CN112127156A - 一种环保型含氟防水剂及其制备方法 - Google Patents
一种环保型含氟防水剂及其制备方法 Download PDFInfo
- Publication number
- CN112127156A CN112127156A CN202011025508.9A CN202011025508A CN112127156A CN 112127156 A CN112127156 A CN 112127156A CN 202011025508 A CN202011025508 A CN 202011025508A CN 112127156 A CN112127156 A CN 112127156A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- environment
- preparation
- emulsifier
- waterproof agent
- 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.)
- Granted
Links
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 51
- 239000011737 fluorine Substances 0.000 title claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 47
- 239000004814 polyurethane Substances 0.000 claims abstract description 36
- 229920002635 polyurethane Polymers 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 239000000539 dimer Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000004945 emulsification Methods 0.000 claims abstract description 27
- 239000012948 isocyanate Substances 0.000 claims abstract description 24
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 125000002091 cationic group Chemical group 0.000 claims abstract description 22
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 22
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 6
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 6
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 claims description 6
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 6
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 6
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 6
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical group [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 5
- 239000003784 tall oil Substances 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- VJYNTADJZPKUAF-UHFFFAOYSA-N diethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](C)(OCC)CCC(F)(F)F VJYNTADJZPKUAF-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 4
- 229960003656 ricinoleic acid Drugs 0.000 claims description 4
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 4
- IJROHELDTBDTPH-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F IJROHELDTBDTPH-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- NYIKUOULKCEZDO-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F NYIKUOULKCEZDO-UHFFFAOYSA-N 0.000 claims description 3
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 claims description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 2
- 235000020778 linoleic acid Nutrition 0.000 claims description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 2
- 239000004744 fabric Substances 0.000 abstract description 18
- 239000000839 emulsion Substances 0.000 abstract description 5
- 238000004043 dyeing Methods 0.000 abstract description 2
- 238000007639 printing Methods 0.000 abstract description 2
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 238000004078 waterproofing Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=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-M 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- 235000012736 patent blue V Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000002940 repellent Effects 0.000 description 5
- 239000005871 repellent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- IIBQVBCHUDWEKV-UHFFFAOYSA-N O1[SiH2]O[SiH2]O[SiH2]1.FC(C=C)(F)F.FC(C=C)(F)F.FC(C=C)(F)F.FC(C=C)(F)F.FC(C=C)(F)F.FC(C=C)(F)F Chemical compound O1[SiH2]O[SiH2]O[SiH2]1.FC(C=C)(F)F.FC(C=C)(F)F.FC(C=C)(F)F.FC(C=C)(F)F.FC(C=C)(F)F.FC(C=C)(F)F IIBQVBCHUDWEKV-UHFFFAOYSA-N 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- SNGREZUHAYWORS-UHFFFAOYSA-M 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound [O-]C(=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-M 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical group CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 241000251539 Vertebrata <Metazoa> Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical group CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- -1 perfluoroalkyl compound Chemical class 0.000 description 1
- 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 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- D06M13/322—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 nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
-
- 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
-
- 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
-
- 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
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
-
- 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
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
-
- 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
-
- 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
- D06M2200/50—Modified hand or grip properties; Softening compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明属于印染助剂技术领域，具体涉及一种环保型含氟防水剂及其制备方法。本发明环保型含氟防水剂的制备方法包括以下步骤：S1)聚氨酯聚合物的制备；将含氟硅烷偶联剂、二聚酸、异氰酸酯和溶剂混合，在50～90℃下反应1～4h，反应结束后，降温至40℃以下，得聚氨酯聚合物；S2)乳化剂溶液的制备；将非离子型乳化剂、阳离子型乳化剂和去离子水投入高剪切乳化分散反应系统中，充分搅拌溶解，得乳化剂溶液；S3)在高剪切乳化分散反应系统运行下，将聚氨酯聚合物加入到乳化剂溶液中高剪切乳化30～60min，即得。本发明防水剂加入的含氟硅烷偶联剂可降解，对环境影响小，且防水剂使织物具有较好的防水性和耐洗性，手感柔软。
Description
技术领域
本发明属于印染助剂技术领域，具体涉及一种环保型含氟防水剂及其制备方法。
背景技术
防水剂在许多特殊领域中有着不可替代的地位，能够赋予纺织品优良的防水防油效果，其中有机氟类防水剂的防水效果最好。
传统的有机氟类防水剂内含有全氟辛烷磺酸盐/酯(PFOS)、全氟辛酸和全氟辛酸铵(PFOA)等，如中国专利CN101845144A公开了一种水基型有机硅氟树脂防水剂及其制备方法，由乳化体系和树脂配方合成，所述乳化体系为十二烷基苯磺酸、全氟辛基磺酸和异构醇聚氧乙烯醚非离子表面活性剂，树脂配方为八甲基环四硅氧烷、六三氟丙烯环三硅氧烷和有机硅偶联剂，在温度为55-65℃，pH为2-4，压力为30-40MPa条件下将所述树脂配方投入到所述乳化体系中后，进行阶段式加热，冷却后调pH到6-8过滤出料而得。虽然该发明能够降解，但在体系中仍加入了全氟辛基磺酸这类型的全氟烷基化合物，现有的研究表明：全氟烷基化合物具有很高的稳定性，能够经受强热、光照、化学作用、微生物作用和高等脊椎动物的代谢作用，因而其在环境、生物体中具有不降解、生物蓄积和多种毒性作用。
为了协调有机氟类防水剂防水效果和降解作用之间的问题，现有的研究不断深入，发现了被视为持久的、可生物累积的、含C8基组分的全氟烷基化合物及其衍生物主要是由电解氟化法产生的，而当生产方法变为调聚反应后，所得到的全氟烷基化合物主要是C6或C6基组分，没有C8基组分，这些C6调聚物基氟碳防水剂很有可能降解为C6Fl3CH：CH2SO3X，而不是C8F17so3X(PFOS)或CaFl5CO2X(PFOA)的调聚物磺酸盐，其毒性远比C8小。为此，有人确信C6调聚物基氟碳防水剂是替代PFOS产品的安全候选物。
发明内容
本发明旨在提供一种环保型含氟防水剂及其制备方法，本发明防水剂加入的含氟硅烷偶联剂可降解，对环境影响小，且防水剂使织物具有较好的防水性和耐洗性，手感柔软。
为了达到上述目的，本发明采用以下技术方案：
一种环保型含氟防水剂的制备方法，包括以下步骤：
S1)聚氨酯聚合物的制备；将含氟硅烷偶联剂、二聚酸、异氰酸酯和溶剂混合，在50～90℃下反应1～4h，反应结束后，降温至40℃以下，得聚氨酯聚合物；
S2)乳化剂溶液的制备；将非离子型乳化剂、阳离子型乳化剂和去离子水投入高剪切乳化分散反应系统中，充分搅拌溶解，得乳化剂溶液；
S3)在高剪切乳化分散反应系统运行下，将步骤S1的聚氨酯聚合物加入到步骤S2的乳化剂溶液中高剪切乳化30～60min，即得；
所述聚氨酯聚合物与乳化剂溶液的质量比为(20～30)：(70～80)。
在本发明中，将不含PFOS、PFOA的基于C4-C6的含氟硅烷偶联剂与异氰酸酯及二聚酸合成了聚氨酯聚合物，再与乳化剂溶液高剪切乳化得到了一种环保型防水剂，含氟硅烷偶联剂使织物具有较好的防水效果，再与二聚酸和异氰酸酯反应能够形成聚氨酯聚合物结构，使织物具有较好的耐洗性，且能够使织物手感柔软，无抓痕出现。
进一步地，所述步骤S1中含氟硅烷偶联剂、二聚酸、异氰酸酯和溶剂的质量比为(5～15)：(35～55)：(30～50)：(10～20)。
进一步地，所述含氟硅烷偶联剂选自九氟己基三乙氧基硅烷、九氟己基三甲氧基硅烷、三氟丙基三甲氧基硅烷和三氟丙基甲基二乙氧基硅烷中的一种或几种。
进一步地，所述二聚酸选自二聚蓖麻油酸、二聚亚麻油酸和二聚妥尔油酸中的一种或几种。
进一步地，所述异氰酸酯选自六亚甲基二异氰酸酯、二苯甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯和二环己基甲烷二异氰酸酯中的一种或几种。
进一步地，所述溶剂选自丙酮、丁酮和甲基异戊基酮中的一种或几种。
进一步地，所述步骤S2中非离子型乳化剂、阳离子乳化剂和去离子水的质量比为(4～8)：(2～6)：(86～94)。
进一步地，所述非离子型乳化剂选自腰果酚聚氧乙烯醚、异构醇聚氧乙烯醚、脂肪酸聚氧乙烯醚中的一种或几种。
进一步地，所述腰果酚聚氧乙烯醚的EO值为7。
进一步地，所述异构醇聚氧乙烯醚的EO值为5～15；所述异构醇聚氧乙烯醚的异构醇为C10-C18醇。
进一步地，所述脂肪酸聚氧乙烯醚的EO值为7～25。
进一步地，所述阳离子乳化剂为十八烷基三甲基氯化铵或阳离子型双子乳化剂。
另一方面，本发明提供任一上述制备方法制得的环保型含氟防水剂。
与现有技术相比，本发明具有以下有益效果：
(1)本发明使用不含PFOS、PFOA的基于C4-C6的含氟硅烷偶联剂与异氰酸酯及二聚酸合成了聚氨酯聚合物，再与乳化剂溶液高剪切乳化得到了一种环保型防水剂，经实验一表明，防水剂具有较好的机械稳定性和储藏稳定性。
(2)本发明防水剂中加入了异氰酸酯，能够降低防水剂的用量，减少对环境的不良影响，经实验二表明，防水剂对20D尼丝纺天兰色织物和300D涤塔夫黑色织物具有较好的初始防水性和耐洗性，同时能够使20D尼丝纺天兰色织物手感柔软，不对其产生抓痕。
具体实施方式
以下通过实施例形式的具体实施方式，对本发明的上述内容作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下实施例。
在本发明中，高剪切乳化分散反应系统采用中国专利CN205435700U公开的一种高剪切乳化分散反应系统；所采用的原料均可从市面上购得；防水剂T-63购自日本大金氟化工中国有限公司。
实施例1、一种环保型含氟防水剂的制备方法
包括以下步骤：
S1)聚氨酯聚合物的制备；将含氟硅烷偶联剂、二聚酸、异氰酸酯和溶剂混合，在60℃下反应3h，反应结束后，降温至40℃以下，得聚氨酯聚合物；
S2)乳化剂溶液的制备；将非离子型乳化剂、阳离子型乳化剂和去离子水投入高剪切乳化分散反应系统中，充分搅拌溶解，得乳化剂溶液；
S3)在高剪切乳化分散反应系统运行下，将步骤S1的聚氨酯聚合物加入到步骤S2的乳化剂溶液中高剪切乳化40min，即得。
其中，
步骤S1中含氟硅烷偶联剂、二聚酸、异氰酸酯和溶剂的质量比为10：40：40：10；含氟硅烷偶联剂为九氟己基三乙氧基硅烷和九氟己基三甲氧基硅烷；二聚酸为二聚蓖麻油酸；异氰酸酯为六亚甲基二异氰酸酯；溶剂为丙酮。
步骤S2中非离子型乳化剂、阳离子乳化剂和去离子水的质量比为4：4：92；非离子型乳化剂为腰果酚聚氧乙烯醚，EO值为7；阳离子乳化剂为十八烷基三甲基氯化铵。
实施例2、一种环保型含氟防水剂的制备方法
包括以下步骤：
S1)聚氨酯聚合物的制备；将含氟硅烷偶联剂、二聚酸、异氰酸酯和溶剂混合，在65℃下反应2.5h，反应结束后，降温至40℃以下，得聚氨酯聚合物；
S2)乳化剂溶液的制备；将非离子型乳化剂、阳离子型乳化剂和去离子水投入高剪切乳化分散反应系统中，充分搅拌溶解，得乳化剂溶液；
S3)在高剪切乳化分散反应系统运行下，将步骤S1的聚氨酯聚合物加入到步骤S2的乳化剂溶液中高剪切乳化45min，即得。
其中，
步骤S1中含氟硅烷偶联剂、二聚酸、异氰酸酯和溶剂的质量比为15：45：30：10；含氟硅烷偶联剂为九氟己基三甲氧基硅烷；二聚酸为二聚蓖麻油酸和二聚妥尔油酸；异氰酸酯为二苯甲烷二异氰酸酯和甲苯二异氰酸酯；溶剂为丁酮。
步骤S2中非离子型乳化剂、阳离子乳化剂和去离子水的质量比为5：6：89。非离子型乳化剂为异构醇聚氧乙烯醚和脂肪酸聚氧乙烯醚；异构醇聚氧乙烯醚的EO值为6，异构醇聚氧乙烯醚的异构醇为C12醇。脂肪酸聚氧乙烯醚的EO值为8。阳离子乳化剂为阳离子型双子乳化剂。
实施例3、一种环保型含氟防水剂的制备方法
包括以下步骤：
S1)聚氨酯聚合物的制备；将含氟硅烷偶联剂、二聚酸、异氰酸酯和溶剂混合，在70℃下反应2.5h，反应结束后，降温至40℃以下，得聚氨酯聚合物；
S2)乳化剂溶液的制备；将非离子型乳化剂、阳离子型乳化剂和去离子水投入高剪切乳化分散反应系统中，充分搅拌溶解，得乳化剂溶液；
S3)在高剪切乳化分散反应系统运行下，将步骤S1的聚氨酯聚合物加入到步骤S2的乳化剂溶液中高剪切乳化30min，即得。
其中，
步骤S1中含氟硅烷偶联剂、二聚酸、异氰酸酯和溶剂的质量比为10：35：40：15；含氟硅烷偶联剂为三氟丙基三甲氧基硅烷和三氟丙基甲基二乙氧基硅烷；二聚酸为二聚妥尔油酸；异氰酸酯为异佛尔酮二异氰酸酯和二环己基甲烷二异氰酸酯；溶剂为丁酮和甲基异戊基酮。
步骤S2中非离子型乳化剂、阳离子乳化剂和去离子水的质量比为4：6：90；非离子型乳化剂为腰果酚聚氧乙烯醚和脂肪酸聚氧乙烯醚，腰果酚聚氧乙烯醚的EO值为7，脂肪酸聚氧乙烯醚的EO值为10；阳离子乳化剂为十八烷基三甲基氯化铵。
实施例4、一种环保型含氟防水剂的制备方法
包括以下步骤：
S1)聚氨酯聚合物的制备；将含氟硅烷偶联剂、二聚酸、异氰酸酯和溶剂混合，在70℃下反应2.5h，反应结束后，降温至40℃以下，得聚氨酯聚合物；
S2)乳化剂溶液的制备；将非离子型乳化剂、阳离子型乳化剂和去离子水投入高剪切乳化分散反应系统中，充分搅拌溶解，得乳化剂溶液；
S3)在高剪切乳化分散反应系统运行下，将步骤S1的聚氨酯聚合物加入到步骤S2的乳化剂溶液中高剪切乳化60min，即得。
其中，
步骤S1中含氟硅烷偶联剂、二聚酸、异氰酸酯和溶剂的质量比为5：35：45：15；含氟硅烷偶联剂为三氟丙基甲基二乙氧基硅烷；二聚酸为二聚妥尔油酸；异氰酸酯为六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯；溶剂为丙酮。
步骤S2中非离子型乳化剂、阳离子乳化剂和去离子水的质量比为8：4：88；非离子型乳化剂为脂肪酸聚氧乙烯醚，EO值为15；阳离子乳化剂为十八烷基三甲基氯化铵。
对比例1、一种环保型含氟防水剂的制备方法
与实施例1类似，区别在于，将二聚酸替换成聚醚多元醇，聚醚多元醇为环氧丙烷-环氧乙烷共聚多元醇，分子量为3000～3500。
对比例2、一种环保型含氟防水剂的制备方法
与实施例1类似，区别在于，将二聚酸替换成丙烯酸十八酯。
对比例3、一种环保型含氟防水剂的制备方法
与实施例1类似，区别在于，聚氨酯聚合物的制备中二聚酸和异氰酸酯替换为六三氟丙烯环三硅氧烷。
试验一、稳定性测试
试验方法：
机械稳定性：在l0mL离心管中加入防水剂，3000r/min离心30分钟，观察防水剂是否出现漂浮、分层和沉淀等不稳定现象。
储藏稳定性：将防水剂置于40℃下保存1个月，观察防水剂是否有凝聚物产生，评价标准为：Ο-完全没有产生凝聚物；△-产生很少凝聚物；×-产生很多凝聚物。
表1稳定性测试结果
| 组别 | 机械稳定性 | 储藏稳定性 |
| 实施例1 | 稳定 | Ο |
| 实施例2 | 稳定 | Ο |
| 实施例3 | 稳定 | Ο |
| 实施例4 | 稳定 | Ο |
从表1可以看出，本发明实施例1～4的防水剂具有较高的机械稳定性和储藏稳定性。
试验二、防水性及耐洗性测试
2.1试验织物：20D尼丝纺天兰色；300D涤塔夫黑色。
2.2试验原料：样品(实施例/对比例/防水剂T-63)+交联剂HF-30C。
2.3工艺条件：一浸一轧→170℃焙烘50秒。
2.4试验方法：
2.4.1初始防水性能：按照标准AATCC22执行。
2.4.2耐洗性能：将试验织物用13克WOB洗衣粉水洗，西门子滚筒洗衣机40℃洗20分钟为一次，再按照标准AATCC22执行。
表2 20D尼丝纺天兰色织物和300D涤塔夫黑色织物的初始防水性能
表3 20D尼丝纺天兰色织物的耐洗性能
表4 300D涤塔夫黑色织物的耐洗性能
表5对20D尼丝纺天兰色织物的观察结果
水洗后观察到各个实施例/对比例的防水剂对300D涤塔夫黑色织物的手感和整理效果相差不明显，均呈现手感柔软，无抓痕，而对20D尼丝纺天兰色织物有明显的不同。
从表2～5可以看出，实施例1～4在使用过程中浓度达到40g/L即能够具有较高的初始防水性，防水性能好，且经过多次水洗后仍有较高的防水性，即耐洗性也比较好。同时，对20D尼丝纺天兰色织物整理后的结果为：手感柔软，无抓痕。
与实施例1相比，对比例1将二聚酸替换成聚醚多元醇，其防水性和耐洗性没有实施例1的好，但手感和整理效果相差不大；对比例2替换了二聚酸，所得到丙烯酸类体系的防水剂对20D尼丝纺天兰色织物和300D涤塔夫黑色织物的防水性和耐水性较差，且对20D尼丝纺天兰色织物手感和整理效果不好；对比例3采用有机硅六三氟丙烯环三硅氧烷也使耐水性和耐洗性变差。而与现有的防水剂相比，本发明的防水剂耐水性更好。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。
Claims (10)
1.一种环保型含氟防水剂的制备方法，其特征在于，包括以下步骤：
S1)聚氨酯聚合物的制备；将含氟硅烷偶联剂、二聚酸、异氰酸酯和溶剂混合，在50～90℃下反应1～4h，反应结束后，降温至40℃以下，得聚氨酯聚合物；
S2)乳化剂溶液的制备；将非离子型乳化剂、阳离子型乳化剂和去离子水投入高剪切乳化分散反应系统中，充分搅拌溶解，得乳化剂溶液；
S3)在高剪切乳化分散反应系统运行下，将步骤S1的聚氨酯聚合物加入到步骤S2的乳化剂溶液中高剪切乳化30～60min，即得；
所述聚氨酯聚合物与乳化剂溶液的质量比为(20～30)：(70～80)。
2.根据权利要求1所述环保型含氟防水剂的制备方法，其特征在于，所述步骤S1中含氟硅烷偶联剂、二聚酸、异氰酸酯和溶剂的质量比为(5～15)：(35～55)：(30～50)：(10～20)。
3.根据权利要求1或2所述环保型含氟防水剂的制备方法，其特征在于，所述含氟硅烷偶联剂选自九氟己基三乙氧基硅烷、九氟己基三甲氧基硅烷、三氟丙基三甲氧基硅烷和三氟丙基甲基二乙氧基硅烷中的一种或几种。
4.根据权利要求1或2所述环保型含氟防水剂的制备方法，其特征在于，所述二聚酸选自二聚蓖麻油酸、二聚亚麻油酸和二聚妥尔油酸中的一种或几种。
5.根据权利要求1或2所述环保型含氟防水剂的制备方法，其特征在于，所述异氰酸酯选自六亚甲基二异氰酸酯、二苯甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯和二环己基甲烷二异氰酸酯中的一种或几种。
6.根据权利要求1或2所述环保型含氟防水剂的制备方法，其特征在于，所述溶剂选自丙酮、丁酮和甲基异戊基酮中的一种或几种。
7.根据权利要求1所述环保型含氟防水剂的制备方法，其特征在于，所述步骤S2中非离子型乳化剂、阳离子乳化剂和去离子水的质量比为(4～8)：(2～6)：(86～94)。
8.根据权利要求1或7所述环保型含氟防水剂的制备方法，其特征在于，所述非离子型乳化剂选自腰果酚聚氧乙烯醚、异构醇聚氧乙烯醚、脂肪酸聚氧乙烯醚中的一种或几种。
9.根据权利要求1或7所述环保型含氟防水剂的制备方法，其特征在于，所述阳离子乳化剂为十八烷基三甲基氯化铵或阳离子型双子乳化剂。
10.根据权利要求1～9任一所述制备方法制得的环保型含氟防水剂。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011025508.9A CN112127156B (zh) | 2020-09-25 | 2020-09-25 | 一种环保型含氟防水剂及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011025508.9A CN112127156B (zh) | 2020-09-25 | 2020-09-25 | 一种环保型含氟防水剂及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112127156A true CN112127156A (zh) | 2020-12-25 |
| CN112127156B CN112127156B (zh) | 2021-04-20 |
Family
ID=73840204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011025508.9A Active CN112127156B (zh) | 2020-09-25 | 2020-09-25 | 一种环保型含氟防水剂及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112127156B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116084205A (zh) * | 2022-12-06 | 2023-05-09 | 浙江氟信新材料科技有限公司 | 一种纸张无氟防水剂及其制备方法 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003946A (zh) * | 2006-12-25 | 2007-07-25 | 山东东岳高分子材料有限公司 | 氟硅改性聚氨酯防水防油处理剂及其制备方法 |
| CN104356915A (zh) * | 2014-11-29 | 2015-02-18 | 朱蕾 | 一种阻燃与防水性水性聚氨酯涂料与胶粘剂的制备方法 |
| CN105037680A (zh) * | 2015-06-23 | 2015-11-11 | 上海东和胶粘剂有限公司 | 一种渗透型改性水性聚氨酯防水剂 |
| KR101807258B1 (ko) * | 2016-11-10 | 2017-12-08 | 한국바이오젠 주식회사 | 불소 함유 실릴화 폴리우레탄 감압점착제 및 이의 제조방법 |
| CN110452347A (zh) * | 2019-07-10 | 2019-11-15 | 广东德美精细化工集团股份有限公司 | 一种具有防水性能的聚氨酯中间体及其制备方法 |
| CN111101384A (zh) * | 2019-12-21 | 2020-05-05 | 福建隆上超纤有限公司 | 一种超疏水生态环保超纤革的制备方法 |
-
2020
- 2020-09-25 CN CN202011025508.9A patent/CN112127156B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003946A (zh) * | 2006-12-25 | 2007-07-25 | 山东东岳高分子材料有限公司 | 氟硅改性聚氨酯防水防油处理剂及其制备方法 |
| CN104356915A (zh) * | 2014-11-29 | 2015-02-18 | 朱蕾 | 一种阻燃与防水性水性聚氨酯涂料与胶粘剂的制备方法 |
| CN105037680A (zh) * | 2015-06-23 | 2015-11-11 | 上海东和胶粘剂有限公司 | 一种渗透型改性水性聚氨酯防水剂 |
| KR101807258B1 (ko) * | 2016-11-10 | 2017-12-08 | 한국바이오젠 주식회사 | 불소 함유 실릴화 폴리우레탄 감압점착제 및 이의 제조방법 |
| CN110452347A (zh) * | 2019-07-10 | 2019-11-15 | 广东德美精细化工集团股份有限公司 | 一种具有防水性能的聚氨酯中间体及其制备方法 |
| CN111101384A (zh) * | 2019-12-21 | 2020-05-05 | 福建隆上超纤有限公司 | 一种超疏水生态环保超纤革的制备方法 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116084205A (zh) * | 2022-12-06 | 2023-05-09 | 浙江氟信新材料科技有限公司 | 一种纸张无氟防水剂及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112127156B (zh) | 2021-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4219625A (en) | Fluorinated polyol esters | |
| US11866538B2 (en) | Polyurethane-acrylate water repellant prepared by double bonds in side chain | |
| CN101157750B (zh) | 含氟聚醚接枝改性水性聚氨酯及其制备和应用 | |
| US4468527A (en) | Fluorinated alcohols | |
| CN104540866A (zh) | 含氟化合物、组合物、制品和方法 | |
| KR20010070118A (ko) | 섬유 재료의 발유 및 발수 가공용 조성물 | |
| CN112127156B (zh) | 一种环保型含氟防水剂及其制备方法 | |
| CN114541148B (zh) | 一种纺织品防水用封闭型异氰酸酯改性硅蜡及其制备方法 | |
| KR20110013373A (ko) | 방오제 조성물과 그 제조 방법, 및 이것을 사용하여 처리된 물품 | |
| CN106480534A (zh) | 一种阳离子可染聚氨酯弹性纤维及其制备方法 | |
| CN113249971B (zh) | 一种核-壳型短链含氟丙烯酸酯织物拒水拒油整理剂及其制备方法和应用 | |
| CN114541147A (zh) | 一种高反应性柔软型无氟防水剂及其制备方法 | |
| CN108841305A (zh) | 一种高阻燃耐冲击性聚氨酯复合涂料的制备方法 | |
| CN111040105B (zh) | 一种柔软型无氟防水剂及其制备方法 | |
| EP1264863A1 (de) | Zusammensetzungen mit Polysiloxanen und weiteren Polymeren | |
| CN107163208B (zh) | 一种耐久环保型含氟纳米三防整理剂及其制备方法和应用 | |
| CN113831494B (zh) | 一种腰果酚类生物抗皱交联剂及其制备方法和应用 | |
| KR20060066169A (ko) | 섬유 재료 처리용 증량제 | |
| CN108951172B (zh) | 一种与氟系防水剂同浴使用的有机硅柔软剂及其制备方法 | |
| CN112745507A (zh) | 含氟硅油、制备方法及其应用 | |
| CN115404699B (zh) | 一种多功能纺织品后整理助剂的制备方法和产品及其应用 | |
| CN114960199B (zh) | 一种纺织品用无氟防水剂及其制备方法 | |
| CN114315564B (zh) | 新型阴离子型氟碳表面活性剂及其制备方法和应用 | |
| CN118307722B (zh) | 一种用于牛仔面料的自交联防水剂的制备方法 | |
| CN111424443A (zh) | 涤锦粘织物短流程染整工艺 |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |