CN117107432A - Waterproof moisture-permeable nanofiber antibacterial film and preparation method thereof - Google Patents
Waterproof moisture-permeable nanofiber antibacterial film and preparation method thereof Download PDFInfo
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- CN117107432A CN117107432A CN202311091095.8A CN202311091095A CN117107432A CN 117107432 A CN117107432 A CN 117107432A CN 202311091095 A CN202311091095 A CN 202311091095A CN 117107432 A CN117107432 A CN 117107432A
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- Prior art keywords
- waterproof
- moisture
- titanium dioxide
- polyurethane
- film
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 62
- 239000002121 nanofiber Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 claims abstract description 69
- 239000004814 polyurethane Substances 0.000 claims abstract description 69
- 238000009987 spinning Methods 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 33
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 28
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 20
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000460 chlorine Substances 0.000 claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- 238000004061 bleaching Methods 0.000 claims abstract description 17
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 12
- ROHTVIURAJBDES-UHFFFAOYSA-N 2-n,2-n-bis(prop-2-enyl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N(CC=C)CC=C)=N1 ROHTVIURAJBDES-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- 239000012046 mixed solvent Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- FZTSHLLXKIOHMN-UHFFFAOYSA-M [O-2].[O-2].S[Ti+4] Chemical compound [O-2].[O-2].S[Ti+4] FZTSHLLXKIOHMN-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 15
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 13
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 11
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- -1 sulfhydryl titanium dioxide Chemical compound 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 claims description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000012650 click reaction Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 229910000077 silane Inorganic materials 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- RFMXKZGZSGFZES-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS.OC(=O)CS.CCC(CO)(CO)CO RFMXKZGZSGFZES-UHFFFAOYSA-N 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920006264 polyurethane film Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent 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
- D04H1/4326—Condensation or reaction polymers
- D04H1/4358—Polyurethanes
-
- 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
- D01F1/103—Agents inhibiting growth of microorganisms
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- 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
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B15/00—Removing liquids, gases or vapours from textile materials in association with treatment of the materials by liquids, gases or vapours
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
- D06B3/10—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/20—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen
- D06L4/22—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents
- D06L4/23—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents using hypohalogenites
Abstract
The invention relates to the technical field of nano antibacterial materials, and discloses a waterproof moisture-permeable nano fiber antibacterial film and a preparation method thereof. The thiolated titanium dioxide and the sulfhydryl end-capped polyurethane are subjected to click reaction with 2, 4-diamino-6-diallyl amino-1, 3, 5-triazine under the action of a photoinitiator to obtain modified polyurethane, the modified polyurethane and polyurethane resin are mixed in a solvent, the obtained spinning solution is spun into a film through an electrostatic spinning process, the polyurethane resin and the modified polyurethane can form an interpenetrating network structure and are uniformly dispersed, a moisture permeable channel is provided for water molecules, the surface energy of the added nano titanium dioxide is reduced after the surface modification of the silane, the effect of bonding a substrate is achieved, the agglomeration of the nano titanium dioxide is effectively avoided, the surface hydrophobicity is improved, the water-proof capability is improved, and the nano titanium dioxide and halogen ammonia introduced by chlorine bleaching treatment have excellent antibacterial performance and the waterproof moisture permeable nano fiber antibacterial film has excellent waterproof moisture permeability and antibacterial efficacy.
Description
Technical Field
The invention relates to the technical field of nano antibacterial materials, in particular to a waterproof moisture-permeable nano fiber antibacterial film and a preparation method thereof.
Background
With the rapid development of economy, the living standard of people is continuously improved, and the clothes are pursued to meet basic wearing requirements and simultaneously have special functions. The waterproof moisture permeable clothing can meet a plurality of functional requirements as outdoor sports equipment, the waterproof moisture permeable clothing can prevent the penetration of rain and snow in rainy and snowy days, sweat steam generated by sports can well penetrate through the fabric and be transmitted to the outside, the dryness of the skin surface of a human body is kept, the waterproof moisture permeable clothing is mainly realized by sticking a layer of waterproof moisture permeable film on the surface of the fabric, the fabric and the film with waterproof moisture permeability are stuck to each other, the waterproof moisture permeable clothing is widely used, and the wearing comfort can be effectively improved.
In the prior art, polyurethane materials are mostly utilized to prepare waterproof moisture-permeable membranes, chinese patent application CN110983801A discloses a preparation method of waterproof moisture-permeable cotton fabrics, firstly, the waterproof and oil-repellent cotton fabrics are prepared, then silane coupling agents are adopted to carry out hydrophobic modification on gas-phase nano silicon dioxide, modified hydrophobic gas-phase nano silicon dioxide, polyvinylpyrrolidone, metal soap defoamer, anionic crosslinking agent and associated thickener are added into waterborne polyurethane to obtain modified waterborne polyurethane coating agents, coating finishing is carried out on the cotton fabrics subjected to the waterproof and oil-repellent treatment, and the waterproof moisture-permeable functional coated cotton fabrics are prepared. Chinese patent CN105968305B discloses a waterproof moisture-permeable polyurethane material and a preparation method thereof, wherein a plurality of hydroxyl groups on the surface of a polyol modified silica nanoparticle are reacted with isocyanate at two ends of a polyurethane prepolymer to form a polyurethane material with a space network structure, so that the strength of the space network structure of the polyurethane is increased to enhance the water resistance, but the air permeability and the antibacterial property of the polyurethane hydrophilic film are poor, and the polyurethane material is easy to wet and deform when meeting water. Chinese patent application CN109280366A discloses a preparation method of an antibacterial waterproof moisture-permeable polyurethane film, which comprises the steps of carrying out surface modification treatment on molybdenum tailings, bamboo charcoal powder and nano titanium dioxide, adding the surface modification treatment to the synthesis process of aqueous polyurethane resin, preparing reinforced polyurethane resin with essential antibacterial property, and carrying out physical blending with beta-cyclodextrin/tetrahydrofuran compound under the condition of participation of nano silver antibacterial liquid to prepare the film, wherein the film has excellent broad-spectrum antibacterial property, mechanical property and water resistance, excellent air-permeability and water resistance, excellent comprehensive performance, but antibacterial agent components are easy to fall off in the use process, and the antibacterial effect is general.
Disclosure of Invention
In order to solve the technical problems, the invention provides a waterproof and moisture-permeable nanofiber antibacterial film and a preparation method thereof, and solves the problems of general waterproof and moisture-permeable effects and poor antibacterial performance of polyurethane films.
In order to achieve the above purpose, the invention discloses a preparation method of a waterproof and moisture permeable nanofiber antibacterial film, which comprises the following steps:
dispersing polyurethane resin and modified polyurethane into a mixed solvent, stirring and mixing to obtain a spinning solution, spinning the spinning solution into a film through an electrostatic spinning process, soaking the film into a sodium hypochlorite solution, performing chlorine bleaching treatment, washing with deionized water after the treatment is finished, and drying in a dryer at 50 ℃ for 2 hours to obtain a waterproof moisture-permeable nanofiber antibacterial film;
the mixed solvent comprises a mixed solvent of N, N-dimethylformamide and butyl acetate;
the volume ratio of the N, N-dimethylformamide to the butyl acetate is 2:3;
the mass ratio of the polyurethane resin to the modified polyurethane to the mixed solvent is 100:38-52:600-1200.
Preferably, in the electrostatic spinning process, the advancing speed of the spinning solution is 0.8mL/h, the spinning voltage is 12kV, and the distance between the spinneret and the receiving roller is 15cm.
Preferably, in the chlorine bleaching treatment process, the sodium hypochlorite solution is sodium hypochlorite aqueous solution with the mass percentage concentration of 0.5%, and the soaking time is 1-2 hours.
Preferably, the thickness of the waterproof and moisture permeable nanofiber antibacterial film is 45-55 μm.
Preferably, the preparation method of the modified polyurethane comprises the following steps:
firstly, ultrasonically dispersing nano titanium dioxide into ethanol, after uniformly dispersing, adding a mercapto silane coupling agent in a nitrogen atmosphere, stirring and mixing, reacting, washing with ethanol after the reaction is finished, centrifuging at 8000r/min, and drying in a vacuum drying oven at 60 ℃ for 12 hours after separation to obtain mercapto titanium dioxide;
uniformly mixing mercapto-terminated polyurethane, mercapto titanium dioxide, 2, 4-diamino-6-diallyl amino-1, 3, 5-triazine (NDAM) and an initiator, reacting for 2-3h, adding Triethylamine (TEA) for neutralization after the reaction is finished, adding deionized water for dispersion, and drying at 80 ℃ for 12h in a drying oven to obtain the modified polyurethane.
Preferably, in the first step, the mass ratio of the nano titanium dioxide to the ethanol to the mercaptosilane coupling agent is 100:3200-3500:82-105.
Preferably, the mercaptosilane coupling agent in the first step comprises at least one of 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane and mercaptopropyl methyl dimethoxy silane.
Preferably, the temperature of the reaction in the step one is 30-40 ℃ and the reaction time is 18-24h.
Preferably, the reaction process in the second step is carried out under ultraviolet irradiation.
Preferably, the mass ratio of the mercapto-terminated polyurethane, the mercapto titanium dioxide, the 2, 4-diamino-6-diallyl amino-1, 3, 5-triazine and the initiator in the second step is 100:5-9:32-45:0.1-0.3.
Preferably, the raw materials for preparing the mercapto-terminated polyurethane comprise polyether glycol and isophorone diisocyanate.
Further, the preparation method of the mercapto-terminated polyurethane in the second step comprises the following steps:
at N 2 Stirring and mixing polyether glycol and isophorone diisocyanate uniformly in an atmosphere, adding dibutyl tin dilaurate, heating to 70 ℃, reacting at constant temperature for 5 hours, adding a dimethylolpropionic acid mixed solution, continuing to react for 5 hours, wherein the solvent of the dimethylolpropionic acid mixed solution is N-methylpyrrolidone, the mass ratio of the dimethylolpropionic acid to the N-methylpyrrolidone is 1:2, adding trimethylol propane tri (2-mercaptoacetate), stirring, cooling to 50 ℃, reacting for 3 hours, and adding polyether glycol, isophorone diisocyanate, dibutyl tin dilaurate, the dimethylolpropionic acid mixed solution and the trimethylol propane tri (2-mercaptoacetate) in a mass ratio of 100:91:0.47:42.5:135, and then adding triethylamine to neutralize the pH of the reaction solution to be neutral to obtain the mercapto-terminated polyurethane.
Further, in the second step, the mass ratio of the mercapto-terminated polyurethane to the mercapto-titanium dioxide to the 2, 4-diamino-6-diallyl-amino-1, 3, 5-triazine to the initiator to the triethylamine to the deionized water is 100:5-9:32-45:0.1-0.3:7-10:420-500.
Preferably, the initiator in the second step is a photoinitiator, and the initiator comprises any one of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone and 2, 2-dimethoxy-2-phenyl acetophenone (DMPA).
Preferably, the waterproof moisture-permeable nanofiber antibacterial film is prepared by the preparation method of the waterproof moisture-permeable nanofiber antibacterial film.
According to the invention, a mercapto silane coupling agent is used for modifying nano titanium dioxide, a mercapto functional group is introduced on the surface of the nano titanium dioxide to obtain mercapto titanium dioxide, the mercapto titanium dioxide and the mercapto end-capped polyurethane undergo a click reaction with 2, 4-diamino-6-diallyl amino-1, 3, 5-triazine under the action of a photoinitiator, the reaction speed is high, the modified polyurethane is obtained after the reaction, the modified polyurethane and polyurethane resin are mixed and dispersed in a mixed solvent to be mixed, a spinning solution is obtained, the spinning solution is spun into a film through an electrostatic spinning process, and the film is subjected to chlorine bleaching treatment through sodium hypochlorite to obtain the waterproof moisture-permeable nanofiber antibacterial film.
Compared with the prior art, the invention has the beneficial effects that:
(1) The nanofiber antibacterial membrane prepared by electrostatic spinning has the advantages of small fiber diameter, high porosity, good pore channel connectivity and excellent waterproof and moisture-conducting effects. The raw materials for preparing the modified polyurethane comprise sulfhydryl-terminated polyurethane, and ether bonds in polyether glycol used in the preparation of the sulfhydryl-terminated polyurethane are typical nonionic hydrophilic groups, so that the modified polyurethane has good moisture conductivity with water molecules, and the moisture conductivity of a matrix is greatly improved.
(2) According to the invention, after the polyurethane resin and the modified polyurethane are mixed in the solvent, the polyurethane resin and the modified polyurethane are spun into a film through an electrostatic spinning process, so that an interpenetrating network structure can be formed, the polyurethane resin and the modified polyurethane are uniformly dispersed, a moisture permeable channel is provided for water molecules, the surface energy of the added nano titanium dioxide is reduced after the surface of the added nano titanium dioxide is modified by silane, the effect of bonding a substrate is achieved, the agglomeration of the nano titanium dioxide is effectively avoided, the surface is hydrophobic, and the waterproof capability is improved.
(3) The nano titanium dioxide has excellent antibacterial effect, electrons on the nano titanium dioxide valence band can be excited to a conduction band under the action of light, so that electron-hole pairs are generated, the electrons migrate to the surface of the nano titanium dioxide, and the formed superoxide radicals react with organic matters in bacteria, so that the bacteria are killed, the bacteria are decomposed, the organic matters in the bacteria react, the oxidation is carried out, and the apoptosis is promoted. Chlorine bleaching treatment, wherein chlorine on sodium hypochlorite is bonded with amino groups, imino groups and the like introduced in polyurethane to form N-Cl, chlorine atoms on the N-Cl have oxidability, halogen in an oxidation state is transferred to a receiving position of microorganisms in a process of contacting with bacteria, and amino groups in mercaptan or chlorinated proteins are oxidized, so that the microorganisms are deactivated, and the prepared substrate has excellent antibacterial performance.
Drawings
FIG. 1 is a flow chart of the preparation of a waterproof moisture permeable nanofiber antimicrobial film in accordance with the present invention;
FIG. 2 is a graph showing the water-proof performance test of the water-proof moisture-permeable films of examples 1 to 8 and comparative examples 1 to 3 of the present invention;
FIG. 3 is a graph showing the moisture permeability test of the waterproof moisture permeable films of examples 1 to 8 and comparative examples 1 to 3 of the present invention;
FIG. 4 is a graph showing the antibacterial property test of the waterproof and moisture-permeable films of examples 1 to 8 and comparative examples 1 to 3 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
The preparation method of the waterproof moisture-permeable nanofiber antibacterial film comprises the following steps:
dispersing polyurethane resin and modified polyurethane into a mixed solvent of N, N-dimethylformamide and butyl acetate in a volume ratio of 2:3, stirring and mixing, wherein the mass ratio of the polyurethane resin to the modified polyurethane to the mixed solvent is 100:38:600, obtaining a spinning solution, spinning the spinning solution into a film through an electrostatic spinning process, wherein the advancing speed of the spinning solution is 0.8mL/h, the spinning voltage is 12kV, the distance between a spinneret and a receiving roller is 15cm, immersing the film into a sodium hypochlorite aqueous solution with a mass percentage concentration of 0.5%, performing chlorine bleaching treatment for 1h, washing with deionized water after the treatment is completed, and drying in a dryer at 50 ℃ for 2h, thereby obtaining the waterproof moisture-permeable nanofiber antibacterial film with a thickness of 45 mu m;
the preparation method of the modified polyurethane comprises the following steps:
firstly, ultrasonically dispersing nano titanium dioxide into ethanol, after uniformly dispersing, adding 3-mercaptopropyl trimethoxy silane in a nitrogen atmosphere, stirring and mixing, wherein the mass ratio of the nano titanium dioxide to the ethanol to the 3-mercaptopropyl trimethoxy silane is 100:3200:82, reacting for 24 hours at 30 ℃, washing with ethanol after the reaction is finished, centrifuging, and drying for 12 hours at 60 ℃ in a vacuum drying oven after separation to obtain mercaptotitanium dioxide;
uniformly mixing the sulfhydryl end-capped polyurethane, the sulfhydryl titanium dioxide, the 2, 4-diamino-6-diallyl amino-1, 3, 5-triazine and the photoinitiator 2, 2-dimethoxy-2-phenylacetophenone with the mass ratio of 100:5:32:0.1, reacting for 2 hours under the condition of ultraviolet irradiation, adding triethylamine to neutralize after the reaction is finished, adding deionized water to disperse, and drying for 12 hours at 80 ℃ in a drying box to obtain the modified polyurethane.
Example 2
The preparation method of the waterproof moisture-permeable nanofiber antibacterial film comprises the following steps:
dispersing polyurethane resin and modified polyurethane into a mixed solvent of N, N-dimethylformamide and butyl acetate in a volume ratio of 2:3, stirring and mixing, wherein the mass ratio of the polyurethane resin to the modified polyurethane to the mixed solvent is 100:42:750, obtaining a spinning solution, spinning the spinning solution into a film through an electrostatic spinning process, wherein the advancing speed of the spinning solution is 0.8mL/h, the spinning voltage is 12kV, the distance between a spinneret and a receiving roller is 15cm, immersing the film into a sodium hypochlorite aqueous solution with a mass percentage concentration of 0.5%, performing chlorine bleaching treatment for 1.5h, washing with deionized water after the treatment is completed, and drying in a dryer at 50 ℃ for 2h to obtain the waterproof and moisture-permeable nanofiber antibacterial film with a thickness of 48 mu m;
the preparation method of the modified polyurethane comprises the following steps:
firstly, ultrasonically dispersing nano titanium dioxide into ethanol, after uniformly dispersing, adding 3-mercaptopropyl trimethoxy silane in a nitrogen atmosphere, stirring and mixing, wherein the mass ratio of the nano titanium dioxide to the ethanol to the 3-mercaptopropyl trimethoxy silane is 100:3400:95, reacting for 22 hours at 35 ℃, washing with ethanol after the reaction is finished, centrifuging, and drying for 12 hours at 60 ℃ in a vacuum drying oven after separation to obtain mercaptotitanium dioxide;
uniformly mixing the sulfhydryl end-capped polyurethane, the sulfhydryl titanium dioxide, the 2, 4-diamino-6-diallyl amino-1, 3, 5-triazine and the photoinitiator 2, 2-dimethoxy-2-phenylacetophenone with the mass ratio of 100:7:40:0.2, reacting for 2.5 hours under the condition of ultraviolet irradiation, adding triethylamine to neutralize after the reaction is finished, adding deionized water to disperse, and drying for 12 hours at 80 ℃ in a drying oven to obtain the modified polyurethane.
Example 3
The preparation method of the waterproof moisture-permeable nanofiber antibacterial film comprises the following steps:
dispersing polyurethane resin and modified polyurethane into a mixed solvent of N, N-dimethylformamide and butyl acetate in a volume ratio of 2:3, stirring and mixing, wherein the mass ratio of the polyurethane resin to the modified polyurethane to the mixed solvent is 100:46:900, obtaining a spinning solution, spinning the spinning solution into a film through an electrostatic spinning process, wherein the advancing speed of the spinning solution is 0.8mL/h, the spinning voltage is 12kV, the distance between a spinneret and a receiving roller is 15cm, immersing the film into a sodium hypochlorite aqueous solution with a mass percentage concentration of 0.5%, performing chlorine bleaching treatment for 1.5h, washing with deionized water after the treatment is completed, and drying in a dryer at 50 ℃ for 2h to obtain the waterproof and moisture-permeable nanofiber antibacterial film with a thickness of 50 mu m;
wherein the preparation method of the modified polyurethane is the same as that of example 2.
Example 4
The preparation method of the waterproof moisture-permeable nanofiber antibacterial film comprises the following steps:
dispersing polyurethane resin and modified polyurethane into a mixed solvent of N, N-dimethylformamide and butyl acetate in a volume ratio of 2:3, stirring and mixing, wherein the mass ratio of the polyurethane resin to the modified polyurethane to the mixed solvent is 100:50:1100, obtaining a spinning solution, spinning the spinning solution into a film through an electrostatic spinning process, wherein the advancing speed of the spinning solution is 0.8mL/h, the spinning voltage is 12kV, the distance between a spinneret and a receiving roller is 15cm, immersing the film into a sodium hypochlorite aqueous solution with a mass percentage concentration of 0.5%, performing chlorine bleaching treatment for 1.5h, washing with deionized water after the treatment is completed, and drying in a dryer at 50 ℃ for 2h to obtain the waterproof and moisture-permeable nanofiber antibacterial film with a thickness of 52 mu m;
wherein the preparation method of the modified polyurethane is the same as that of example 2.
Example 5
The preparation method of the waterproof moisture-permeable nanofiber antibacterial film comprises the following steps:
dispersing polyurethane resin and modified polyurethane into a mixed solvent of N, N-dimethylformamide and butyl acetate in a volume ratio of 2:3, stirring and mixing, wherein the mass ratio of the polyurethane resin to the modified polyurethane to the mixed solvent is 100:52:1200, obtaining a spinning solution, spinning the spinning solution into a film through an electrostatic spinning process, wherein the advancing speed of the spinning solution is 0.8mL/h, the spinning voltage is 12kV, the distance between a spinneret and a receiving roller is 15cm, immersing the film into a sodium hypochlorite aqueous solution with a mass percentage concentration of 0.5%, performing chlorine bleaching treatment for 2 hours, washing with deionized water after the treatment is completed, and drying in a dryer at 50 ℃ for 2 hours, thereby obtaining the waterproof moisture-permeable nanofiber antibacterial film with a thickness of 55 mu m;
the preparation method of the modified polyurethane comprises the following steps:
firstly, ultrasonically dispersing nano titanium dioxide into ethanol, after uniformly dispersing, adding 3-mercaptopropyl trimethoxysilane in a nitrogen atmosphere, stirring and mixing, wherein the mass ratio of the nano titanium dioxide to the ethanol to the 3-mercaptopropyl trimethoxysilane is 100:3500:105, reacting for 24 hours at 40 ℃, washing with ethanol after the reaction is finished, centrifuging, and drying for 12 hours at 60 ℃ in a vacuum drying oven after separation to obtain mercaptotitanium dioxide;
uniformly mixing the sulfhydryl end-capped polyurethane, the sulfhydryl titanium dioxide, the 2, 4-diamino-6-diallyl amino-1, 3, 5-triazine and the photoinitiator 2, 2-dimethoxy-2-phenylacetophenone with the mass ratio of 100:9:45:0.3, reacting for 3 hours under the condition of ultraviolet irradiation, adding triethylamine to neutralize after the reaction is finished, adding deionized water to disperse, and drying for 12 hours at 80 ℃ in a drying box to obtain the modified polyurethane.
Example 6
A method for preparing a waterproof moisture-permeable nanofiber antibacterial membrane was the same as in example 4;
the preparation method of the modified polyurethane was the same as in example 4, except that 3-mercaptopropyl trimethoxysilane was replaced with 3-mercaptopropyl triethoxysilane in the preparation of mercaptotitanium dioxide.
Example 7
A method for preparing a waterproof moisture-permeable nanofiber antibacterial membrane was the same as in example 4;
the preparation method of the modified polyurethane is the same as that of example 4, except that 3-mercaptopropyl trimethoxysilane is replaced with mercaptopropyl methyl dimethoxy silane in the preparation of mercaptotitanium dioxide.
Example 8
A method for preparing a waterproof moisture-permeable nanofiber antibacterial membrane was the same as in example 4;
the preparation method of the modified polyurethane is the same as that of example 4, except that 2, 2-dimethoxy-2-phenylacetophenone serving as a photoinitiator is replaced by 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone in the preparation process of the modified polyurethane.
Comparative example 1
The preparation method of the waterproof moisture-permeable membrane is the same as that of the waterproof moisture-permeable nanofiber antibacterial membrane in example 4; except that after the electrostatic spinning is completed, chlorine bleaching treatment is not performed;
wherein the preparation method of the modified polyurethane is the same as that of example 4.
Comparative example 2
The preparation method of the waterproof moisture-permeable film comprises the following steps:
dispersing polyurethane resin, mercapto-terminated polyurethane and mercapto titanium dioxide into a mixed solvent of N, N-dimethylformamide and butyl acetate in a volume ratio of 2:3, stirring and mixing, wherein the mass ratio of the polyurethane resin to the mercapto-terminated polyurethane to the mercapto-terminated titanium dioxide to the mixed solvent is 100:46.8:3.2:1100, obtaining a spinning solution, spinning the spinning solution into a film through an electrostatic spinning process, wherein the advancing speed of the spinning solution is 0.8mL/h, the spinning voltage is 12kV, the distance between a spinneret and a receiving roller is 15cm, soaking the film into a sodium hypochlorite aqueous solution with a mass percentage concentration of 0.5%, performing chlorine bleaching treatment for 1.5h, washing with deionized water after the treatment, and drying in a dryer at 50 ℃ for 2h to obtain the waterproof moisture-permeable film with a thickness of 52 mu m.
The preparation method of the sulfhydryl titanium dioxide comprises the following steps:
firstly, ultrasonically dispersing nano titanium dioxide into ethanol, after uniformly dispersing, adding 3-mercaptopropyl trimethoxy silane in a nitrogen atmosphere, stirring and mixing, wherein the mass ratio of the nano titanium dioxide to the ethanol to the 3-mercaptopropyl trimethoxy silane is 100:3400:95, reacting for 22 hours at 35 ℃, washing with ethanol after the reaction is finished, centrifuging, and drying for 12 hours at 60 ℃ in a vacuum drying oven after separation to obtain the mercaptotitanium dioxide.
Comparative example 3
The preparation method of the waterproof moisture-permeable film comprises the following steps:
dispersing polyurethane resin and sulfhydrylation titanium dioxide into a mixed solvent of N, N-dimethylformamide and butyl acetate with the volume ratio of 2:3, stirring and mixing, wherein the mass ratio of the polyurethane resin to the sulfhydrylation titanium dioxide to the mixed solvent is 146.8:3.2:1100, obtaining a spinning solution, spinning the spinning solution into a film through an electrostatic spinning process, wherein the advancing speed of the spinning solution is 0.8mL/h in the electrostatic spinning process, the spinning voltage is 12kV, the distance between a spinneret and a receiving roller is 15cm, soaking the film into a sodium hypochlorite aqueous solution with the mass percentage concentration of 0.5%, carrying out chlorine bleaching treatment for 1.5h, washing with deionized water after the treatment is finished, and drying in a dryer at 50 ℃ for 2h to obtain a waterproof moisture-permeable film with the thickness of 52 mu m;
the preparation method of the sulfhydryl titanium dioxide comprises the following steps:
firstly, ultrasonically dispersing nano titanium dioxide into ethanol, after uniformly dispersing, adding 3-mercaptopropyl trimethoxy silane in a nitrogen atmosphere, stirring and mixing, wherein the mass ratio of the nano titanium dioxide to the ethanol to the 3-mercaptopropyl trimethoxy silane is 100:3400:95, reacting for 22 hours at 35 ℃, washing with ethanol after the reaction is finished, centrifuging, and drying for 12 hours at 60 ℃ in a vacuum drying oven after separation to obtain the mercaptotitanium dioxide.
The preparation method of the mercapto-terminated polyurethane in the examples and the comparative examples of the present invention comprises the following steps:
at N 2 Stirring and mixing polyether glycol and isophorone diisocyanate uniformly in an atmosphere, adding dibutyl tin dilaurate, heating to 70 ℃, reacting at constant temperature for 5 hours, adding a dimethylolpropionic acid mixed solution, continuing to react for 5 hours, wherein the solvent of the dimethylolpropionic acid mixed solution is N-methylpyrrolidone, the mass ratio of the dimethylolpropionic acid to the N-methylpyrrolidone is 1:2, adding trimethylol propane tri (2-mercaptoacetate), stirring, cooling to 50 ℃, reacting for 3 hours, and adding polyether glycol, isophorone diisocyanate, dibutyl tin dilaurate, the dimethylolpropionic acid mixed solution and the trimethylol propane tri (2-mercaptoacetate) in a mass ratio of 100:91:0.47:42.5:135, and then adding triethylamine to neutralize the pH of the reaction solution to be neutral to obtain the mercapto-terminated polyurethane. The polyurethane resins used in the examples and comparative examples of the present invention were purchased from Zhejiang Huafeng synthetic resin Co., ltd, model JF-S-WV7025; nanometer titanium dioxide is purchased fromXuan Chengjing New Material Co., ltd., model JR05, average particle size 5nm; ultraviolet irradiation reaction is initiated under the irradiation of EA-180/FE ultraviolet lamp of Spectroline company of America; in the preparation process of the mercapto-terminated polyurethane, polyether glycol is purchased from Shandong polymer Co., ltd, model N210.
The films prepared in examples 1 to 8 and comparative examples 1 to 3 were selected as samples, and were subjected to corresponding tests, the test methods and test results are as follows:
(1) And (3) water pressure resistance test: the water pressure resistance detection adopts JISL1092B standard, the water pressure resistance tester is used for testing samples, each sample is tested 5 times, and the average value is obtained;
(2) Moisture permeability test: the moisture permeability is detected by adopting ASTME96-1995BW standard, the temperature is kept at 23 ℃ through a constant temperature and constant humidity box, the relative humidity is 50%, each sample is tested for 5 times, and the average value is obtained;
(3) Antibacterial performance test: antibacterial performance test with reference to AATCC100-2012 standard, using staphylococcus aureus as gram positive bacteria, escherichia coli as gram negative bacteria as test strain, calculating antibacterial rate;
the test results are shown in table 1:
TABLE 1
As can be seen from the test results of Table 1, the film material prepared by the scheme of the invention has excellent waterproof capability and good moisture permeability, and the corresponding sample water pressure resistance values in examples 1 to 5 are improved from 7949mmH 2 O is increased to 8417mmH 2 O, the waterproof performance is greatly improved. The samples of examples 1-5 showed an increase in moisture permeability, wherein example 5 showed a moisture permeability of 12507 g.m -2 ·d -1 . The samples corresponding to examples 1-5 have excellent antibacterial rates against both E.coli and Staphylococcus aureus. Examples 6-8 have the same parameters as the preparation method of example 4, respectively modified mercaptosilane coupling agent and mercaptosilane coupling agentThe coupling agent and the photoinitiator have small influence on the waterproof and moisture permeability and the antibacterial performance of the sample. After electrostatic spinning in comparative example 1, the antibacterial performance is greatly reduced without chlorine bleaching treatment, the influence of waterproof moisture permeability is small, no click reaction occurs on the mercapto-terminated polyurethane and the mercapto titanium dioxide in comparative example 2, the dispersibility of the mercapto titanium dioxide is reduced, the waterproof moisture permeability is reduced, no active group is introduced, the antibacterial performance is still poor after chlorine bleaching treatment, and in comparative example 3, only the polyurethane resin and the mercapto-modified titanium dioxide are used for electrostatic spinning, and both the waterproof moisture permeability and the antibacterial performance are greatly reduced.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made hereto without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the waterproof and moisture permeable nanofiber antibacterial membrane is characterized by comprising the following steps of:
uniformly mixing mercapto-terminated polyurethane, mercapto titanium dioxide, 2, 4-diamino-6-diallyl amino-1, 3, 5-triazine and an initiator, reacting, adding triethylamine for neutralization after the reaction is finished, adding deionized water for dispersion, and drying to obtain modified polyurethane;
dispersing polyurethane resin and modified polyurethane into a mixed solvent, stirring and mixing to obtain a spinning solution, spinning the spinning solution into a film through an electrostatic spinning process, soaking the film into a sodium hypochlorite solution, performing chlorine bleaching treatment, washing with deionized water after the treatment is completed, and drying to obtain a waterproof moisture-permeable nanofiber antibacterial film;
the mass ratio of the polyurethane resin to the modified polyurethane to the mixed solvent is 100:38-52:600-1200.
2. The method for preparing the waterproof and moisture permeable nanofiber antibacterial membrane according to claim 1, wherein in the electrostatic spinning process, the advancing speed of the spinning solution is 0.8mL/h, the spinning voltage is 12kV, and the distance between the spinneret and the receiving roller is 15cm.
3. The method for preparing the waterproof and moisture permeable nanofiber antibacterial membrane according to claim 1, wherein in the chlorine bleaching treatment process, sodium hypochlorite solution is sodium hypochlorite aqueous solution with the mass percentage concentration of 0.5%, and the soaking time is 1-2h.
4. The method for preparing a waterproof and moisture-permeable nanofiber antibacterial film according to claim 1, wherein the thickness of the waterproof and moisture-permeable nanofiber antibacterial film is 45-55 μm.
5. The method for preparing the waterproof and moisture permeable nanofiber antibacterial membrane according to claim 1, wherein the mixed solvent comprises N, N-dimethylformamide and butyl acetate; the volume ratio of the N, N-dimethylformamide to the butyl acetate is 2:3.
6. The method for preparing the waterproof and moisture permeable nanofiber antibacterial membrane according to claim 5, wherein the method for preparing the thiolated titanium dioxide comprises the following steps: dispersing nano titanium dioxide into ethanol by ultrasonic, adding a sulfhydryl silane coupling agent in a nitrogen atmosphere after uniform dispersion, stirring and mixing to react, washing with ethanol after the reaction is completed, centrifuging at 8000r/min, drying in a vacuum drying oven at 60 ℃ for 12 hours after separation, and obtaining the sulfhydryl titanium dioxide.
7. The method for preparing a waterproof and moisture permeable nanofiber antibacterial film according to claim 6, wherein the mercaptosilane coupling agent comprises at least one of 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane and mercaptopropyl methyl dimethoxy silane.
8. The method for preparing the waterproof and moisture-permeable nanofiber antibacterial film according to claim 1, wherein the mass ratio of the mercapto-terminated polyurethane to the mercapto-titanium dioxide to the 2, 4-diamino-6-diallylamino-1, 3, 5-triazine to the initiator is 100:5-9:32-45:0.1-0.3.
9. The method for preparing the waterproof and moisture permeable nanofiber antibacterial membrane according to claim 1, wherein the initiator is a photoinitiator and comprises any one of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and 2, 2-dimethoxy-2-phenylacetophenone.
10. A waterproof moisture-permeable nanofiber antibacterial film prepared by the method for preparing a waterproof moisture-permeable nanofiber antibacterial film according to any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117468163A (en) * | 2023-12-25 | 2024-01-30 | 江苏青昀新材料有限公司 | Self-cleaning flash evaporation sheet and rolling process thereof |
| CN117672435A (en) * | 2024-01-31 | 2024-03-08 | 广元水木新材料科技有限公司 | Automatic fiber yarn layout method and system based on nanofiber preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117468163A (en) * | 2023-12-25 | 2024-01-30 | 江苏青昀新材料有限公司 | Self-cleaning flash evaporation sheet and rolling process thereof |
| CN117468163B (en) * | 2023-12-25 | 2024-03-26 | 江苏青昀新材料有限公司 | Self-cleaning flash evaporation sheet and rolling process thereof |
| CN117672435A (en) * | 2024-01-31 | 2024-03-08 | 广元水木新材料科技有限公司 | Automatic fiber yarn layout method and system based on nanofiber preparation |
| CN117672435B (en) * | 2024-01-31 | 2024-04-09 | 广元水木新材料科技有限公司 | Automatic fiber yarn layout method and system based on nanofiber preparation |
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