organic silicon, color paste and solvent through the organic silicon and coating the PU resin on the surface of a TPU film.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a PTFE double-component waterproof moisture-permeable film and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
the graphene has super van der waals force and conjugate acting force, a three-dimensional structure is easily formed, so that the graphene is poor in dispersibility in an organic phase and a water phase solvent, and the nano silicon dioxide is easy to agglomerate and is not easy to disperse in the solvent.
The purpose of the invention can be realized by the following technical scheme:
a PTFE double-component waterproof moisture permeable membrane comprises a modified PTFE membrane and a modified polyurethane membrane layer coated on the surface of the modified PTFE membrane;
the PTFE double-component waterproof moisture-permeable film is prepared by the following method:
firstly, adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring for 15min in an ice bath, adding potassium chlorate, continuing to stir for 30min, then heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, and continuing to react for 10min to obtain a graphene oxide solution;
secondly, adding polycarbonate diol and hexanediol into a three-neck flask, adding butanone, heating in a water bath at 40-45 ℃, stirring at the rotating speed of 140r/min for 10min, then adding toluene diisocyanate, stirring at a constant speed, heating to 65-70 ℃, reacting for 3h to obtain a prepolymer, and controlling the weight ratio of the polycarbonate diol to the hexanediol to the butanone to the toluene diisocyanate to be 10: 0.1-0.2: 5-8: 3-5;
thirdly, adding the graphene oxide solution prepared in the first step into the prepared prepolymer, preserving heat at 70 ℃ and reacting for 3 hours, then adding dimethylolpropionic acid, stirring at a constant speed, continuing to preserve heat and react for 3 hours, then cooling to 40-45 ℃, adding triethylamine, and stirring at a constant speed for 1 hour to prepare a modified polyurethane emulsion;
and fourthly, coating the modified polyurethane emulsion on the surface of the modified PTFE film, and drying to obtain the PTFE double-component waterproof moisture-permeable film.
The method is characterized in that superstrong van der Waals force and conjugate acting force exist among graphene, a three-dimensional structure is easily formed, and the dispersibility of the graphene in an organic phase and a water phase solvent is poor; and secondly, preparing a prepolymer from polycarbonate diol, hexanediol and other raw materials, adding a graphene oxide solution as a modifier, and adding dimethylolpropionic acid as a chain extender to prepare the modified polyurethane emulsion.
Further, in the first step, the weight ratio of the graphene, the sodium nitrate, the 98% concentrated sulfuric acid, the potassium chlorate, the deionized water and the 10% aqueous hydrogen peroxide solution is controlled to be 2: 1-2: 0.1-0.2: 10-15: 4-5.
Further, in the third step, the weight ratio of the graphene oxide solution, the dimethylolpropionic acid and the triethylamine is controlled to be 1: 200-300: 100-200, and the graphene oxide solution is 0.2 percent of the mass of the polycarbonate diol.
Further, the modified PTFE membrane is made by the following method:
s1, filtering PTFE dispersion resin through an 8-mesh screen at 15-20 ℃, uniformly mixing the PTFE dispersion resin with a lubricant according to a weight ratio of 5: 1, transferring the mixture into a vacuum drying oven at 30-45 ℃ for drying, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa, drying for 8-10h, extruding and pressing to obtain a prefabricated product, drying the prefabricated product in the vacuum drying oven at 50 ℃ for 10h to obtain a material A, adding the material A into deionized water, and magnetically stirring for 20min to obtain an emulsion B with the mass fraction of 60%;
step S2, uniformly mixing absolute ethyl alcohol and deionized water according to the weight ratio of 1: 1 to prepare a mixed solvent, then adding hydrochloric acid with the substance amount concentration of 0.01mol/L, magnetically stirring at the rotating speed of 120r/min for 5min, then dropwise adding KH550, controlling the dropwise adding time to be 10min, uniformly stirring for 3min after the dropwise adding is finished, adding tetraethoxysilane while stirring, continuously stirring for 4h at a uniform speed to prepare a suspension, filtering and washing to prepare hydrophilic silicon dioxide nanoparticles, and controlling the weight ratio of the mixed solvent, the hydrochloric acid, the KH550 and the tetraethoxysilane to be 100: 0.1-0.2: 1: 10;
step S3, uniformly mixing 10 mass percent of PVA solution with 60 mass percent of emulsion B, adding 3 mass percent of boric acid solution, uniformly mixing, adding the hydrophilic silica nanoparticles prepared in the step S2 to prepare spinning solution, performing electrostatic spinning to prepare a nascent fiber membrane, transferring the nascent fiber membrane to a muffle furnace, heating to 350-380 ℃ at the heating rate of 3-5 ℃/min, and preserving heat for 2h to prepare the modified PTFE membrane.
Step S1, mixing PTFE dispersion resin and a lubricant, pressing to obtain a prefabricated product, drying in a vacuum drying oven at 50 ℃ for 10 hours to remove the lubricant, so that the PTFE dispersion resin is in a hollow structure, dispersing the prefabricated product in deionized water to obtain emulsion B, wherein nano-silica particles are easy to agglomerate, step S2, adding hydrochloric acid and KH550, preparing hydrophilic nano-silica particles by ethyl orthosilicate, wherein the particles have a large number of hydroxyl groups, can form hydrogen bonds with an aqueous solution, prevent self-agglomeration and uniformly disperse in the solution, step S3, mixing PVA solution and emulsion B, adding boric acid, the boric acid can be complexed with PVA, further increasing the viscosity of the prepared spinning solution, mixing PVA as a matrix polymer with PTFE, adding nano-silica, preparing a modified PTFE membrane by calcining, and decomposing PVA in the calcining process, the purity of the modified PTFE membrane can be guaranteed, the modified PTFE membrane is of a hollow structure, and the added nano silicon dioxide particles can increase the roughness and the pores of the surface of the prepared fiber and endow the fiber with excellent air permeability and moisture permeability.
Further, the lubricant is one or two of paraffin or stearic acid amide which are mixed according to any proportion.
Further, the weight ratio of the PVA solution, the emulsion B, the boric acid solution and the hydrophilic silica nanoparticles is controlled to be 1: 3: 0.01: 0.1 in step S3.
A preparation method of a PTFE double-component waterproof moisture-permeable film comprises the following steps:
firstly, adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring for 15min in an ice bath, adding potassium chlorate, continuing to stir for 30min, then heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, and continuing to react for 10min to obtain a graphene oxide solution;
secondly, adding polycarbonate diol and hexanediol into a three-neck flask, adding butanone, heating in a water bath at 40-45 ℃, stirring at the rotating speed of 140r/min for 10min, then adding toluene diisocyanate, stirring at a constant speed, heating to 65-70 ℃, reacting for 3h to obtain a prepolymer, and controlling the weight ratio of the polycarbonate diol to the hexanediol to the butanone to the toluene diisocyanate to be 10: 0.1-0.2: 5-8: 3-5;
thirdly, adding the graphene oxide solution prepared in the first step into the prepared prepolymer, preserving heat at 70 ℃ and reacting for 3 hours, then adding dimethylolpropionic acid, stirring at a constant speed, continuing to preserve heat and react for 3 hours, then cooling to 40-45 ℃, adding triethylamine, and stirring at a constant speed for 1 hour to prepare a modified polyurethane emulsion;
and fourthly, coating the modified polyurethane emulsion on the surface of the modified PTFE film, and drying to obtain the PTFE double-component waterproof moisture-permeable film.
The invention has the beneficial effects that:
(1) the invention relates to a PTFE double-component waterproof moisture permeable membrane, which comprises a modified PTFE membrane and a modified polyurethane membrane layer coated on the surface of the modified PTFE membrane, wherein in the preparation process of the modified PTFE membrane, PTFE dispersion resin and a lubricant are mixed and pressed to prepare a prefabricated product, the lubricant can be removed after drying in a vacuum drying oven at 50 ℃ for 10h, so that the PTFE dispersion resin is in a hollow structure, then the prefabricated product is dispersed in deionized water to prepare emulsion B, nano-silica particles are easy to agglomerate, hydrochloric acid and KH550 are added in step S2, hydrophilic nano-silica particles are prepared by tetraethoxysilane, a large number of hydroxyl groups are arranged on the particles, hydrogen bonds can be formed between the particles and an aqueous solution, the self-agglomeration is prevented, the particles are uniformly dispersed in the solution, the PVA solution and the emulsion B are mixed in step S3, then boric acid is added, the boric acid can be complexed with PVA, so that the viscosity of the, PVA is used as a matrix polymer to be mixed with PTFE, nano-silica is added, then the modified PTFE membrane is prepared by calcination, the PVA is decomposed in the calcination process, the purity of the modified PTFE membrane can be ensured, the modified PTFE membrane is of a hollow structure, and the roughness and the pores of the surface of the prepared fiber can be increased by adding nano-silica particles, so that the fiber is endowed with excellent air permeability and moisture permeability.
(2) In the preparation process of the modified polyurethane film layer, graphene oxide is prepared under the action of potassium chlorate, 10% hydrogen peroxide water solution and the like in the first step, the graphene oxide can be dispersed in water and can also be dispersed in an organic solvent, and rich oxygen-containing functional groups are added on the surface of the graphene oxide, so that the graphene oxide is not easy to agglomerate; and secondly, preparing a prepolymer from polycarbonate diol, hexanediol and other raw materials, adding a graphene oxide solution as a modifier, and adding dimethylolpropionic acid as a chain extender to prepare the modified polyurethane emulsion.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A PTFE double-component waterproof moisture permeable membrane comprises a modified PTFE membrane and a modified polyurethane membrane layer coated on the surface of the modified PTFE membrane;
the PTFE double-component waterproof moisture-permeable film is prepared by the following method:
firstly, adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring for 15min in an ice bath, adding potassium chlorate, continuously stirring for 30min, heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, and continuously reacting for 10min to obtain a graphene oxide solution, wherein the weight ratio of the graphene, the sodium nitrate, the 98% concentrated sulfuric acid, the potassium chlorate, the deionized water and the 10% aqueous hydrogen peroxide is controlled to be 2: 1: 0.1: 10: 4;
secondly, adding polycarbonate diol and hexanediol into a three-neck flask, adding butanone, heating in a water bath at 40 ℃, stirring at the rotating speed of 140r/min for 10min, then adding toluene diisocyanate, stirring at a constant speed, heating to 65 ℃, reacting for 3h to obtain a prepolymer, and controlling the weight ratio of the polycarbonate diol to the hexanediol, the butanone and the toluene diisocyanate to be 10: 0.1: 5: 3;
thirdly, adding the graphene oxide solution prepared in the first step into the prepared prepolymer, preserving heat at 70 ℃ and reacting for 3 hours, then adding dimethylolpropionic acid, stirring at a constant speed, continuing to preserve heat and react for 3 hours, then cooling to 40 ℃, adding triethylamine, stirring at a constant speed for 1 hour to prepare a modified polyurethane emulsion, wherein the weight ratio of the graphene oxide solution, the dimethylolpropionic acid and the triethylamine is controlled to be 1: 200: 100, and the graphene oxide solution is 0.2 percent of the mass of the polycarbonate diol;
and fourthly, coating the modified polyurethane emulsion on the surface of the modified PTFE film, and drying to obtain the PTFE double-component waterproof moisture-permeable film.
The modified PTFE membrane is prepared by the following method:
s1, filtering PTFE dispersion resin through an 8-mesh screen at 15 ℃, uniformly mixing the PTFE dispersion resin with stearic acid amide according to the weight ratio of 5: 1, transferring the mixture into a 30 ℃ vacuum drying oven for drying, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa and the drying time to be 8h, extruding and pressing to obtain a prefabricated product, placing the prefabricated product into a 50 ℃ vacuum drying oven for drying for 10h to obtain a material A, adding the material A into deionized water, and magnetically stirring for 20min to obtain an emulsion B with the mass fraction of 60%;
step S2, uniformly mixing absolute ethyl alcohol and deionized water according to the weight ratio of 1: 1 to prepare a mixed solvent, then adding hydrochloric acid with the substance amount concentration of 0.01mol/L, magnetically stirring at the rotating speed of 120r/min for 5min, then dropwise adding KH550, controlling the dropwise adding time to be 10min, uniformly stirring for 3min after the dropwise adding is finished, adding tetraethoxysilane while stirring, continuously stirring for 4h at a uniform speed to prepare a suspension, filtering and washing to prepare hydrophilic silicon dioxide nano particles, and controlling the weight ratio of the mixed solvent, the hydrochloric acid, the KH550 and the tetraethoxysilane to be 100: 0.1: 1: 10;
step S3, uniformly mixing 10% of PVA solution and 60% of emulsion B, adding 3% of boric acid solution, uniformly mixing, adding the hydrophilic silica nanoparticles prepared in step S2 to prepare spinning solution, performing electrostatic spinning to prepare a nascent fiber membrane, transferring the nascent fiber membrane to a muffle furnace, heating to 350 ℃ at a heating rate of 3 ℃/min, and preserving heat for 2 hours to prepare the modified PTFE membrane.
Example 2
A PTFE double-component waterproof moisture permeable membrane comprises a modified PTFE membrane and a modified polyurethane membrane layer coated on the surface of the modified PTFE membrane;
the PTFE double-component waterproof moisture-permeable film is prepared by the following method:
firstly, adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring for 15min in an ice bath, adding potassium chlorate, continuously stirring for 30min, heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, and continuously reacting for 10min to obtain a graphene oxide solution, wherein the weight ratio of the graphene, the sodium nitrate, the 98% concentrated sulfuric acid, the potassium chlorate, the deionized water and the 10% aqueous hydrogen peroxide is controlled to be 2: 1: 2: 0.2: 12: 4;
secondly, adding polycarbonate diol and hexanediol into a three-neck flask, adding butanone, heating in a water bath at 40 ℃, stirring at the rotating speed of 140r/min for 10min, then adding toluene diisocyanate, stirring at a constant speed, heating to 65 ℃, reacting for 3h to obtain a prepolymer, and controlling the weight ratio of the polycarbonate diol to the hexanediol, the butanone and the toluene diisocyanate to be 10: 0.2: 6: 4;
thirdly, adding the graphene oxide solution prepared in the first step into the prepared prepolymer, preserving heat at 70 ℃ and reacting for 3 hours, then adding dimethylolpropionic acid, stirring at a constant speed, continuing to preserve heat and react for 3 hours, then cooling to 40 ℃, adding triethylamine, stirring at a constant speed for 1 hour to prepare a modified polyurethane emulsion, wherein the weight ratio of the graphene oxide solution, the dimethylolpropionic acid and the triethylamine is controlled to be 1: 220: 120, and the graphene oxide solution is 0.2 percent of the mass of the polycarbonate diol;
and fourthly, coating the modified polyurethane emulsion on the surface of the modified PTFE film, and drying to obtain the PTFE double-component waterproof moisture-permeable film.
The modified PTFE membrane is prepared by the following method:
s1, filtering PTFE dispersion resin through an 8-mesh screen at 15 ℃, uniformly mixing the PTFE dispersion resin with stearic acid amide according to the weight ratio of 5: 1, transferring the mixture into a 30 ℃ vacuum drying oven for drying, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa and the drying time to be 8h, extruding and pressing to obtain a prefabricated product, placing the prefabricated product into a 50 ℃ vacuum drying oven for drying for 10h to obtain a material A, adding the material A into deionized water, and magnetically stirring for 20min to obtain an emulsion B with the mass fraction of 60%;
step S2, uniformly mixing absolute ethyl alcohol and deionized water according to the weight ratio of 1: 1 to prepare a mixed solvent, then adding hydrochloric acid with the substance amount concentration of 0.01mol/L, magnetically stirring at the rotating speed of 120r/min for 5min, then dropwise adding KH550, controlling the dropwise adding time to be 10min, uniformly stirring for 3min after the dropwise adding is finished, adding tetraethoxysilane while stirring, continuously stirring for 4h at a uniform speed to prepare a suspension, filtering and washing to prepare hydrophilic silicon dioxide nano particles, and controlling the weight ratio of the mixed solvent, the hydrochloric acid, the KH550 and the tetraethoxysilane to be 100: 0.1: 1: 10;
step S3, uniformly mixing 10% of PVA solution and 60% of emulsion B, adding 3% of boric acid solution, uniformly mixing, adding the hydrophilic silica nanoparticles prepared in step S2 to prepare spinning solution, performing electrostatic spinning to prepare a nascent fiber membrane, transferring the nascent fiber membrane to a muffle furnace, heating to 350 ℃ at a heating rate of 3 ℃/min, and preserving heat for 2 hours to prepare the modified PTFE membrane.
Example 3
A PTFE double-component waterproof moisture permeable membrane comprises a modified PTFE membrane and a modified polyurethane membrane layer coated on the surface of the modified PTFE membrane;
the PTFE double-component waterproof moisture-permeable film is prepared by the following method:
firstly, adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring for 15min in an ice bath, adding potassium chlorate, continuously stirring for 30min, heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, and continuously reacting for 10min to obtain a graphene oxide solution, wherein the weight ratio of the graphene, the sodium nitrate, the 98% concentrated sulfuric acid, the potassium chlorate, the deionized water and the 10% aqueous hydrogen peroxide is controlled to be 2: 1: 2: 0.2: 13: 5;
secondly, adding polycarbonate diol and hexanediol into a three-neck flask, adding butanone, heating in a water bath at 40 ℃, stirring at the rotating speed of 140r/min for 10min, then adding toluene diisocyanate, stirring at a constant speed, heating to 65 ℃, reacting for 3h to obtain a prepolymer, and controlling the weight ratio of the polycarbonate diol to the hexanediol to the butanone to the toluene diisocyanate to be 10: 0.2: 6: 5;
thirdly, adding the graphene oxide solution prepared in the first step into the prepared prepolymer, preserving heat at 70 ℃ and reacting for 3 hours, then adding dimethylolpropionic acid, stirring at a constant speed, continuing to preserve heat and react for 3 hours, then cooling to 40 ℃, adding triethylamine, stirring at a constant speed for 1 hour to prepare a modified polyurethane emulsion, wherein the weight ratio of the graphene oxide solution, the dimethylolpropionic acid and the triethylamine is controlled to be 1: 280: 180, and the graphene oxide solution is 0.2% of the mass of the polycarbonate diol;
and fourthly, coating the modified polyurethane emulsion on the surface of the modified PTFE film, and drying to obtain the PTFE double-component waterproof moisture-permeable film.
The modified PTFE membrane is prepared by the following method:
s1, filtering PTFE dispersion resin through an 8-mesh screen at 15 ℃, uniformly mixing the PTFE dispersion resin with stearic acid amide according to the weight ratio of 5: 1, transferring the mixture into a 30 ℃ vacuum drying oven for drying, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa and the drying time to be 8h, extruding and pressing to obtain a prefabricated product, placing the prefabricated product into a 50 ℃ vacuum drying oven for drying for 10h to obtain a material A, adding the material A into deionized water, and magnetically stirring for 20min to obtain an emulsion B with the mass fraction of 60%;
step S2, uniformly mixing absolute ethyl alcohol and deionized water according to the weight ratio of 1: 1 to prepare a mixed solvent, then adding hydrochloric acid with the substance amount concentration of 0.01mol/L, magnetically stirring at the rotating speed of 120r/min for 5min, then dropwise adding KH550, controlling the dropwise adding time to be 10min, uniformly stirring for 3min after the dropwise adding is finished, adding tetraethoxysilane while stirring, continuously stirring for 4h at a uniform speed to prepare a suspension, filtering and washing to prepare hydrophilic silicon dioxide nano particles, and controlling the weight ratio of the mixed solvent, the hydrochloric acid, the KH550 and the tetraethoxysilane to be 100: 0.1: 1: 10;
step S3, uniformly mixing 10% of PVA solution and 60% of emulsion B, adding 3% of boric acid solution, uniformly mixing, adding the hydrophilic silica nanoparticles prepared in step S2 to prepare spinning solution, performing electrostatic spinning to prepare a nascent fiber membrane, transferring the nascent fiber membrane to a muffle furnace, heating to 350 ℃ at a heating rate of 3 ℃/min, and preserving heat for 2 hours to prepare the modified PTFE membrane.
Example 4
A PTFE double-component waterproof moisture permeable membrane comprises a modified PTFE membrane and a modified polyurethane membrane layer coated on the surface of the modified PTFE membrane;
the PTFE double-component waterproof moisture-permeable film is prepared by the following method:
firstly, adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring for 15min in an ice bath, adding potassium chlorate, continuously stirring for 30min, heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, and continuously reacting for 10min to obtain a graphene oxide solution, wherein the weight ratio of the graphene, the sodium nitrate, the 98% concentrated sulfuric acid, the potassium chlorate, the deionized water and the 10% aqueous hydrogen peroxide is controlled to be 2: 1: 2: 0.2: 15: 5;
secondly, adding polycarbonate diol and hexanediol into a three-neck flask, adding butanone, heating in a water bath at 40 ℃, stirring at the rotating speed of 140r/min for 10min, then adding toluene diisocyanate, stirring at a constant speed, heating to 65 ℃, reacting for 3h to obtain a prepolymer, and controlling the weight ratio of the polycarbonate diol to the hexanediol to the butanone to the toluene diisocyanate to be 10: 0.2: 8: 5;
thirdly, adding the graphene oxide solution prepared in the first step into the prepared prepolymer, preserving heat at 70 ℃ and reacting for 3 hours, then adding dimethylolpropionic acid, stirring at a constant speed, continuing to preserve heat and react for 3 hours, then cooling to 40 ℃, adding triethylamine, stirring at a constant speed for 1 hour to prepare a modified polyurethane emulsion, wherein the weight ratio of the graphene oxide solution, the dimethylolpropionic acid and the triethylamine is controlled to be 1: 300: 200, and the graphene oxide solution is 0.2 percent of the mass of the polycarbonate diol;
and fourthly, coating the modified polyurethane emulsion on the surface of the modified PTFE film, and drying to obtain the PTFE double-component waterproof moisture-permeable film.
The modified PTFE membrane is prepared by the following method:
s1, filtering PTFE dispersion resin through an 8-mesh screen at 15 ℃, uniformly mixing the PTFE dispersion resin with stearic acid amide according to the weight ratio of 5: 1, transferring the mixture into a 30 ℃ vacuum drying oven for drying, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa and the drying time to be 8h, extruding and pressing to obtain a prefabricated product, placing the prefabricated product into a 50 ℃ vacuum drying oven for drying for 10h to obtain a material A, adding the material A into deionized water, and magnetically stirring for 20min to obtain an emulsion B with the mass fraction of 60%;
step S2, uniformly mixing absolute ethyl alcohol and deionized water according to the weight ratio of 1: 1 to prepare a mixed solvent, then adding hydrochloric acid with the substance amount concentration of 0.01mol/L, magnetically stirring at the rotating speed of 120r/min for 5min, then dropwise adding KH550, controlling the dropwise adding time to be 10min, uniformly stirring for 3min after the dropwise adding is finished, adding tetraethoxysilane while stirring, continuously stirring for 4h at a uniform speed to prepare a suspension, filtering and washing to prepare hydrophilic silicon dioxide nano particles, and controlling the weight ratio of the mixed solvent, the hydrochloric acid, the KH550 and the tetraethoxysilane to be 100: 0.1: 1: 10;
step S3, uniformly mixing 10% of PVA solution and 60% of emulsion B, adding 3% of boric acid solution, uniformly mixing, adding the hydrophilic silica nanoparticles prepared in step S2 to prepare spinning solution, performing electrostatic spinning to prepare a nascent fiber membrane, transferring the nascent fiber membrane to a muffle furnace, heating to 350 ℃ at a heating rate of 3 ℃/min, and preserving heat for 2 hours to prepare the modified PTFE membrane.
Comparative example 1
Compared with the example 1, the preparation method of the comparative example, which replaces the modified polyurethane emulsion with the polyurethane emulsion, is as follows:
and coating the polyurethane emulsion on the surface of the modified PTFE film, and drying to obtain the PTFE double-component waterproof moisture-permeable film.
Comparative example 2
In comparison with example 1, this comparative example was prepared by replacing the modified PTFE membrane with a PTFE membrane as follows:
firstly, adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring for 15min in an ice bath, adding potassium chlorate, continuously stirring for 30min, heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, and continuously reacting for 10min to obtain a graphene oxide solution, wherein the weight ratio of the graphene, the sodium nitrate, the 98% concentrated sulfuric acid, the potassium chlorate, the deionized water and the 10% aqueous hydrogen peroxide is controlled to be 2: 1: 0.1: 10: 4;
secondly, adding polycarbonate diol and hexanediol into a three-neck flask, adding butanone, heating in a water bath at 40 ℃, stirring at the rotating speed of 140r/min for 10min, then adding toluene diisocyanate, stirring at a constant speed, heating to 65 ℃, reacting for 3h to obtain a prepolymer, and controlling the weight ratio of the polycarbonate diol to the hexanediol, the butanone and the toluene diisocyanate to be 10: 0.1: 5: 3;
thirdly, adding the graphene oxide solution prepared in the first step into the prepared prepolymer, preserving heat at 70 ℃ and reacting for 3 hours, then adding dimethylolpropionic acid, stirring at a constant speed, continuing to preserve heat and react for 3 hours, then cooling to 40 ℃, adding triethylamine, stirring at a constant speed for 1 hour to prepare a modified polyurethane emulsion, wherein the weight ratio of the graphene oxide solution, the dimethylolpropionic acid and the triethylamine is controlled to be 1: 200: 100, and the graphene oxide solution is 0.2 percent of the mass of the polycarbonate diol;
and fourthly, coating the modified polyurethane emulsion on the surface of the modified PTFE film, and drying to obtain the PTFE double-component waterproof moisture-permeable film.
Comparative example 3
The comparative example is a waterproof moisture-permeable film in the market.
The moisture permeability, elongation and tear strength of examples 1 to 4 and comparative examples 1 to 3 were measured, and the results are shown in the following table;
from the above table, it can be seen that the moisture permeability of examples 1-4 is 185887-224h), the elongation is between 263 and 272 percent, and the crack initiation strength is between 2.2 and 2.5N/cm; the comparative examples 1 to 3 had a moisture permeability of 60852-125693 (g/m)224h), the elongation is between 110 and 213 percent, and the crack initiation strength is between 1.5 and 2.1N/cm; therefore, PVA is used as a matrix polymer to be mixed with PTFE, nano-silica is added, then the modified PTFE membrane is prepared by calcination, the PVA is decomposed in the calcination process, the purity of the modified PTFE membrane can be ensured, the modified PTFE membrane is of a hollow structure, and the roughness and the pores of the surface of the prepared fiber can be increased by adding nano-silica particles, so that the fiber is endowed with excellent air permeability and moisture permeability.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to 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 do not necessarily 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.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. A PTFE double-component waterproof moisture permeable membrane is characterized by comprising a modified PTFE membrane and a modified polyurethane membrane layer coated on the surface of the modified PTFE membrane;
the PTFE double-component waterproof moisture-permeable film is prepared by the following method:
firstly, adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring for 15min in an ice bath, adding potassium chlorate, continuing to stir for 30min, then heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, and continuing to react for 10min to obtain a graphene oxide solution;
secondly, adding polycarbonate diol and hexanediol into a three-neck flask, adding butanone, heating in a water bath at 40-45 ℃, stirring at the rotating speed of 140r/min for 10min, then adding toluene diisocyanate, stirring at a constant speed, heating to 65-70 ℃, reacting for 3h to obtain a prepolymer, and controlling the weight ratio of the polycarbonate diol to the hexanediol to the butanone to the toluene diisocyanate to be 10: 0.1-0.2: 5-8: 3-5;
thirdly, adding the graphene oxide solution prepared in the first step into the prepared prepolymer, preserving heat at 70 ℃ and reacting for 3 hours, then adding dimethylolpropionic acid, stirring at a constant speed, continuing to preserve heat and react for 3 hours, then cooling to 40-45 ℃, adding triethylamine, and stirring at a constant speed for 1 hour to prepare a modified polyurethane emulsion;
and fourthly, coating the modified polyurethane emulsion on the surface of the modified PTFE film, and drying to obtain the PTFE double-component waterproof moisture-permeable film.
2. The PTFE two-component waterproof moisture-permeable membrane as claimed in claim 1, wherein in the first step, the weight ratio of graphene, sodium nitrate, 98% concentrated sulfuric acid, potassium chlorate, deionized water and 10% aqueous hydrogen peroxide is controlled to be 2: 1-2: 0.1-0.2: 10-15: 4-5.
3. The PTFE two-component waterproof moisture-permeable membrane as claimed in claim 1, wherein in the third step, the weight ratio of the graphene oxide solution, dimethylolpropionic acid and triethylamine is controlled to be 1: 200-300: 100-200, and the graphene oxide solution is 0.2% of the mass of the polycarbonate diol.
4. The PTFE two-component waterproof moisture permeable membrane of claim 1, wherein the modified PTFE membrane is prepared by the following method:
s1, filtering PTFE dispersion resin through an 8-mesh screen at 15-20 ℃, uniformly mixing the PTFE dispersion resin with a lubricant according to a weight ratio of 5: 1, transferring the mixture into a vacuum drying oven at 30-45 ℃ for drying, controlling the vacuum degree of the vacuum drying oven to be-0.10 MPa, drying for 8-10h, extruding and pressing to obtain a prefabricated product, drying the prefabricated product in the vacuum drying oven at 50 ℃ for 10h to obtain a material A, adding the material A into deionized water, and magnetically stirring for 20min to obtain an emulsion B with the mass fraction of 60%;
step S2, uniformly mixing absolute ethyl alcohol and deionized water according to the weight ratio of 1: 1 to prepare a mixed solvent, then adding hydrochloric acid with the substance amount concentration of 0.01mol/L, magnetically stirring at the rotating speed of 120r/min for 5min, then dropwise adding KH550, controlling the dropwise adding time to be 10min, uniformly stirring for 3min after the dropwise adding is finished, adding tetraethoxysilane while stirring, continuously stirring for 4h at a uniform speed to prepare a suspension, filtering and washing to prepare hydrophilic silicon dioxide nanoparticles, and controlling the weight ratio of the mixed solvent, the hydrochloric acid, the KH550 and the tetraethoxysilane to be 100: 0.1-0.2: 1: 10;
step S3, uniformly mixing 10 mass percent of PVA solution with 60 mass percent of emulsion B, adding 3 mass percent of boric acid solution, uniformly mixing, adding the hydrophilic silica nanoparticles prepared in the step S2 to prepare spinning solution, performing electrostatic spinning to prepare a nascent fiber membrane, transferring the nascent fiber membrane to a muffle furnace, heating to 350-380 ℃ at the heating rate of 3-5 ℃/min, and preserving heat for 2h to prepare the modified PTFE membrane.
5. The PTFE two-component waterproof and moisture-permeable film according to claim 4, wherein the lubricant is one or two of paraffin or stearic acid amide mixed according to any proportion.
6. The PTFE two-component waterproof moisture-permeable membrane according to claim 4, wherein the weight ratio of the PVA solution, the emulsion B, the boric acid solution and the hydrophilic silica nanoparticles is controlled to be 1: 3: 0.01: 0.1 in step S3.
7. The preparation method of the PTFE double-component waterproof moisture-permeable film according to claim 1, which is characterized by comprising the following steps:
firstly, adding graphene into a beaker, adding sodium nitrate and 98% concentrated sulfuric acid, stirring for 15min in an ice bath, adding potassium chlorate, continuing to stir for 30min, then heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, heating to 75 ℃, reacting for 30min, adding 10% aqueous hydrogen peroxide, and continuing to react for 10min to obtain a graphene oxide solution;
secondly, adding polycarbonate diol and hexanediol into a three-neck flask, adding butanone, heating in a water bath at 40-45 ℃, stirring at the rotating speed of 140r/min for 10min, then adding toluene diisocyanate, stirring at a constant speed, heating to 65-70 ℃, reacting for 3h to obtain a prepolymer, and controlling the weight ratio of the polycarbonate diol to the hexanediol to the butanone to the toluene diisocyanate to be 10: 0.1-0.2: 5-8: 3-5;
thirdly, adding the graphene oxide solution prepared in the first step into the prepared prepolymer, preserving heat at 70 ℃ and reacting for 3 hours, then adding dimethylolpropionic acid, stirring at a constant speed, continuing to preserve heat and react for 3 hours, then cooling to 40-45 ℃, adding triethylamine, and stirring at a constant speed for 1 hour to prepare a modified polyurethane emulsion;
and fourthly, coating the modified polyurethane emulsion on the surface of the modified PTFE film, and drying to obtain the PTFE double-component waterproof moisture-permeable film.
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