CN114763676A - Fluoride-free waterproof breathable antibacterial finishing agent and preparation method and application thereof - Google Patents
Fluoride-free waterproof breathable antibacterial finishing agent and preparation method and application thereof Download PDFInfo
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- CN114763676A CN114763676A CN202210301422.7A CN202210301422A CN114763676A CN 114763676 A CN114763676 A CN 114763676A CN 202210301422 A CN202210301422 A CN 202210301422A CN 114763676 A CN114763676 A CN 114763676A
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- CN
- China
- Prior art keywords
- component
- finishing agent
- fluorine
- waterproof breathable
- free waterproof
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 105
- -1 polysiloxane Polymers 0.000 claims abstract description 83
- 239000004744 fabric Substances 0.000 claims abstract description 69
- 239000011505 plaster Substances 0.000 claims abstract description 57
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 57
- 238000002156 mixing Methods 0.000 claims abstract description 40
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 32
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 24
- 239000004094 surface-active agent Substances 0.000 claims abstract description 24
- 238000005303 weighing Methods 0.000 claims abstract description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- 239000000853 adhesive Substances 0.000 claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 37
- 239000000178 monomer Substances 0.000 claims description 26
- 238000005096 rolling process Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- 238000007598 dipping method Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 239000013067 intermediate product Substances 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 14
- 239000005052 trichlorosilane Substances 0.000 claims description 14
- DMZWVCJEOLBQCZ-UHFFFAOYSA-N chloro(ethenyl)silane Chemical compound Cl[SiH2]C=C DMZWVCJEOLBQCZ-UHFFFAOYSA-N 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- 229940075529 glyceryl stearate Drugs 0.000 claims description 5
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 4
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 4
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 4
- 229950011392 sorbitan stearate Drugs 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 2
- FUNOCWSUSIUVJO-UHFFFAOYSA-N but-1-enyl-chloro-methylsilane Chemical compound C[SiH](Cl)C=CCC FUNOCWSUSIUVJO-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 230000035699 permeability Effects 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000004753 textile Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 14
- 229910052731 fluorine Inorganic materials 0.000 description 14
- 239000011737 fluorine Substances 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 239000005871 repellent Substances 0.000 description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000675 fabric finishing Substances 0.000 description 6
- 238000009962 finishing (textile) Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000002940 repellent Effects 0.000 description 5
- YCMWEGOONYILCI-UHFFFAOYSA-N chloro-ethenyl-ethyl-methylsilane Chemical compound CC[Si](C)(Cl)C=C YCMWEGOONYILCI-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000175 potential carcinogenicity Toxicity 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 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
- D06M15/19—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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
- D06M11/42—Oxides or hydroxides of copper, silver or gold
-
- 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
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/152—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
-
- 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
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
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- 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
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- 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
- D06M15/53—Polyethers
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- 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
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- 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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to the field of preparation and application of textile chemicals, and discloses a fluorine-free waterproof breathable antibacterial finishing agent, and a preparation method and application thereof. The finishing agent comprises the following components: 60-80 parts of a component A, 5-10 parts of a component B and 30-50 parts of a component C; the component A comprises hyperbranched polysiloxane, a surfactant and an emulsifier; the component B comprises nano cuprous oxide, a silane coupling agent and an antioxidant; the component C is a polyurethane adhesive. Green and environment-friendly, low production cost, good waterproof and breathable finishing effect and long-acting antibacterial effect after treatment. The preparation method of the finishing agent comprises the steps of weighing and mixing raw materials. The finishing agent is applied to plaster cloth finishing to enhance the air permeability, the water repellency and the antibacterial property of the plaster cloth, and is easy for industrial production, simple in application method and low in cost.
Description
Technical Field
The invention relates to the field of preparation and application of textile chemicals, in particular to a fluoride-free waterproof breathable antibacterial finishing agent and a preparation method and application thereof.
Background
With the development of economy and technology, the pursuit of good life of people is continuously reflected in the aspects of object development. On the basis of the traditional fabric, besides the simple cold-dispelling and warm-keeping wearability, people also put forward many demands on the functionalized characteristics of the fabric, such as water repellency, oil repellency, air permeability, antistatic property, weather resistance, light weight, quick drying, ultraviolet resistance and the like. The fabric finishing agent is a finishing agent which can endow the fabric with some specific functional characteristics or special performance while keeping the original wearability.
For many years, researchers have conducted a great deal of research on functional finishing of fabrics, particularly water repellent functional finishing. Among the numerous water-repellent finishes, fluorine-containing water-repellent agents are currently the most widely used in fabric finishing. The water repellent fabric has excellent water and oil repellent characteristics, is washable, does not influence the original characteristics of the fabric, and is favored by manufacturers and consumers. At present, a great number of reports related to fluorine-containing fabric finishing agents exist, the production of the fluorine-containing fabric finishing agents is monopolized by foreign companies, and the fluorine-containing fabric finishing agents used in China mainly depend on foreign imports. However, the fluorine-containing monomer required in the fluorine-containing finishing agent is expensive, so that the cost of the fluorine-containing finishing agent is high. In addition, chemicals with potential carcinogenicity, such as perfluorooctanoic acid, perfluorooctanoic acid salts, perfluorooctane sulfonic acid and the like, are required in the production process of the fluorine-containing finishing agent, so that certain safety risk exists. Thus, there is a need for improvements over existing fluorochemical water repellent finishes.
Chinese patent publication discloses a water-based hollow fluorine-silicon composite water-repellent breathable fabric finishing agent and a preparation method thereof, the effective component of the finishing agent is a hollow fluorine-containing polyacrylate-siloxane composite polymeric polymer shell, and an organic silicon monomer is introduced in a free radical polymerization manner while the good water repellency of a C-F long-chain polymer emulsion is kept, so that the organic silicon monomer and the fluorine-containing monomer are subjected to a cross-linking synergistic effect, and the water resistance, the washing resistance and the softness of the fabric are enhanced. In addition, the unique hollow structure not only enhances the air permeability, but also improves the light scattering performance and reduces the cost. This improved process still requires the use of fluorine-containing ingredients in the finish and the manufacturing process is difficult to apply industrially. Chinese patent publication No. CN110205821A discloses a green fluorine-free waterproof finishing agent and application thereof in fiber products. The organic silicon water repellent finishing agent overcomes the defects of the existing product, is easy for industrial production, has simple application method and low cost, and has good application prospect and economic benefit. However, silicone finishes are required to overcome the problems of insufficient mechanical strength, poor adhesion, and no improvement in the antimicrobial or air permeability properties of the fabric surface.
Disclosure of Invention
The invention provides a fluorine-free waterproof breathable antibacterial finishing agent and a preparation method and application thereof, aiming at solving the problems that the conventional finishing agent has large using amount of fluorine-containing substances and the fluorine-free finishing agent is difficult to have the breathable antibacterial effect. The molecular topological structure of the hyperbranched polysiloxane is utilized to reduce the viscosity of the system, enhance the air permeability, and simultaneously improve the dispersibility and stability of the nano cuprous oxide of the antibacterial agent, thereby having long-acting antibacterial performance. The application in plaster cloth finishing can enhance the air permeability, water repellency and antibacterial property of the plaster cloth, and is easy for industrial production, simple in application method and low in cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
a fluoride-free waterproof breathable antibacterial finishing agent comprises the following components in parts by weight: 60-80 parts of a component A, 5-10 parts of a component B and 30-50 parts of a component C; the component A comprises hyperbranched polysiloxane, a surfactant and an emulsifier; the component B comprises nano cuprous oxide, a silane coupling agent and an antioxidant; the component C is a polyurethane adhesive.
For the fluorine-free waterproof breathable antibacterial finishing agent, the finishing agent is endowed with excellent waterproof performance by utilizing the organic silicon component, and the hyperbranched polysiloxane can fully utilize the highly branched molecular topological structure in the molecular structure, so that the problems that long-chain molecules of the traditional organic silicon finishing agent are easy to wind intermolecular chains and have poor viscosity are avoided, the viscosity of the finishing agent is reduced, and the use of the finishing agent is convenient. In addition, the hyperbranched polysiloxane structure also has more two-dimensional or three-dimensional network structures, and the tissue structure inside the fabric fiber can be changed after the solid gel is formed on the surface of the fabric, so that the gaps are enlarged and increased, and the air permeability of the fabric is improved. Meanwhile, nano cuprous oxide is added into the finishing agent as an antibacterial agent. The nano cuprous oxide has application in the aspect of oxidation resistance, but the long-acting antibacterial effect of the nano cuprous oxide is difficult to ensure because the nano cuprous oxide is easily oxidized in the using process. The hyperbranched polysiloxane surface in the finishing agent formula prepared by the invention has a certain amount of hydroxyl groups, so that the nano cuprous oxide can be bonded to the hyperbranched polysiloxane surface, on one hand, the nano cuprous oxide has better dispersibility, on the other hand, the oxidation of the nano cuprous oxide can be reduced, and the nano cuprous oxide can play an antibacterial role for a long time. The polyurethane-based adhesive can enhance the adhesion of the finish to the fabric surface, allowing the finish to adhere firmly to the fabric surface.
Preferably, the preparation method of the hyperbranched polysiloxane comprises the following steps:
(1) monomer synthesis: dissolving vinyl chlorosilane and a tertiary amine compound in a solvent, adding trichlorosilane, wherein the mass ratio of the vinyl chlorosilane to the tertiary amine compound to the trichlorosilane is (2-3): (4-5): 1, uniformly mixing, reacting at 20-25 ℃ for 12-18 h, filtering to remove precipitates, and distilling under reduced pressure to remove the solvent to obtain a monomer;
(2) polysiloxane synthesis: dissolving the monomer obtained in the step (1) in a solvent, adding a catalyst, stirring and reacting at 20-25 ℃ for 18-24 h, adding methanol with the volume 2-4 times of the total volume of the system, stirring, and filtering to obtain an intermediate product;
(3) hydroxyl end sealing: adding peroxybenzoic acid into the intermediate product obtained in the step (2), stirring and reacting for 2-4 h at 20-25 ℃, adding alkali to adjust the pH to 8-11, stirring and reacting for 1-2 h at 60-80 ℃, filtering, washing and drying to obtain the hyperbranched polysiloxane.
Under the alkaline condition of the tertiary amine compound, trichlorosilane and vinyl chlorosilane can generate a halogenated silane substitution reaction to prepare the monomer for synthesizing polysiloxane. In the process of synthesizing polysiloxane, a hydrosilylation reaction is utilized to enable a silicon-hydrogen bond and vinyl to generate an addition reaction, and multi-branched hyperbranched polysiloxane is generated. And then, converting vinyl at the end of the hyperbranched polysiloxane into epoxy by using peroxybenzoic acid, and then carrying out ring opening under an alkaline condition to obtain hydroxyl-end-sealed hyperbranched polysiloxane for the preparation process of the fluorine-free waterproof breathable antibacterial finishing agent.
Preferably, the vinyl chlorosilane is one of dimethylvinylchlorosilane, methylethylvinylchlorosilane, and methylvinyldichlorosilane, or a combination thereof, and the tertiary amine compound is one of tributylamine, trimethylamine, triethylamine, and dodecyldimethylamine.
Preferably, the catalyst is one of a Speier catalyst or a Karstedt catalyst, and the addition amount of the catalyst is 30-50 ppm. Platinum-based catalysts can catalyze hydrosilylation reactions.
Preferably, the mass ratio of the hyperbranched polysiloxane, the surfactant and the emulsifier in the component A is (90-95): 1-5, and the mass ratio of the nano cuprous oxide, the silane coupling agent and the antioxidant in the component B is (1-2): 5-10): 0-0.1. The addition of the surfactant and the emulsifier can enhance the compatibility of the hyperbranched polysiloxane in a system and reduce the viscosity of the system. The silane coupling agent can enhance the dispersibility and compatibility of the nano cuprous oxide. The antioxidant can prevent the nano cuprous oxide from being oxidized before the components are mixed.
Preferably, the surfactant is one or a combination of sodium dodecyl sulfate, sodium dodecyl sulfate and polyoxyethylene sorbitan fatty acid ester, the emulsifier is one or a combination of polyethylene glycol octyl phenyl ether, glyceryl stearate, sorbitan stearate and bis-PEG/PPG-14/14 polydimethylsiloxane, and the antioxidant is one of 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether and tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
A preparation method of a fluorine-free waterproof breathable antibacterial finishing agent comprises the following steps:
(a) component preparation: weighing and mixing hyperbranched polysiloxane, surfactant and emulsifier according to the mass ratio to obtain a component A; weighing and mixing nano cuprous oxide, a silane coupling agent and an antioxidant according to the mass ratio to obtain a component B;
(b) and (3) mixing finishing agents: weighing 60-80 parts of the component A, 5-10 parts of the component B and 30-50 parts of the component C polyurethane adhesive in parts by weight, and blending under stirring to obtain the fluorine-free waterproof breathable antibacterial finishing agent.
In the preparation process, the components are prepared according to the proportion respectively, and then are mixed and stirred uniformly at high speed to obtain the fluorine-free waterproof breathable antibacterial finishing agent. The preparation method is simple and convenient, and the formula does not contain fluorine-containing components, so that the cost can be reduced, and the possible environmental pollution caused by fluorine-containing processing aids can be avoided.
The application of the fluorine-free waterproof breathable antibacterial finishing agent in plaster cloth finishing comprises the steps of finishing the diluted fluorine-free waterproof breathable antibacterial finishing agent on the surface of plaster cloth by a two-dipping and two-rolling method, and then baking.
The common medical plaster cloth has poor waterproof and air-permeable performance and does not have an antibacterial function, and the fluoride-free waterproof air-permeable antibacterial finishing agent is adopted to finish the plaster cloth, so that the waterproof performance of the plaster cloth can be improved, and the problem of drug effect loss or even infection caused by water immersion in the use process is avoided. Meanwhile, the air permeability of the plaster cloth is improved, and better comfort is provided. The infection rate is reduced by the antibacterial component. The finishing agent can be fully attached to the surface of the plaster cloth by adopting a two-dipping and two-rolling method, so that a better finishing effect is obtained, and the industrial production is easy to realize.
Preferably, the concentration of the fluorine-free waterproof breathable antibacterial finishing agent is 8-12 g/L. The low concentration of the fluorine-free waterproof breathable antibacterial finishing agent can result in unobvious finishing effect, and the high concentration increases the production cost on one hand and is not beneficial to the uniform adhesion of the finishing agent on the other hand.
Preferably, the soaking time is 25-35 min, the rolling residual rate is 65-75%, the speed is 70-90 m/h, and the baking process comprises the steps of preheating for 2-3 min at 115-125 ℃, and baking for 20-40 s at 170-180 ℃.
Therefore, the invention has the following beneficial effects: (1) the provided fluoride-free waterproof breathable antibacterial finishing agent is green and environment-friendly, low in production cost, good in waterproof breathable finishing effect and capable of providing a long-acting antibacterial effect after treatment; (2) hyperbranched polysiloxane is used in the fluorine-free waterproof breathable antibacterial finishing agent, so that the viscosity of the finishing agent system is reduced through a branch structure, and the breathable finishing effect of the finishing agent is enhanced; (3) nano cuprous oxide is added as an antibacterial agent, and a large amount of hydroxyl on the surface of the hyperbranched polysiloxane is used for preventing the nano cuprous oxide from being rapidly oxidized and losing efficacy, so that a long-acting antibacterial effect is provided; (4) the application in plaster cloth finishing can enhance the air permeability, water repellency and antibacterial property of the plaster cloth, and is easy for industrial production, simple in application method and low in cost.
Detailed Description
The invention is further described below with reference to specific embodiments. It is to be understood that these embodiments are suitable for illustrating the basic principles, main features and advantages of the present invention, and the present invention is not limited by the scope of the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not noted are generally those used in routine experiments.
Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art.
Example 1
Preparation of mono-and hyperbranched polysiloxane
(1) Monomer synthesis: dissolving dimethylvinylchlorosilane and triethylamine in diethyl ether, adding trichlorosilane, uniformly mixing, reacting at 22 ℃ for 16h, filtering to remove precipitates, and distilling under reduced pressure to remove the solvent to obtain a monomer, wherein the mass ratio of dimethylvinylchlorosilane to triethylamine to trichlorosilane is 2:5: 1;
(2) polysiloxane synthesis: dissolving the monomer obtained in the step (1) in toluene, adding 40ppm Karstedt catalyst, stirring and reacting for 20 hours at 22 ℃, adding methanol with the volume 3 times of the total volume of the system, stirring and filtering to obtain an intermediate product;
(3) hydroxyl end sealing: adding peroxybenzoic acid into the intermediate product obtained in the step (2), stirring and reacting for 3h at 22 ℃, adding sodium hydroxide to adjust the pH value to 10, stirring and reacting for 2h at 70 ℃, filtering, washing and drying to obtain the hyperbranched polysiloxane.
Preparation of fluoride-free waterproof breathable antibacterial finishing agent
(a) Component preparation: weighing the hyperbranched polysiloxane prepared in the first step, a surfactant and an emulsifier according to a mass ratio of 93:3:3, wherein the surfactant is sodium dodecyl sulfate, and the emulsifier is polyethylene glycol octyl phenyl ether, and fully mixing to obtain a component A; weighing nano cuprous oxide, a silane coupling agent and an antioxidant according to the mass ratio of 1.5:8:0.05, wherein the silane coupling agent is gamma-aminopropyltriethoxysilane, and the antioxidant is 2, 6-tertiary butyl-4-methylphenol, and fully mixing to obtain a component B;
(b) mixing finishing agents: weighing 70 parts of the component A, 8 parts of the component B and 40 parts of the component C polyurethane adhesive in parts by weight, and blending under stirring to obtain the fluorine-free waterproof breathable antibacterial finishing agent.
Surface finishing of plaster cloth
And (4) finishing the fluorine-free waterproof breathable antibacterial finishing agent prepared in the second step on the surface of the plaster cloth by a two-dipping two-rolling method, and baking to obtain the finished plaster cloth. Wherein, the concentration of the fluorine-free waterproof breathable antibacterial finishing agent is 10 g/L. The parameters of the two-dipping and two-rolling process are as follows: the soaking time is 30min, the rolling residual rate is 70%, the speed is 80m/h, and the baking process comprises the steps of preheating for 3min at 120 ℃ and baking for 30s at 175 ℃.
Example 2
Preparation of mono-and hyperbranched polysiloxane
(1) Monomer synthesis: dissolving methyl ethyl vinyl chlorosilane and tributylamine in ether, adding trichlorosilane, uniformly mixing the methyl ethyl vinyl chlorosilane, the tributylamine and the trichlorosilane in a mass ratio of 3:4:1, reacting at 20 ℃ for 18 hours, filtering to remove precipitates, and distilling under reduced pressure to remove a solvent to obtain a monomer;
(2) polysiloxane synthesis: dissolving the monomer obtained in the step (1) in xylene, adding 50ppm Karstedt catalyst, stirring and reacting for 24 hours at 20 ℃, adding methanol with 4 times of the total volume of the system, stirring and filtering to obtain an intermediate product;
(3) hydroxyl end sealing: adding peroxybenzoic acid into the intermediate product obtained in the step (2), stirring and reacting for 4h at 20 ℃, adding potassium hydroxide to adjust the pH to 11, stirring and reacting for 2h at 60 ℃, filtering, washing and drying to obtain the hyperbranched polysiloxane.
Preparation of fluoride-free waterproof breathable antibacterial finishing agent
(a) Component preparation: weighing the hyperbranched polysiloxane prepared in the first step, a surfactant and an emulsifier according to a mass ratio of 95:5:5, wherein the surfactant is a mixture of sodium dodecyl sulfate and polyoxyethylene sorbitan fatty acid ester in a mass ratio of 1:1, and the emulsifier is sorbitan stearate, and fully mixing to obtain a component A; weighing nano cuprous oxide, a silane coupling agent and an antioxidant according to the mass ratio of 2:10:0.1, wherein the silane coupling agent is gamma-aminopropyltriethoxysilane, and the antioxidant is bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether, and fully mixing to obtain a component B;
(b) and (3) mixing finishing agents: weighing 80 parts of the component A, 10 parts of the component B and 50 parts of the component C polyurethane adhesive in parts by weight, and blending under stirring to obtain the fluorine-free waterproof breathable antibacterial finishing agent.
Surface finishing of plaster cloth
And (4) finishing the fluoride-free waterproof breathable antibacterial finishing agent prepared in the second step on the surface of the plaster cloth by a two-dipping two-rolling method, and baking to obtain the finished plaster cloth. Wherein, the concentration of the fluorine-free waterproof breathable antibacterial finishing agent is 12 g/L. The parameters of the two-dipping and two-rolling process are the same as those of the example 1.
Example 3
Preparation of mono-and hyperbranched polysiloxane
(1) Monomer synthesis: dissolving vinyl chlorosilane and tributylamine in diethyl ether, adding trichlorosilane, wherein the vinyl chlorosilane is dimethylvinylchlorosilane and methyl vinyl dichlorosilane in a mass ratio of 3:1, the vinyl chlorosilane, the tributylamine and the trichlorosilane in a mass ratio of 2:5:1, uniformly mixing, reacting at 25 ℃ for 12 hours, filtering to remove precipitates, and distilling under reduced pressure to remove a solvent to obtain a monomer;
(2) polysiloxane synthesis: dissolving the monomer obtained in the step (1) in toluene, adding 30ppm Karstedt catalyst, stirring and reacting at 25 ℃ for 18h, adding methanol 2 times of the total volume of the system, stirring and filtering to obtain an intermediate product;
(3) hydroxyl end sealing: adding peroxybenzoic acid into the intermediate product obtained in the step (2), stirring and reacting for 2h at 25 ℃, adding potassium hydroxide to adjust the pH to 8, stirring and reacting for 1h at 80 ℃, filtering, washing and drying to obtain the hyperbranched polysiloxane.
Preparation of fluoride-free waterproof breathable antibacterial finishing agent
(a) Component preparation: weighing the hyperbranched polysiloxane prepared in the first step, a surfactant and an emulsifier according to a mass ratio of 90:1:1, wherein the surfactant is a mixture of sodium dodecyl sulfate and polyoxyethylene sorbitan fatty acid ester according to a mass ratio of 1:1, and the emulsifier is a mixture of polyethylene glycol octyl phenyl ether and glyceryl stearate according to a mass ratio of 2:1, and fully mixing to obtain a component A; weighing nano cuprous oxide and a silane coupling agent according to the mass ratio of 1:5, wherein the silane coupling agent is gamma-aminopropyltriethoxysilane, and fully mixing to obtain a component B;
(b) and (3) mixing finishing agents: 60 parts of the component A, 5 parts of the component B and 30 parts of the component C polyurethane adhesive are weighed according to the parts by weight, and are blended under stirring to obtain the fluorine-free waterproof breathable antibacterial finishing agent.
Surface finishing of plaster cloth
And (4) finishing the fluoride-free waterproof breathable antibacterial finishing agent prepared in the second step on the surface of the plaster cloth by a two-dipping two-rolling method, and baking to obtain the finished plaster cloth. Wherein the concentration of the fluorine-free waterproof breathable antibacterial finishing agent is 8 g/L. The parameters of the two-dipping and two-rolling process are the same as those of the example 1.
Example 4
Preparation of mono-and hyperbranched polysiloxane
(1) Monomer synthesis: dissolving vinyl chlorosilane and trimethylamine into ether, adding trichlorosilane, wherein the vinyl chlorosilane is methyl ethyl vinyl chlorosilane and methyl vinyl dichlorosilane in a mass ratio of 2:1, the vinyl chlorosilane is methyl ethyl vinyl chlorosilane and methyl vinyl dichlorosilane in a mass ratio of 3:5:1, uniformly mixing, reacting for 15 hours at 22 ℃, filtering to remove precipitates, and distilling under reduced pressure to remove the solvent to obtain a monomer;
(2) and (3) polysiloxane synthesis: dissolving the monomer obtained in the step (1) in xylene, adding 40ppm Karstedt catalyst, stirring and reacting for 20 hours at 22 ℃, adding methanol with 4 times of the total volume of the system, stirring and filtering to obtain an intermediate product;
(3) hydroxyl end sealing: and (3) adding peroxybenzoic acid into the intermediate product obtained in the step (2), stirring and reacting for 3 hours at 22 ℃, adding tetramethylethylenediamine to adjust the pH value to 9, stirring and reacting for 2 hours at 70 ℃, filtering, washing and drying to obtain the hyperbranched polysiloxane.
Preparation of fluoride-free waterproof breathable antibacterial finishing agent
(a) Component preparation: weighing the hyperbranched polysiloxane prepared in the first step, a surfactant and an emulsifier according to a mass ratio of 95:3:3, wherein the surfactant is a mixture of sodium dodecyl sulfate and sodium dodecyl sulfate in a mass ratio of 1:1, and the emulsifier is bis-PEG/PPG-14/14 polydimethylsiloxane, and fully mixing to obtain a component A; weighing nano cuprous oxide, a silane coupling agent and an antioxidant according to the mass ratio of 1:6:0.03, wherein the silane coupling agent is gamma-aminopropyltriethoxysilane, and the antioxidant is tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and fully mixing to obtain a component B;
(b) mixing finishing agents: 75 parts of the component A, 8 parts of the component B and 35 parts of the component C polyurethane adhesive are weighed according to the parts by weight, and are blended under stirring to obtain the fluorine-free waterproof breathable antibacterial finishing agent.
Surface finishing of plaster cloth
And (3) finishing the surface of the plaster cloth by adopting the fluorine-free waterproof breathable antibacterial finishing agent prepared in the second step according to the method in the embodiment 1 through a two-dipping two-rolling method to obtain the finished plaster cloth.
Example 5
Preparation of mono-and hyperbranched polysiloxane
(1) Monomer synthesis: dissolving dimethylvinylchlorosilane and dodecyldimethylamine in diethyl ether, adding trichlorosilane, wherein the mass ratio of dimethylvinylchlorosilane to dodecyldimethylamine to trichlorosilane is 2:5:1, uniformly mixing, reacting at 25 ℃ for 18h, filtering to remove precipitates, and distilling under reduced pressure to remove a solvent to obtain a monomer;
(2) polysiloxane synthesis: dissolving the monomer obtained in the step (1) in a solvent, adding 50ppm Karstedt catalyst, stirring and reacting for 20 hours at 25 ℃, adding methanol with 2 times of the total volume of the system, stirring and filtering to obtain an intermediate product;
(3) hydroxyl end sealing: adding peroxybenzoic acid into the intermediate product obtained in the step (2), stirring and reacting for 3h at 25 ℃, adding sodium hydroxide to adjust the pH value to 10, stirring and reacting for 2h at 70 ℃, filtering, washing and drying to obtain the hyperbranched polysiloxane.
Preparation of fluoride-free waterproof breathable antibacterial finishing agent
(a) Component preparation: weighing the hyperbranched polysiloxane prepared in the first step, a surfactant and an emulsifier according to a mass ratio of 93:2:4, wherein the surfactant is sodium dodecyl sulfate, and the emulsifier is glyceryl stearate, and fully mixing to obtain a component A; weighing nano cuprous oxide, a silane coupling agent and an antioxidant according to the mass ratio of 1.5:6:0.05, wherein the silane coupling agent is gamma-aminopropyltriethoxysilane, and the antioxidant is bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether, and fully mixing to obtain a component B;
(b) and (3) mixing finishing agents: 60 parts of the component A, 5 parts of the component B and 35 parts of the component C polyurethane adhesive are weighed according to the parts by weight, and are blended under stirring to obtain the fluorine-free waterproof breathable antibacterial finishing agent.
Surface finishing of plaster cloth
And (3) finishing the surface of the plaster cloth by adopting the fluorine-free waterproof breathable antibacterial finishing agent prepared in the second step according to the method in the embodiment 1 through a two-dipping two-rolling method to obtain the finished plaster cloth.
Example 6
First, hyperbranched polysiloxanes were prepared as in example 1.
Preparation of fluoride-free waterproof breathable antibacterial finishing agent
(a) Component preparation: weighing the hyperbranched polysiloxane prepared in the first step, a surfactant and an emulsifier according to a mass ratio of 90:3:3, wherein the surfactant is polyoxyethylene sorbitan fatty acid ester, and the emulsifier is a mixture of glyceryl stearate and sorbitan stearate in a mass ratio of 1:1, and fully mixing to obtain a component A; weighing nano cuprous oxide, a silane coupling agent and an antioxidant according to the mass ratio of 2:8:0.05, wherein the silane coupling agent is gamma-aminopropyltriethoxysilane, and the antioxidant is 2, 6-tertiary butyl-4-methylphenol, and fully mixing to obtain a component B;
(b) mixing finishing agents: 65 parts of the component A, 5 parts of the component B and 30 parts of the component C polyurethane adhesive are weighed according to the parts by weight, and are blended under stirring to obtain the fluorine-free waterproof breathable antibacterial finishing agent.
Surface finishing of plaster cloth
And (3) finishing the surface of the plaster cloth by adopting the fluorine-free waterproof breathable antibacterial finishing agent prepared in the second step according to the method in the embodiment 1 through a two-dipping two-rolling method to obtain the finished plaster cloth.
Example 7
First, hyperbranched polysiloxanes were prepared as in example 1.
Preparation of fluoride-free waterproof breathable antibacterial finishing agent
(a) Component preparation: weighing the hyperbranched polysiloxane prepared in the first step, a surfactant and an emulsifier according to a mass ratio of 90:3:1, wherein the surfactant is a mixture of sodium dodecyl sulfate and polyoxyethylene sorbitan fatty acid ester according to a mass ratio of 1:2, and the emulsifier is polyethylene glycol octyl phenyl ether, and fully mixing to obtain a component A; weighing nano cuprous oxide and a silane coupling agent according to the mass ratio of 1:5, wherein the silane coupling agent is gamma-aminopropyltriethoxysilane, and fully mixing to obtain a component B;
(b) and (3) mixing finishing agents: weighing 75 parts of the component A, 8 parts of the component B and 30 parts of the component C polyurethane adhesive in parts by weight, and blending under stirring to obtain the fluorine-free waterproof breathable antibacterial finishing agent.
Surface finishing of plaster cloth
And (3) finishing the surface of the plaster cloth by adopting the fluorine-free waterproof breathable antibacterial finishing agent prepared in the second step according to the method in the embodiment 1 through a two-dipping two-rolling method to obtain the finished plaster cloth.
Example 8
The fluorine-free waterproof breathable antibacterial finishing agent prepared in the example 1 is finished on the surface of the plaster cloth by a two-dipping two-rolling method, and then baking is carried out to obtain the finished plaster cloth. Wherein, the concentration of the fluorine-free waterproof breathable antibacterial finishing agent is 8 g/L. The parameters of the two-dipping and two-rolling process are as follows: the soaking time is 35min, the rolling residual rate is 75%, the speed is 70m/h, and the baking process comprises the steps of preheating for 3min at 115 ℃ and baking for 40s at 170 ℃.
Example 9
The fluorine-free waterproof breathable antibacterial finishing agent prepared in the example 1 is finished on the surface of the plaster cloth by a two-dipping two-rolling method, and then baking is carried out to obtain the finished plaster cloth. Wherein, the concentration of the fluorine-free waterproof breathable antibacterial finishing agent is 12 g/L. The parameters of the two-dipping and two-rolling process are as follows: the soaking time is 25min, the rolling residual rate is 65%, the speed is 90m/h, and the baking process comprises the steps of preheating for 2min at 125 ℃ and baking for 20s at 180 ℃.
Comparative example 1
This comparative example differs from example 1 only in that no hydroxyl capping is carried out during the preparation of the hyperbranched polysiloxane of step one.
Comparative example 2
The surface of the plaster cloth is finished by using a conventional commercially available polydimethylsiloxane organic silicon finishing agent.
Comparative example 3
This comparative example differs from example 1 in that a fluorine-free waterproof breathable antibacterial finishing agent was prepared using a conventional commercially available polydimethylsiloxane silicone finishing agent as component a, and the plaster cloth surface was finished.
Comparative example 4
This comparative example is a patch of ointment without finishing.
For the plaster cloths prepared in examples 1 to 9 and comparative examples 1 to 3, the water-phase contact angle of the plaster cloth was tested according to AATCC-22 to characterize the water repellency, the breaking strength of the plaster cloth was tested according to ASTM D5034-95, the time required for passing 100mL of air was tested by using a permeability tester to characterize the permeability, the antibacterial properties of the plaster cloths after 0-time washing and 5-time washing were measured according to the national standard GB1759-2002 of the people's republic of china, the experimental strains were staphylococcus aureus and escherichia coli, and the results are shown in table 1 below.
Table 1 plaster cloth Performance test
According to the test results in the table above, compared with the plaster cloth which is not finished in the comparative example 4, the fluorine-free waterproof breathable antibacterial finishing agent prepared in the examples 1 to 9 can significantly improve the water phase contact angle of the surface of the plaster cloth when being used for finishing the plaster cloth, which indicates that the finishing can endow the surface of the plaster cloth with good water repellency. Meanwhile, the air permeability time is reduced, and the air permeability of the plaster cloth is obviously improved. Because the finishing agent uses the nano cuprous oxide and the hyperbranched polysiloxane, the plaster cloth has good and long antibacterial performance, and the antibacterial rate of staphylococcus aureus and escherichia coli is 99% under the condition of 0-time washing or 5-time washing.
Comparative example 1 the terminal of the hyperbranched polysiloxane is not subjected to hydroxyl end sealing in the preparation process, and the terminal of the hyperbranched polysiloxane prepared by the method is mainly based on vinyl and carbon chains, so that the binding capacity and the oxidation resistance of the hyperbranched polysiloxane to the nano cuprous oxide are reduced, and the antibacterial activity of the hyperbranched polysiloxane is reduced. Particularly, the bacteriostatic rate of the washing liquid after 5 times of washing on staphylococcus aureus and escherichia coli is obviously lower than that of the washing liquid in examples 1-9, which shows that the long-acting antibacterial property of the washing liquid is poor. The common organic silicon finishing agent is used in the comparative examples 2 and 3, and the common organic silicon finishing agent mainly comprises linear long-chain silane, so that the bonding capability of the common organic silicon finishing agent to the surface of the fabric is poor on one hand, the viscosity is high, and the oxygen resistance distance is large on the other hand, so that after the common organic silicon finishing agent is used as the finishing agent to finish the plaster cloth, the water repellency and the air permeability of the surface of the plaster cloth are not improved as compared with the examples 1-9. In comparative example 3, nano cuprous oxide is added, but nano cuprous oxide is more difficult to uniformly disperse in linear long-chain silane, and antioxidant protection cannot be obtained, so that the antibacterial property of the nano cuprous oxide is significantly lower than that of examples 1 to 9.
Claims (10)
1. A fluoride-free waterproof breathable antibacterial finishing agent is characterized by comprising the following components in parts by weight: 60-80 parts of a component A, 5-10 parts of a component B and 30-50 parts of a component C; the component A comprises hyperbranched polysiloxane, a surfactant and an emulsifier; the component B comprises nano cuprous oxide, a silane coupling agent and an antioxidant; the component C is a polyurethane adhesive.
2. The fluorine-free waterproof breathable antibacterial finishing agent according to claim 1, wherein the preparation method of the hyperbranched polysiloxane comprises the following steps:
(1) monomer synthesis: dissolving vinyl chlorosilane and a tertiary amine compound in a solvent, adding trichlorosilane, uniformly mixing, reacting at 20-25 ℃ for 12-18 h, filtering to remove precipitates, and distilling under reduced pressure to remove the solvent to obtain a monomer, wherein the mass ratio of the vinyl chlorosilane to the tertiary amine compound to the trichlorosilane is (2-3) to (4-5) to 1;
(2) polysiloxane synthesis: dissolving the monomer obtained in the step (1) in a solvent, adding a catalyst, stirring and reacting at 20-25 ℃ for 18-24 h, adding methanol with the volume 2-4 times of the total volume of the system, stirring, and filtering to obtain an intermediate product;
(3) hydroxyl end sealing: and (3) adding peroxybenzoic acid into the intermediate product obtained in the step (2), stirring and reacting for 2-4 hours at 20-25 ℃, adding alkali to adjust the pH value to 8-11, stirring and reacting for 1-2 hours at 60-80 ℃, filtering, washing and drying to obtain the hyperbranched polysiloxane.
3. The fluorine-free waterproof breathable antibacterial finishing agent according to claim 2, wherein the vinyl chlorosilane is one of dimethylvinylchlorosilane, methylethylvinylchlorosilane, and methyl vinyldichlorosilane, or a combination thereof, and the tertiary amine compound is one of tributylamine, trimethylamine, triethylamine, and dodecyldimethylamine.
4. The fluorine-free waterproof breathable antibacterial finishing agent as claimed in claim 2, wherein the catalyst is one of Speier catalyst or Karstedt catalyst, and the addition amount of the catalyst is 30-50 ppm.
5. The fluorine-free waterproof breathable antibacterial finishing agent as claimed in claim 1, wherein the mass ratio of the hyperbranched polysiloxane, the surfactant and the emulsifier in the component A is (90-95): 1-5: (1-5), and the mass ratio of the nano cuprous oxide, the silane coupling agent and the antioxidant in the component B is (1-2): 5-10): 0-0.1.
6. The fluorine-free waterproof breathable antibacterial finishing agent of claim 1, wherein the surfactant is one or a combination of sodium dodecyl sulfate, sodium dodecyl sulfate and polyoxyethylene sorbitan fatty acid ester, the emulsifier is one or a combination of polyethylene glycol octyl phenyl ether, glyceryl stearate, sorbitan stearate, bis-PEG/PPG-14/14 polydimethylsiloxane, and the antioxidant is one of 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) sulfide, and pentaerythrityl tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ].
7. A preparation method of the fluorine-free waterproof breathable antibacterial finishing agent as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
(a) component preparation: weighing and mixing the hyperbranched polysiloxane, the surfactant and the emulsifier according to the mass ratio to obtain a component A; weighing and mixing nano cuprous oxide, a silane coupling agent and an antioxidant according to the mass ratio to obtain a component B;
(b) and (3) mixing finishing agents: weighing 60-80 parts of the component A, 5-10 parts of the component B and 30-50 parts of the component C polyurethane adhesive in parts by weight, and blending under stirring to obtain the fluorine-free waterproof breathable antibacterial finishing agent.
8. The application of the fluorine-free waterproof breathable antibacterial finishing agent as claimed in any one of claims 1 to 6 in plaster cloth finishing is characterized in that the diluted fluorine-free waterproof breathable antibacterial finishing agent is finished on the surface of plaster cloth by a two-dipping and two-rolling method and then baked.
9. The application of the fluorine-free waterproof breathable antibacterial finishing agent in plaster cloth finishing is characterized in that the concentration of the fluorine-free waterproof breathable antibacterial finishing agent is 8-12 g/L.
10. The application of the fluorine-free waterproof breathable antibacterial finishing agent in plaster cloth finishing is characterized in that the soaking time is 25-35 min, the rolling residual rate is 65-75%, the speed is 70-90 m/h, and the baking process comprises preheating at 115-125 ℃ for 2-3 min, and baking at 170-180 ℃ for 20-40 s.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5102930A (en) * | 1988-07-19 | 1992-04-07 | Shin-Etsu Chemical Company, Limited | Silicone-based fabric finishing agent and fabric material finished therewith |
| JP2017088509A (en) * | 2015-11-04 | 2017-05-25 | 旭化成株式会社 | Antibacterial member |
| WO2021132172A1 (en) * | 2019-12-24 | 2021-07-01 | 三井化学株式会社 | Water repellent composition, method for producing water repellent composition, and textile product |
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2022
- 2022-03-24 CN CN202210301422.7A patent/CN114763676A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5102930A (en) * | 1988-07-19 | 1992-04-07 | Shin-Etsu Chemical Company, Limited | Silicone-based fabric finishing agent and fabric material finished therewith |
| JP2017088509A (en) * | 2015-11-04 | 2017-05-25 | 旭化成株式会社 | Antibacterial member |
| WO2021132172A1 (en) * | 2019-12-24 | 2021-07-01 | 三井化学株式会社 | Water repellent composition, method for producing water repellent composition, and textile product |
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