CN116446182A - Super-hydrophobic fabric and preparation method and application thereof - Google Patents
Super-hydrophobic fabric and preparation method and application thereof Download PDFInfo
- Publication number
- CN116446182A CN116446182A CN202310308129.8A CN202310308129A CN116446182A CN 116446182 A CN116446182 A CN 116446182A CN 202310308129 A CN202310308129 A CN 202310308129A CN 116446182 A CN116446182 A CN 116446182A
- Authority
- CN
- China
- Prior art keywords
- fabric
- hydrophobic
- super
- silicone oil
- modified cellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004744 fabric Substances 0.000 title claims abstract description 250
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 229920002678 cellulose Polymers 0.000 claims abstract description 92
- 239000001913 cellulose Substances 0.000 claims abstract description 92
- 229920000742 Cotton Polymers 0.000 claims abstract description 74
- 229920002545 silicone oil Polymers 0.000 claims abstract description 63
- 239000002159 nanocrystal Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 13
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 229920003043 Cellulose fiber Polymers 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 4
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 3
- PMQIWLWDLURJOE-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F PMQIWLWDLURJOE-UHFFFAOYSA-N 0.000 claims description 3
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004627 regenerated cellulose Substances 0.000 claims description 2
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims description 2
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 claims description 2
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 10
- 238000005096 rolling process Methods 0.000 abstract description 5
- 238000002791 soaking Methods 0.000 abstract description 5
- 239000000675 fabric finishing Substances 0.000 abstract description 2
- 238000009962 finishing (textile) Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 74
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 27
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 22
- 238000000926 separation method Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 18
- 239000003921 oil Substances 0.000 description 16
- 235000019198 oils Nutrition 0.000 description 16
- 239000010410 layer Substances 0.000 description 13
- 230000035699 permeability Effects 0.000 description 12
- 239000000725 suspension Substances 0.000 description 11
- 239000000835 fiber Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 235000019476 oil-water mixture Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 244000137852 Petrea volubilis Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- -1 heptadecafluorodecyl Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000647 material safety data sheet Toxicity 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 125000005371 silicon functional group Chemical group 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/05—Cellulose or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The invention discloses a super-hydrophobic fabric, a preparation method and application thereof, wherein the super-hydrophobic function is realized through the cooperation of modified cellulose nanocrystalline and an organosilicon waterproof agent, the fabric has particularly excellent hydrophobic performance, and the preparation method is simple. Firstly, modifying cellulose nanocrystals by heptadecafluorodecyl trimethoxy silane, and dispersing the modified cellulose nanocrystals in a solution containing hydroxyl silicone oil and hydrogen silicone oil; soaking cotton fabric, taking out, and drying to obtain super-hydrophobic fabric; the surface super-hydrophobic layer is composed of modified cellulose nanocrystalline cooperated with organic silicon, the fabric finished by the silicone oil containing modified CNCs shows perfect super-hydrophobic property, the contact angle reaches 169.3 degrees, and the rolling angle reaches 4.9+/-0.1 degrees. The fabric finishing process is completed at room temperature, the production and preparation process is simple, the reaction condition is mild, the operation is safe, and the expansion production is easy.
Description
Technical Field
The invention relates to a super-hydrophobic fabric and a preparation method thereof, in particular to a preparation method of the super-hydrophobic fabric by an impregnation method, wherein a fiber surface layer of the impregnated super-hydrophobic fabric is a modified cellulose nanocrystalline synergistic organic silicon coating; belongs to the technical field of functional textiles and preparation thereof.
Background
Cellulose is the oldest and most abundant biomass material on earth, which is formed by plants through photosynthesis, which is the most basic framework material for all plants, and it is estimated that the total amount of cellulose produced by plants on earth exceeds five thousand billion tons, which is the most concise, most common renewable resource. Cellulose belongs to natural polysaccharide polymers, countless cellulose polymer chains are intertwined and are arranged together in a relative sequence to form cellulose fibers. The hydroxyl groups in the cellulose polymer chain are bonded with the hydrogen atoms on the hydroxyl groups in the adjacent polymers in the form of hydrogen bonds to form compact crystalline regions, and only a small number of amorphous regions exist in the cellulose fibers. The cellulose nanometer material belongs to natural high molecular materials, and is different from inorganic nanometer materials, the inorganic nanometer materials generally have stable and single chemical molecular composition and structural form, the cellulose nanometer materials have various properties and structures, and not only is the physical size of cellulose fiber simply changed in a nanometer way, but also the performance of the cellulose nanometer material is far superior to the performance of cellulose per se due to the fact that the high molecular form and molecular weight of the cellulose nanometer material are greatly changed, and the activity of functional groups is also enhanced.
In the context of sustainable development, research cost-effective and environmentally friendly superhydrophobic surfaces have attracted increasing scientific interest. However, practical application of superhydrophobic surfaces is still hampered by the complex and costly preparation process. Constructing superhydrophobic surfaces by mimicking the "lotus effect" is a research hotspot for materials science. Typically, nanoparticles (ZnO, siO 2 、TiO 2 Carbon nanotubes) are fixed on the surface of the substrate by sol-gel, electrostatic spinning, 3D printing and other modes, and are used for constructing the superhydrophobic surface. However, widely used inorganic nanoparticles are expensive and may cause environmental pollution.
Disclosure of Invention
The invention adopts an impregnation-drying method to prepare the super-hydrophobic surface. And selecting a fabric as a base material, and loading the modified cellulose nanocrystalline on the surface of the fabric. Firstly, silane is grafted on the surface of cellulose nanocrystalline through chemical reaction and dispersed in organosilicon treatment liquid to form fabric finishing liquid. And (3) after the fabric is immersed in the finishing liquid, heating and curing in an oven to obtain the super-hydrophobic fabric. The method prepares the cellulose nanocrystalline-fiber composite material only by a simple dipping-drying method, and the fibers and the nanoparticles are connected very stably through covalent bonds.
The technical scheme for realizing the aim of the invention is as follows:
a super-hydrophobic fabric comprises a fabric and a surface finishing layer thereof, wherein the finishing layer comprises a modified cellulose nanocrystalline roughening layer and an organosilicon film layer. The substrate of the super-hydrophobic fabric is cellulose fiber base fabric, including cotton, hemp and regenerated cellulose fiber base fabric or blended fabric of any two of the above; the surface finishing layer of the fabric is composed of modified cellulose nanocrystalline cooperated with organic silicon, and the super-hydrophobic fabric is formed by the coaction of the cellulose nanocrystalline by constructing a rough morphology and a low-surface energy substance.
The invention prepares the super-hydrophobic surface by a dipping-drying strategy, selects the fabric as a cellulose fiber base material, and ensures firm combination of the base material and the cellulose nanometer crystal boundary surface. The invention constructs a rough morphology on the surface of a cellulose-based fabric by modified cellulose nanocrystalline, and forms a hydrophobic coating with an organosilicon film. The coating structure is schematically as follows:
wherein R1 comprises tridecafluorooctyl, heptadecafluorodecyl, octadecyl and hexadecyl; m represents a repeating unit, preferably 20 to 200.
According to the super-hydrophobic fabric, modified cellulose nanocrystals are loaded on the surface of fabric fibers. Due to the existence of Van der Waals force between the cellulose nanocrystals and the cellulose fiber substrate, the cellulose nanocrystals are agglomerated and coated on the surface of the fiber, so that the roughness of the surface of the fabric is greatly increased. The improvement of the surface roughness of the fiber cooperates with the low surface energy of the organic silicon in the surface film layer to provide the superhydrophobic function under the combined action.
In the invention, the cellulose nano material has the advantages of reproducibility, low density, biocompatibility and degradability, and simultaneously has high specific strength and high specific surface area, and the surface of the cellulose nano material is provided with a large number of hydroxyl groups, so that the cellulose nano material can be subjected to chemical modification based on the hydroxyl groups to prepare the functional material with excellent performance. The modified cellulose nanocrystals are fluorine-containing silane or fluorine-free silane modified cellulose nanocrystals; the organic silicon comprises hydrogen-containing silicone oil and hydroxyl silicone oil. Preferably, the fluorine-containing silane comprises one or more of tridecafluorooctyl trimethoxysilane, tridecafluorooctyl triethoxysilane, heptadecafluorodecyl trimethoxysilane and heptadecafluorodecyl triethoxysilane; the fluorine-free silane comprises one or more of octadecyl trimethoxy silane, octadecyl triethoxy silane, hexadecyl trimethoxy silane or hexadecyl triethoxy silane. The mass ratio of the fluorine-containing silane or the fluorine-free silane to the cellulose nanocrystalline is (2-8) to 1, preferably (4-6) to 1.
The invention discloses a preparation method of the super-hydrophobic fabric, which comprises the steps of immersing the fabric in a solution containing modified cellulose nanocrystalline and organic silicon, and then taking out and drying the fabric to obtain the super-hydrophobic fabric.
In the invention, modified cellulose nanocrystalline is dispersed in organosilicon treatment liquid to obtain solution containing modified cellulose nanocrystalline and organosilicon; the organic silicon treatment liquid comprises hydrogen-containing silicone oil, hydroxyl silicone oil, a solvent and a catalyst; the modified cellulose nanocrystalline is added into the organosilicon treating fluid in the form of modified cellulose nanocrystalline dispersion liquid. The mass ratio of the hydroxyl-terminated silicone oil to the hydrogen-containing silicone oil is (0.5-5) to 1, preferably (1-2) to 1. The sum of the dosages of the modified cellulose nanocrystalline, the hydrogen-containing silicone oil and the hydroxyl silicone oil and the volume ratio of the solvent are (0.01-0.1) g to (0.1-0.5) g to 50mL, preferably (0.03-0.06) g to (0.2-0.4) g to 50mL.
As an example, the preparation method of the superhydrophobic fabric of the invention comprises the following steps:
(1) Adding a silane coupling agent (containing fluorine or not containing fluorine) into the mixture of ethanol and water, regulating the pH value, adding cellulose nanocrystalline, and stirring for reacting for a certain time; after the reaction is finished, centrifugally collecting and reacting to obtain modified cellulose nanocrystalline, and cleaning with ethanol to remove excessive unreacted silane coupling agent;
(2) Taking hydroxyl silicone oil and hydrogen silicone oil, and dispersing the hydroxyl silicone oil and the hydrogen silicone oil in an anhydrous alcohol solvent together with a catalyst to form an organosilicon treatment liquid; then adding the modified cellulose nanocrystalline, and stirring to form uniform dispersion liquid; soaking the fabric in the dispersion liquid for a certain time, taking out, and drying in an oven to completely remove the alcohol solvent to obtain the super-hydrophobic fabric; preferably, repeated dipping-drying is beneficial to completely covering the surface of the fabric with the silicone oil-modified cellulose nanocrystalline coating.
In the invention, in the step (1), the time for grafting modification (stirring reaction) of the cellulose nanocrystals is 1-8 hours, preferably 5-7 hours; in the step (2), the soaking time is 5 s-60 min, preferably 10 s-5 min, most preferably 10 s-60 s, and the soaking time refers to the soaking time each time; the number of times of impregnation is 1 to 10 times, preferably 2 to 5 times, and the number of times of drying is 1 to 10 times, preferably 2 to 5 times.
In the present invention, the impregnation is carried out under stirring; and (3) performing heat curing after the preferred dipping-drying to obtain the super-hydrophobic fabric.
In the invention, the alcohol solvent used in the organic silicon treatment fluid is any one or a mixture of any two of methanol, ethanol and isopropanol, and the catalyst is any one of dibutyltin dilaurate, tin acetylacetonate and manganese acetylacetonate; the dosage of the catalyst accounts for 1 to 5 percent of the total mass of the silicone oil.
According to the method, the fabric is selected as a base material only through a simple dipping-drying method, the groups are grafted on the surface of the cellulose nanocrystalline through chemical reaction and dispersed in the organosilicon low-surface-energy substance, and the cotton fabric is dipped and then crosslinked and cured in an oven to obtain the superhydrophobic fabric.
Compared with the prior art, the technical scheme provided by the invention has the beneficial effects that:
1. the fiber surface of the super-hydrophobic fabric is firmly combined between cellulose fibers and cellulose nanocrystalline particles, and the silicon functional groups connected to the surface of the cellulose nanocrystalline particles and the outermost organosilicon coating can be bonded through covalent bonds, so that the combination is very stable, and the finished fabric is water-resistant.
2. The super-hydrophobic fabric prepared by the method combines the unique advantages of softness, ventilation, multiple specific surface areas, multiple pores and adjustable structural performance of the fabric, and has very important significance for improving the wearability, multifunction and additional value application prospect of the fabric.
3. The super-hydrophobic fabric prepared by the method has excellent chemical durability and mechanical stability, which is very important for finishing the fabric in severe environment.
4. The preparation method provided by the invention has the advantages that the superhydrophobic fabric is prepared by a simple dipping-drying process, the production method is simple, the reaction condition in the production process is mild, the operation is easy, and the large-scale production and the popularization are easy.
Drawings
Fig. 1 is a diagram of a process for preparing a superhydrophobic fabric.
Fig. 2 is a Scanning Electron Microscope (SEM) image of a raw cotton fabric with wrinkles on the surface.
Fig. 3 is a Scanning Electron Microscope (SEM) image (a) of unmodified cellulose nanocrystals, and a Scanning Electron Microscope (SEM) image (B) of modified cellulose nanocrystals of example one.
Fig. 4 is a Scanning Electron Microscope (SEM) image of a cotton fabric finished with silicone oil (modified cellulose nanocrystals added) of example one.
FIG. 5 is the Water Contact Angle (WCA) values of cotton fabric after finishing with silicone oil (modified cellulose nanocrystals added) of example one.
Fig. 6 is EDS for cotton fabric after finishing with silicone oil (modified cellulose nanocrystals added) of example one.
Fig. 7 is a mechanical stability test of cotton fabric after finishing with silicone oil (modified cellulose nanocrystals added) example one: a sand paper abrasion test process (a) and a picture (b) of the contact angle changing along with the abrasion period; tape peel test procedure (c); trend of contact angle with the adhesive cycle (d).
Fig. 8 is a Scanning Electron Microscope (SEM) image of a cotton fabric finished with the example disiloxane and added with modified cellulose nanocrystals.
FIG. 9 is the Water Contact Angle (WCA) values of cotton fabrics finished with the silicone oil of the example and with modified cellulose nanocrystals added.
Fig. 10 is the Water Contact Angle (WCA) value of cotton fabric finished with the silicone oil of example and added with modified cellulose nanocrystals.
FIG. 11 is a Scanning Electron Microscope (SEM) image of a cotton fabric finished with a silicone oil of comparative example.
FIG. 12 is the Water Contact Angle (WCA) values of cotton fabric finished with silicone oil of comparative example.
Fig. 13 is the change in contact angle of the finished fabric at different silicone oil ratios: the amount of hydroxyl-terminated silicone oil was fixed at 0.2g (a); the amount of hydrogen-containing silicone oil was fixed at 0.1g (b).
Fig. 14 shows the contact angle change (b) after finishing the fabric at different contents (a) of modified CNCs and different times of impregnation.
FIG. 15 is a self-cleaning (chalk powder (a 1-a 3) and methylene blue powder (b 1-b 3)) and stain resistance test (c 1-c 3) image of finished cotton fabric.
FIG. 16 is a separation of n-heptane/water mixture (a 1-a 4) and carbon tetrachloride/water mixture (b 1-b 4) using a superhydrophobic coated fabric oil-water mixture; a coated fabric was used to remove n-heptane (c 1-c 3) floating on the water surface and carbon tetrachloride layer sinking to the water bottom.
Fig. 17 is a graph showing the relationship (b) between the separation efficiency (a) of 10 cycles of oil-water separation and the adsorption capacity of the cotton fabric after finishing, which was subjected to 40 separation cycles.
Fig. 18 is a graph showing WCA values (c) at different times and WCA values (d) at different pH for cotton fabrics after finishing at ph=3 (a), ph=12 (b), 1M NaCl soak.
Detailed Description
The invention discloses a super-hydrophobic fabric, which provides surface roughening for modified cellulose nanocrystals and low surface energy imparted by silicone oil, and provides a super-hydrophobic function under the synergistic effect of the modified cellulose nanocrystals. The super-hydrophobic fabric comprises a fabric, cellulose nanocrystals grafted with a hydrophobic chain segment and low-surface-energy substances provided by silicone oil; the super-hydrophobic fabric is formed by the combined action of rough morphology and low-surface energy substances. The cellulose nanocrystalline disclosed by the invention is introduced with a silicon-based functional group in the modification process, can have good compatibility with silicone oil in the treatment fluid, and has good compatibility and interface combination characteristics with a surface silicone oil film layer when a roughened morphology is formed, so that the process and application performance are excellent.
Referring to fig. 1, the superhydrophobic fabric is obtained by a simple dipping and drying strategy, cellulose nanocrystals are modified by silane, then the modified cellulose nanocrystals are dispersed in an organosilicon treatment liquid, and then a cellulose-based fabric is dipped for a certain time and dried at a certain temperature to obtain a product.
The technical scheme of the invention is further described below with reference to the accompanying drawings and examples, wherein the raw materials are conventional commodities, the raw material cotton fabric is hydrophilic fabric (100% desizing, see fig. 2), and the hydrogen-containing silicone oil is 1.6% hydrogen; specific preparation operations and tests are conventional techniques, and experiments are carried out in air unless otherwise specified.
And (5) preparing cellulose nanocrystals. Cutting absorbent cotton into small pieces of 2-5mm, treating with 5% NaOH (w/w) water solution for 4 hr, and stirring at normal temperature (weight ratio of cotton to NaOH water solution is 1:100). The treated cotton was then thoroughly washed with deionized water and repeated 5 times to ensure complete washing of the caustic soda and neutral PH, and the washed cotton was then dried overnight in an oven at 60 ℃. Under the condition of 64% sulfuric acid hydrolysis (acid slurry ratio is 9 mL/g), the treatment temperature is kept at 50 ℃ and stirred for 2 hours, and the influence of hydrolysis time on hydrolysis is examined. The cotton to acid ratio was maintained at 1:20.5 times of water was used to dilute and stop the reaction, which was maintained until the suspension was delaminated. The suspension at 8000 rpm was used as a starting material and centrifuged for 10 minutes. The collected samples were dialyzed into deionized water to neutrality. And finally, freeze-drying the sample at the temperature of minus 60 ℃ for 48 hours to obtain the cellulose nanocrystalline powder.
Example 1
Cellulose nanocrystalline modification. 2.8g of heptadecafluorodecyl trimethoxysilane is added dropwise into a stirred mixture of 60 mL ethanol/water (V (ethanol): V (water) =9:1) at room temperature, the pH is regulated to 5 by glacial acetic acid, then the mixture is transferred to a reaction kettle, 0.5g of cellulose nanocrystalline powder is added, the mixture is continuously stirred for 30 min, the temperature is raised to 85 ℃ and reacts for 6 hours under the protection of nitrogen, after the reaction is finished, the precipitate after the reaction is collected by centrifugation and is washed by ethanol, the washed product is centrifuged for 10min at 4000 r/min, and the supernatant is removed, so that a modified CNCs (F-CNCs) suspension (dispersion liquid, the solid content of which is 4.95 percent, g/g) is obtained. In fig. 3, (a) is a Scanning Electron Microscope (SEM) image of unmodified cellulose nanocrystals, and (b) is a Scanning Electron Microscope (SEM) image of modified cellulose nanocrystals, the average particle size of which is 380nm, and the average particle size of which is 873nm.
And (3) preparing the super-hydrophobic fabric. 0.2. 0.2g of hydroxyl-terminated silicone oil (average molecular weight: 5000, viscosity: 100 cps), 0.1. 0.1g of hydrogen-containing silicone oil (average molecular weight: 2000, viscosity: 60 cps), and 0.01. 0.01g of dibutyltin dilaurate were completely dispersed in an anhydrous isopropanol solution of 50mL, and then a modified CNCs suspension of 1g was added thereto, and stirred to form a uniform dispersion. A piece of the original fabric of 5 cm ×5 cm was immersed in the above dispersion for 15 s, then taken out, dried in an oven at 80 ℃ for 10min, and the process (immersing-drying) was repeated 2 more times; the impregnation process is carried out with conventional stirring. Finally, curing the fabric dried for the 3 rd time at 80 ℃ for 1 h to obtain the super-hydrophobic fabric. Fig. 4 is a Scanning Electron Microscope (SEM) image of cotton fabric after silicone oil finishing (modified cellulose nanocrystalline addition).
Contact angle test. The contact angle test is carried out on the finished cotton fabric by adopting a DSA100 type full-automatic microscopic liquid drop wettability measuring instrument of German Kruss company, water is selected as a test liquid drop, the liquid drop volume is 5 mu L, and the average value is obtained after 5 times of test. Fig. 5 is the Water Contact Angle (WCA) value of cotton fabric after silicone oil finishing (modified cellulose nanocrystals added). The water contact angle of the cotton fabric after finishing is 169.3 degrees, and the rolling angle is 4.9 degrees, which shows that the cotton fabric after modified finishing has super-hydrophobic performance.
EDS energy spectrum test. The components of the finished cotton fabric were analyzed by EDS spectroscopy, and FIG. 6 shows the content and distribution of the finished EDS elements. The non-finished cotton fabric only contains C, O, H elements, and Si and F elements appear in the finished cotton fabric, and the percentage content of the Si and F elements is 8.75 percent and 8.44 percent, which indicates that the modified cellulose nanocrystalline is successfully attached to the surface of the fabric.
The sandpaper wears. The stability and fastness of the finished fabrics were characterized by the sandpaper abrasion test. The abrasion test method of the sand paper comprises the following steps: the finished fabric was cut to the appropriate size, the sample was placed face down on 600 mesh sandpaper, a weight of 100 g was loaded, one end of the sample was held with forceps to move 100 mm in the horizontal direction, and then returned to 100 mm, completing a wear cycle. Fig. 7 is a sandpaper abrasion contact angle of cotton fabric after silicone oil finishing (modified cellulose nanocrystalline addition), with a hydrophobic angle of 167.1 ° after 10 abrasion cycles. The adhesive tape was applied to the coated surface with a load and then peeled off from the coated surface, showing the relationship between the coating wettability and the number of tape peels. After ten adhesion tests, the contact angle was reduced from 169.3 ° to 152.9 °, and the superhydrophobicity was still maintained.
Fabric air permeability test. And (3) carrying out air permeability characterization on raw cotton and finished cotton fabric by adopting a full-automatic air permeability meter (YG 461G). Test pressure: 200 Pa, test area: 20 cm 2 Caliber: 4 phi. Each sample was tested 5 times to average. The average value of the air permeability of the raw cotton fabric is 390.8mm/s, the average value of the air permeability of the finished cotton fabric is 348.8mm/s, and the air permeability is reduced by only 10.7 percent compared with that of the untreated cotton fabric. While finishing cotton fabrics, it is desirable to impart excellent superhydrophobicity to the fabrics without affecting the wearability of the cotton fabrics, and to have a certain mechanical fastness, so as to widen the practical application of the cotton fabrics. The whiteness, the stiffness and the breaking strength of the finished fabric are tested, the whiteness of raw cotton is 88.3 percent, the whiteness of the finished cotton fabric is 88.8 percent, the whiteness is almost unchanged before and after finishing, and particularly, the influence of the impregnation finishing of the invention on the air permeability of the fabric is very low; the bending rigidity and breaking strength of cotton fabrics before and after finishing are respectively tested, and the flexibility of raw cotton is 10.7 mm and the breaking strength is 391.38 mNThe result of the cotton fabric after finishing per cm is 11.3 mm and the breaking strength is 492.4 mN per cm. Therefore, the invention improves the wearability of cotton fabrics by coating finishing.
The surface pores of the emulsion finishing fabric prepared in the prior art are reduced, the channel of gas molecules penetrating through the fabric is closed, the air permeability of the fabric is obviously reduced, the reduction reaches 23%, and the whiteness is reduced from the initial 85.5% to 72.2%. In the prior art, nano silicon dioxide particles (SNP) are adopted to improve the surface roughness structure of the fabric, and ethylenediamine tetraacetic acid (EDTA) is introduced to improve the durability of the super-hydrophobic fabric, so that the air permeability of the prepared fabric is reduced by 50%. In the prior art, a uniform and compact film is directionally deposited on the surface of the fabric in situ by adopting electrochemical driving hydrosol, so that the cotton fabric has super-hydrophobic property, the hydrosol is electrochemically deposited to form a hydrophobic film, and the air permeability of the fabric is reduced by more than 20% after final treatment compared with that before treatment. The prior art uses nano TiO to make cotton fabric 2 After finishing, the hydrophobic organosilicon quaternary ammonium salt antibacterial agent is applied to the fabric in a single-sided discontinuous printing mode, so that the single-sided super-hydrophobic fabric is prepared, and the air permeability of the cotton fabric is reduced by 20%. The comparison shows that the air permeability of the super-hydrophobic fabric prepared by the invention is slightly reduced.
Thermal performance testing. The initial degradation temperature of raw cotton and coated fabric is almost maintained at about 320 ℃ according to a TGA curve (heating rate is 10 ℃/min, test atmosphere is nitrogen, and temperature range is 30-600 ℃). The quality of the raw cotton fabric is rapidly degraded because as the temperature increases, the crystallization area in the raw cotton fiber is broken down to generate intermediate products such as glucose and gas. The final decomposition temperature was 437℃and the corresponding carbon residue was 9.46%. The thermal stability of the cotton fabric is greatly improved due to the existence of the silicone oil composite structural film with good thermal stability, the thermodynamic curve of the cotton fabric after finishing deviates rightward, the final degradation temperature is about 466 ℃, the carbon residue rate is 11.30%, and compared with the raw cotton fabric, the carbon residue rate is improved, and the stability is good.
The superhydrophobic coated fabric is subjected to a rubbing test of a soaping-resistant and rubbing-resistant fastness meter, the change of the contact angle value of the coated fabric to water is observed, and when the washing (standard synthetic detergent concentration is 4 g/L, the temperature is 40 ℃, the time is 30 min for one cycle, and 10 steel balls are put) period reaches 3 times, the water contact angle of the surface of the fabric is reduced from 169.3 degrees to 148.3 degrees, and only about 13 percent is reduced, so that the good washing resistance of the coated fabric is indicated. After 2000 rubs using a rubbing fastness tester (YG 571-II) different from that of sandpaper, the contact angle was still 153.7 degrees, exhibiting good durability.
Example two
Cellulose nanocrystalline modification. The modified CNCs (F-CNCs) suspension was obtained in the same manner as in the example I except that heptadecafluorodecyl trimethoxysilane was replaced with 2.8g heptadecafluorodecyl triethoxysilane.
And (3) preparing the super-hydrophobic fabric. 0.2g of a hydroxy silicone oil (number average molecular weight: 3200, viscosity: 80 cps), 0.1g of a hydrogen-based silicone oil (number average molecular weight: 2000, viscosity: 60 cps), 0.01g of dibutyltin dilaurate were completely dispersed in an anhydrous isopropanol solution of 50mL, and then, a modified cellulose nanocrystal suspension of 1g was added, followed by stirring to form a uniform dispersion. A piece of the original fabric of 5 cm ×5 cm was immersed in the above dispersion for 15 s, then taken out, dried in an oven at 80 ℃ for 10min, and the process (immersing-drying) was repeated 1 time; the dipping process should be performed under stirring; and curing the fabric dried for the 2 nd time at 80 ℃ for 1 h to obtain the super-hydrophobic fabric. Fig. 8 is a Scanning Electron Microscope (SEM) image of a cotton fabric finished with silicone oil and added with modified cellulose nanocrystals. Fig. 9 is the Water Contact Angle (WCA) value of cotton fabric finished with silicone oil and modified cellulose nanocrystals added. The water contact angle of the finished cotton fabric is 160 degrees, and the rolling angle is 9 degrees, which shows that the modified cotton fabric has super-hydrophobic performance.
Example III
Cellulose nanocrystalline modification. The heptadecafluorodecyl trimethoxysilane of example one was replaced with 2g octadecyltrimethoxysilane, and the remainder were the same, to obtain a modified CNCs (F-CNCs) suspension.
And (3) preparing the super-hydrophobic fabric. Referring to example one, the dipping-drying was repeated 5 times, and the fabric dried at 6 th time was cured at 80c for 1 h as the rest, to obtain a superhydrophobic fabric. Fig. 10 is the Water Contact Angle (WCA) value of cotton fabric finished with silicone oil and modified cellulose nanocrystals added. The water contact angle of the cotton fabric after finishing is 156 degrees, which indicates that the cotton fabric after modified finishing has hydrophobic property.
Comparative example one
And (3) preparing the super-hydrophobic fabric. Referring to example one, the modified cellulose nanocrystalline suspension was omitted: 0.2g of hydroxy silicone oil (number average molecular weight: 5000, viscosity: 100 cps), 0.1g of hydrogen-based silicone oil (number average molecular weight: 2000, viscosity: 60 cps), 0.01g of dibutyltin dilaurate were completely dispersed in an anhydrous isopropanol solution of 50 mL; a piece of the original fabric of 5 cm ×5 cm was immersed in the above solution for 15 s, then taken out, dried in an oven at 80 ℃ for 10min, and the process (immersing-drying) was repeated 2 times; the impregnation process is carried out with conventional stirring. Finally, the 3 rd dried fabric was cured at 80 ℃ for 1 h to give a hydrophobic fabric.
Fig. 11 is a Scanning Electron Microscope (SEM) image of a cotton fabric finished with silicone oil. Fig. 12 is a Water Contact Angle (WCA) value of cotton fabric after silicone oil finishing, and the water contact angle of cotton fabric after finishing is 140 °.
Comparative example two
Cellulose nanocrystalline modification. The heptadecafluorodecyl trimethoxysilane of example one was replaced with 2g phenyltrimethoxysilane, and the remainder were the same, to obtain a modified CNCs (F-CNCs) suspension.
And (3) preparing the super-hydrophobic fabric. Referring to example one, finally, the 3 rd dried fabric was cured at 80 ℃ for 1 h to obtain a hydrophobic fabric, and the water contact angle of the finished cotton fabric was 145 °. Indicating that the modified and finished cotton fabric has hydrophobic property.
Comparative example three
And (3) preparing the super-hydrophobic fabric. Referring to example one, the modified CNCs suspension of 1g was replaced with 0.05g of cellulose nanocrystalline powder (unmodified cellulose nanocrystalline), and the rest were the same, and the 3 rd dried fabric was cured at 80 ℃ for 1 h to obtain a hydrophobic fabric, and the water contact angle of the finished cotton fabric was 141 °.
Comparative example four
And (3) preparing the super-hydrophobic fabric. Referring to example one, only 0.3 of the hydroxyl-terminated silicone oil of g was used, the hydrogen-containing silicone oil was omitted, and the rest was the same, and the 3 rd dried fabric was cured at 80 ℃ for 1 h to obtain a hydrophobic fabric, and the water contact angle of the finished cotton fabric was 131.3 °.
And (3) preparing the super-hydrophobic fabric. According to the first reference example, only 0.3 g hydrogen-containing silicone oil is adopted, hydroxyl-terminated silicone oil is omitted, the rest is the same, the 3 rd dried fabric is solidified at 80 ℃ for 1 h, the hydrophobic fabric is obtained, the water contact angle of the finished cotton fabric is 142 degrees, the finished fabric becomes hard and brittle, and the flexibility of the fabric is lost.
Example IV
The amounts of hydroxyl terminated silicone oil (PHMS) and hydrogen containing silicone oil (MSDS) were varied based on the first example, and the water contact angles of the resultant fabrics were the same as the rest, as shown in FIG. 13. The method has the advantages that the fabric is finished by mixing and dissolving hydrogen-containing silicone oil and hydroxyl-terminated silicone oil in isopropanol in a certain proportion, a firm and flexible three-dimensional reticular structure film is formed on the surface of the fiber, and the hydrophobic performance of the fabric is obviously improved.
The amount of modified CNCs suspension was changed based on the first example, and the water contact angle of the resulting fabric was the same as the rest, as shown in fig. 14 a. On the basis of example one, the number of times of dipping-drying was changed, and the water contact angle of the resultant fabric was the same as that of the rest, see b in fig. 14.
Example five
The wettability of the superhydrophobic coated fabric (example one) was evaluated by WCA value and WSA value tests. The initial water contact angle of the super-hydrophobic coated fabric is 169.3 degrees, and after standing for 5min, 10min and 15 min, the water contact angle still reaches 168.2 degrees, 166.1 degrees and 162.3 degrees, so that the coated fabric is proved to be super-hydrophobic and has good water repellency stability.
Example six
A coated fabric prepared by the method of the example is exemplified.
In order to study the self-cleaning performance of the finished cotton fabric, methylene blue powder and chalk powder are used as pollutants. As shown in fig. 15, the superhydrophobic coated fabric was fixed on a glass slide surface and placed obliquely on a glass dish. As the water drops fall down, contaminants adhering to the fabric are carried away as the water drops roll down, and it is clear from the figure that the fabric surface is not contaminated with contaminants. In addition, the stain resistance of the superhydrophobic coated fabric was also tested, and the coated fabric was immersed in methylene blue-dyed water and then removed from the water, and found that the fabric was not stained with blue stains. The results show that the super-hydrophobic coated fabric prepared by the invention has excellent self-cleaning and anti-staining properties.
As shown in fig. 16, the oil-water separation performance after finishing the fabric was measured. First, n-heptane and carbon tetrachloride were dyed with oil red to represent oils and organic solvents with densities less than and greater than water, respectively. When the superhydrophobic coated fabric is contacted with an n-heptane layer floating on the water surface, the coated fabric rapidly absorbs the n-heptane layer on the water surface clean due to its excellent lipophilicity and the rough structure of the surface. Also, carbon tetrachloride can be absorbed cleanly by putting the coated fabric under the water surface with tweezers to contact with the carbon tetrachloride oil layer, and meanwhile, the excellent hydrophobicity ensures that no water drops are attached to the coated fabric when the coated fabric is taken out of the water. The adsorption capacity of the finished fabric to carbon tetrachloride and n-heptane can reach 4.50 times and 2.67 times of the self-quality. Meanwhile, the repeated oil absorption recycling performance of the coated fabric is researched, and the super-hydrophobic coated fabric prepared by the method has better recycling performance. After 40 oil absorption-separation cycle experiments, the absorption capacity of the super-hydrophobic coated fabric to the oil phase is basically unchanged, which indicates that the basic structure of the super-hydrophobic coated fabric is not destroyed after 40 oil absorption-separation cycle experiments. And meanwhile, the coated fabric absorbed with the oil is directly washed by ethanol and then dried, so that the coated fabric can be reused. The coated fabric prepared by the method has practicability in the oil spilling field and the water body purifying field.
It is often not sufficient to immerse the coated fabric directly in an oil-water mixture to absorb oil to achieve oil-water separation. The separation of the large amount of the oil-water mixture allows for the filtration of the oil-water mixture with a two-dimensional material like a fabric. In this experiment, the separation performance of the finished fabric was evaluated by an oil-water separator, and as can be seen from fig. 16, a measuring cylinder was filled with 10 ml methylene blue dyed deionized water and 10 ml oil red dyed oil phase, and injected into an oil-water separator, and when it contacted the coated fabric, the oil droplets were rapidly absorbed and collected in a conical flask below, while being impermeable to water, and remained on top of the coated fabric, thereby achieving separation of the oil phase and the water phase. In the experiments, two incompatible oil-water mixtures (n-heptane/water mixture and carbon tetrachloride/water mixture) were used to perform the oil-water separation experiments. When a mixture of n-heptane and water is poured onto the surface of the coated fabric, the n-heptane, because of its lower density than water, is first poured from the cylinder, contacts and immediately wets the surface of the coated fabric, and quickly flows down through the coated fabric, with water trapped above the coated fabric. The difference compared to the separation experiments of carbon tetrachloride/water mixtures is that the order in which the aqueous or oil phase is poured from the measuring cylinder is different. Carbon tetrachloride has a higher density than water, so that the water phase contacts the surface of the superhydrophobic fabric and is trapped, and when carbon tetrachloride is poured onto the surface of the superhydrophobic fabric, the carbon tetrachloride with the higher density quickly penetrates through the water layer to contact the surface of the coated fabric and flows into the conical flask, and no water is apparent to penetrate. The hydrophobic and oleophilic properties of the superhydrophobic coated fabric are determining factors for the formation of oil-water separation. As shown in FIG. 17, after 10 separation cycles, the coated fabric still has higher separation efficiency, can reach more than 99%, and shows good oil-water separation performance and circulation capacity.
The chemical durability of the finished fabric plays a critical role in practical application, and the super-hydrophobic fabric also often faces the challenge of severe environment in practical application. The coated fabrics were tested for WCA testing using 5 μl of water droplets at different pH (ranging from 2 to 14), and the results in fig. 18 show that the coated fabrics all exhibited superhydrophobicity over the ph=2 to 14, with WCA values greater than 150 °. The coated fabric 30 h was treated with strong acid and alkali solutions having ph=3 and 12, and the change in WCA value was measured, and thus the long-term durability of the coated fabric was evaluated. After the acid treatment of 30 h, the WCA value of the coated fabric was still higher than 150 °, and the hydrophobicity was still maintained. After alkaline conditions of 30 h, the WCA value of the coated fabric was reduced to below 150 °, but still above 120 °, indicating that the coated fabric still had hydrophobic properties. After 30 h treatment with 1M NaCl solution, the WCA also remained above 150℃and still exhibited good hydrophobicity. This shows that the prepared coated fabric has good stability, and the super-hydrophobic coated fabric prepared by the method can be used in severe environments.
The surface of the raw cotton fabric has a plurality of gully-shaped structures and a certain rough feeling, and meanwhile, water drops contact the surface of the cotton fabric because of the hydrophilicity of the cotton fabric, so that the fabric can be quickly infiltrated. The surface of the fabric finished by the silicone oil becomes very smooth, the fiber is coated with a layer of film, the hydrophobic angle of the fabric finished by the silicone oil can reach 140 degrees, and the fabric has no rolling angle, but is not super-hydrophobic, the fabric finished by the silicone oil containing the modified CNCs shows perfect super-hydrophobic, the contact angle reaches 169.3 degrees, the rolling angle is 4.9+/-0.1 degrees, cellulose nanocrystalline is fixed on the surface of the fiber, and a plurality of nano particles are coagulated together due to the action of covalent bonds, van der Waals force and hydrophobic force. The oil-water separation test is carried out on the coated fabric, and the separation efficiency can still reach more than 99% after ten oil-water separation cycles. After the fabric is treated for 30 h times under the conditions of acid (pH=3), alkali (pH=13) and 1M NaCl, sand paper is circularly rubbed for 50 times, adhesive tape is adhered for 10 times, and the fabric still has good hydrophobic property after being circularly rubbed for 2000 times by a rubbing fastness meter and after being soaped for 3 times, and has excellent stability and circulation capacity. Meanwhile, the super-hydrophobic fabric also has good application prospect in the fields of self-cleaning, anti-contamination, oil absorption and oil-water separation.
Claims (10)
1. The super-hydrophobic fabric comprises a fabric and a surface finishing layer thereof, and is characterized in that the finishing layer comprises a modified cellulose nanocrystalline roughened layer and an organosilicon film layer.
2. The superhydrophobic fabric of claim 1, wherein the fabric comprises a cotton, hemp, regenerated cellulose fiber-based fabric, or a blend of any two of the foregoing.
3. The superhydrophobic fabric of claim 1, wherein the modified cellulose nanocrystals are fluorosilane-modified cellulose nanocrystals or non-fluorosilane-modified cellulose nanocrystals; the organic silicon comprises hydrogen-containing silicone oil and hydroxyl silicone oil.
4. The superhydrophobic fabric of claim 3, wherein the fluorine-containing silane comprises one or more of tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane; the fluorine-free silane comprises one or more of octadecyl trimethoxy silane, octadecyl triethoxy silane, hexadecyl trimethoxy silane or hexadecyl triethoxy silane.
5. The method for preparing the super-hydrophobic fabric according to claim 1, wherein the fabric is immersed in a solution containing modified cellulose nanocrystals and organic silicon, and then taken out and dried to obtain the super-hydrophobic fabric.
6. The method for preparing the superhydrophobic fabric according to claim 5, wherein modified cellulose nanocrystals are dispersed in an organosilicon treatment liquid to obtain a solution containing modified cellulose nanocrystals and organosilicon; the organic silicon treatment fluid comprises hydrogen-containing silicone oil, hydroxyl silicone oil, a solvent and a catalyst.
7. The method for preparing a superhydrophobic fabric according to claim 6, wherein the solvent is any one or more of methanol, ethanol, and isopropanol; the catalyst is one of dibutyl tin dilaurate, tin acetylacetonate and manganese acetylacetonate; the dosage of the catalyst accounts for 1 to 5 percent of the total mass of the silicone oil.
8. The method for preparing a superhydrophobic fabric according to claim 5, wherein the number of times of impregnation is 1 to 10 and the number of times of drying is 1 to 10.
9. Use of modified cellulose nanocrystals, organic silicon, for the preparation of the superhydrophobic fabric of claim 1.
10. Use of the superhydrophobic fabric of claim 1 in the preparation of a flexible hydrophobic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310308129.8A CN116446182A (en) | 2023-03-27 | 2023-03-27 | Super-hydrophobic fabric and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310308129.8A CN116446182A (en) | 2023-03-27 | 2023-03-27 | Super-hydrophobic fabric and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116446182A true CN116446182A (en) | 2023-07-18 |
Family
ID=87124826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310308129.8A Pending CN116446182A (en) | 2023-03-27 | 2023-03-27 | Super-hydrophobic fabric and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116446182A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116856194A (en) * | 2023-08-18 | 2023-10-10 | 齐鲁工业大学(山东省科学院) | Nanocellulose-based super-hydrophobic coating and preparation method thereof |
-
2023
- 2023-03-27 CN CN202310308129.8A patent/CN116446182A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116856194A (en) * | 2023-08-18 | 2023-10-10 | 齐鲁工业大学(山东省科学院) | Nanocellulose-based super-hydrophobic coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Facile and scalable fabrication of superhydrophobic and superoleophilic PDMS-co-PMHS coating on porous substrates for highly effective oil/water separation | |
| Deng et al. | Facile one-step preparation of robust hydrophobic cotton fabrics by covalent bonding polyhedral oligomeric silsesquioxane for ultrafast oil/water separation | |
| Foorginezhad et al. | Fabrication of stable fluorine-free superhydrophobic fabrics for anti-adhesion and self-cleaning properties | |
| Jannatun et al. | A facile cross-linking approach to fabricate durable and self-healing superhydrophobic coatings of SiO2-PVA@ PDMS on cotton textile | |
| Li et al. | Superhydrophobic/superoleophilic cotton fabrics treated with hybrid coatings for oil/water separation | |
| Xue et al. | Fabrication of superhydrophobic and superoleophilic textiles for oil–water separation | |
| Cao et al. | Robust fluorine-free superhydrophobic PDMS–ormosil@ fabrics for highly effective self-cleaning and efficient oil–water separation | |
| Chen et al. | Rosin acid and SiO2 modified cotton fabric to prepare fluorine-free durable superhydrophobic coating for oil-water separation | |
| Xu et al. | One-pot preparation of robust, ultraviolet-proof superhydrophobic cotton fabrics for self-cleaning and oil/water separation | |
| CN109837758B (en) | Preparation method of fabric super-hydrophobic surface | |
| CN110644240B (en) | Preparation method of multifunctional durable and self-repairing super-hydrophobic fabric surface | |
| Anjum et al. | Self-assembled nanomanipulation of silica nanoparticles enable mechanochemically robust super hydrophobic and oleophilic textile | |
| Wu et al. | Durable superhydrophobic and photocatalytic cotton modified by PDMS with TiO2 supported bamboo charcoal nanocomposites | |
| Zhang et al. | Design and fabrication of polydopamine based superhydrophobic fabrics for efficient oil–water separation | |
| Teng et al. | Robust superhydrophobic surface fabrication by fluorine-free method on filter paper for oil/water separation | |
| Yu et al. | Biomimetic fabrication of superhydrophobic loofah sponge: robust for highly efficient oil–water separation in harsh environments | |
| Lin et al. | Fabrication and performance of a novel 3D superhydrophobic material based on a loofah sponge from plant | |
| Yang et al. | A water-rich system of constructing durable and fluorine-free superhydrophobic surfaces for oil/water separation | |
| Yang et al. | A less harmful system of preparing robust fabrics for integrated self-cleaning, oil-water separation and water purification | |
| Li et al. | Durable superhydrophobic and oleophobic cotton fabric based on the grafting of fluorinated POSS through silane coupling and thiol-ene click reaction | |
| CN116446182A (en) | Super-hydrophobic fabric and preparation method and application thereof | |
| CN111888800B (en) | Grafting modified cotton material and preparation method and application thereof | |
| Jiang et al. | Synthesis of superhydrophobic fluoro-containing silica sol coatings for cotton textile by one-step sol–gel process | |
| Xie et al. | Facile fabrication of superhydrophobic polyester fabric based on rapid oxidation polymerization of dopamine for oil–water separation | |
| Wang et al. | Hydrophilic PVDF membrane with versatile surface functions fabricated via cellulose molecular coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |