CN114409853B - 一种无氟防水剂及其制备方法 - Google Patents
一种无氟防水剂及其制备方法 Download PDFInfo
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- CN114409853B CN114409853B CN202210116433.8A CN202210116433A CN114409853B CN 114409853 B CN114409853 B CN 114409853B CN 202210116433 A CN202210116433 A CN 202210116433A CN 114409853 B CN114409853 B CN 114409853B
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- Prior art keywords
- monomer
- fluorine
- acrylate
- mass
- polyisocyanate
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004970 Chain extender Substances 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 238000004132 cross linking Methods 0.000 claims abstract description 21
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 18
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 18
- 150000003077 polyols Chemical class 0.000 claims abstract description 18
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 3
- -1 polyoxyethylene Polymers 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000000839 emulsion Substances 0.000 claims description 27
- 239000004814 polyurethane Substances 0.000 claims description 24
- 229920002635 polyurethane Polymers 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000004078 waterproofing Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 10
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 9
- VUYXVWGKCKTUMF-UHFFFAOYSA-N tetratriacontaethylene glycol monomethyl ether Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO VUYXVWGKCKTUMF-UHFFFAOYSA-N 0.000 claims description 9
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 239000000600 sorbitol Substances 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 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 7
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002563 ionic surfactant Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002280 amphoteric surfactant Substances 0.000 claims description 4
- 229960003237 betaine Drugs 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000005871 repellent Substances 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- WLCFKPHMRNPAFZ-UHFFFAOYSA-M didodecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC WLCFKPHMRNPAFZ-UHFFFAOYSA-M 0.000 claims description 3
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 2
- 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 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- YBRQEOLOGGLDGM-UHFFFAOYSA-M dodecyl-bis(2-hydroxyethyl)-methylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(CCO)CCO YBRQEOLOGGLDGM-UHFFFAOYSA-M 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 2
- 229920003009 polyurethane dispersion Polymers 0.000 claims description 2
- 235000011067 sorbitan monolaureate Nutrition 0.000 claims description 2
- 230000002940 repellent Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004383 yellowing Methods 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000001556 precipitation Methods 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid 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
- 238000009987 spinning Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XICKVYVGOLMHHQ-UHFFFAOYSA-N CC1C(C)(C)C(C)(C)CCC1.N=C=O.N=C=O Chemical compound CC1C(C)(C)C(C)(C)CCC1.N=C=O.N=C=O XICKVYVGOLMHHQ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000010028 chemical finishing Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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- 238000010561 standard procedure Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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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
- D06M15/568—Reaction products of isocyanates with polyethers
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Abstract
本申请公开了一种无氟防水剂,由以下质量百分比的原料制成:多异氰酸酯1~5%;低聚多元醇5~20%;扩链剂0.05~1%;丙烯酸交联单体0.2~2%;乳化剂0.1~2%;单体A 1~10%;单体B 2~15%;引发剂0.01~1%;余量为水。本申请还提供一种无氟防水剂的制备方法。本申请提供的无氟防水剂配方及制备方法所制得的无氟防水剂,具有防水效果优良、耐洗性好、不黄变的优点。
Description
技术领域
本申请涉及防水剂技术领域,特别是涉及一种无氟防水剂及其制备方法。
背景技术
穿戴被水或液体润湿的织物会引起人体不适感,因此在纺织品后整理上,防水整理一直以来有强烈的市场需求。纺织品的防水整理一般是通过物理构造或化学整理的方法,降低其表面自由能,使处理后的纺织品表面张力低于水或者液体,从而不被润湿。
长久以来,工业界主流的使用氟系织物防水剂作为织物防水的主要手段,但氟系织物防水剂,特别是碳八防水剂含有全氟辛酸(PFOA)等影响环境生态的物质,而在国外如欧美日韩等国家和地区已经被禁用;且被视为碳八防水剂的替代者碳六防水剂从长久来看依然逃脱不了被禁用的命运。因此,开发替代氟系防水剂的无氟防水剂,是本领域技术人员亟待解决的技术问题。
发明内容
为解决上述技术问题,本发明的第一个目的为提供一种无氟防水剂;本发明的第二个目的为提供一种无氟防水剂的制备方法;本申请提供的无氟防水剂配方及制备方法所制得的无氟防水剂,具有防水效果优良、耐洗性好、不黄变的优点。
本发明提供的技术方案如下:
一种无氟防水剂,由以下质量百分比的原料制成:
多异氰酸酯1~5%;
低聚多元醇5~20%;
扩链剂0.05~1%;
丙烯酸交联单体0.2~2%;
乳化剂0.1~2%;
单体A 1~10%;
单体B 2~15%;
引发剂0.01~1%;
余量为水。
优选地,多异氰酸酯为异佛尔酮二异氰酸酯,1,6-己基二异氰酸酯,二环己基甲烷二异氰酸酯,四甲基环己基甲烷二异氰酸酯中的一种或几种;和/或,
低聚多元醇为聚乙二醇,聚乙二醇具体为PEG-800,PEG-1000,PEG-1500、PEG-2000中的一种或多种。
优选地,多异氰酸酯与低聚多元醇的摩尔比为1:1~2。更优选多异氰酸酯与低聚多元醇的摩尔比为1:1.05~1.5。
优选地,扩链剂为亲水性扩链剂,亲水性扩链剂具体为N-甲基二乙醇胺、二乙醇胺、三乙醇胺,或者二乙烯三胺与环氧氯丙烷的加合物中的一种或多种。
优选地,亲水性扩链剂溶于溶剂中使用,溶剂为N-甲基吡咯烷酮、丁酮或乙酸丁酯中的一种或多种。
优选地,丙烯酸交联单体为甲基丙烯酸羟乙酯、丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酸羟丙酯中的一种或多种;和/或,
乳化剂为离子型表面活性剂和非离子型表面活性剂的复合物;其中,离子型表面活性剂具体为阳离子表面活性剂、两性表面活性剂中的任意一种或多种;非离子型表面活性剂具体为异构醇聚氧乙烯醚、聚氧乙烯山梨醇脂肪酸酯、山梨醇酯、脂肪酸聚氧乙烯醚、聚氧乙烯脂肪醇醚、烷基酚聚氧乙烯醚中的任意一种或多种。
优选地,阳离子表面活性剂为十二烷基三甲基氯化铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、十八烷基三甲基氯化铵、双十二烷基二甲基氯化铵、双十八烷基二甲基氯化铵、双椰油烷基二甲基氯化铵、十二烷基双羟乙基甲基氯化铵、酯基季胺盐tep-88中的任意一种或多种;
两性表面活性剂为烷基甜菜碱、烷基硫代甜菜碱、脂肪酸酰胺丙基甜菜碱等中的一种或多种;
非离子型表面活性剂中,异构醇聚氧乙烯醚具体为1303、1305、1306、1308、1310中的一种或多种;聚氧乙烯山梨醇脂肪酸酯具体为吐温-20、吐温-40、吐温-60、吐温80中的一种或多种;山梨醇酯具体为司盘-20、司盘-40、司盘-60、司盘-80中的一种或多种;脂肪酸聚氧乙烯醚具体为AEO-7、AEO-9、AEO-15中的一种或多种;聚氧乙烯脂肪醇醚具体为平平加O-10、平平加O-15、平平加O-20、平平加O-25中的一种或多种;烷基酚聚氧乙烯醚具体为OP-10、TX-10或NP-10中的一种或多种。
优选地,乳化剂中,离子型表面活性剂的质量分数为20~70%,余量为非离子表面活性剂。更优选离子型表面活性剂的质量分数为30~60%。
优选地,单体A为主链碳数原子大于等于8的丙烯酸酯,单体B为主链碳原子数小于等于4的的丙烯酸酯。
优选地,单体A丙烯酸十二酯、丙烯酸十八酯,丙烯酸异癸酯、丙烯酸异辛酯的一种或多种;单体B为丙烯酸丁酯、丙烯酸乙酯、丙烯酸甲酯中的一种或多种;和/或,
单体A和单体B的质量比为1:1~3。更优选单体A和单体B的质量比为1:1.2~2.5。
优选地,引发剂为V50,VA044、VA-061、过硫酸铵中的一种。
一种上述任一项所述的无氟防水剂的制备方法,包括以下步骤:
(1)水性丙烯酸聚氨酯乳液的制备:将真空脱水的多异氰酸酯与低聚多元醇混合,在氮气保护下,加热至75~85℃反应2~3h,加入扩链剂,并在催化剂二丁基二月桂酸锡作用下,反应0.5~1h后加入丙烯酸交联单体再反应1~2h,出料,加入有机酸调节pH值至7~8,在剪切力作用下加入多异氰酸酯、低聚多元醇和丙烯酸交联单体质量之和2~4倍质量的去离子水制得水性丙烯酸聚氨酯乳液;
(2)丙烯酸酯改性聚氨酯水分散体的制备:取上述乳液加入乳化剂,乳化剂质量占乳液中多异氰酸酯、低聚多元醇和丙烯酸交联单体质量之和的0.5~4%;然后在氮气保护下,升温至60~70℃,加入单体A和单体B混匀,加入单体A和单体B质量之和1~3倍质量的去离子水,缓慢加入引发剂,升温至引发剂反应温度反应3~4h,然后升温至引发剂保温温度保温3~4h,降温至40~60℃过滤,即得无氟防水剂。
本申请提供的无氟防水剂及其制备方法,具有防水效果优良、耐洗性好、不黄变的优点。本申请提供的无氟防水剂,用丙烯酸和聚氨酯两类聚合物,在微观状态下制备得到丙烯酸改性聚氨酯水分散体,不仅可以弥补单一聚氨酯水分散体自增稠性差、固含量偏低、乳胶膜的耐水性差,光泽性较差的问题,也可以弥补单一丙烯酸水分散体热粘冷脆、柔韧性差、不耐溶剂的问题,利用两者获得优势互补性能。本申请提供的丙烯酸酯改性聚氨酯水分散体可以将聚氨酯较高的拉伸强度和冲击强度、优异的耐磨性与丙烯酸酯树脂良好的附着力、耐候性,较低的成本有机结合,制备出高固含、低成本以及达到使用要求的水性树脂,作为防水剂使用,以达到防水效果优良、耐洗性好、不黄变的效果。
本申请提供的无氟防水剂,多异氰酸酯与低聚多元醇的摩尔比为1:1~2,根据所用的聚乙二醇不同,进行计算。例如使用PEG-1500时其分子量为1500,再换算成摩尔比,确定各组分的用量。
本申请提供的方法,先将多异氰酸酯、低聚多元醇、扩链剂、丙烯酸交联单体反应,并调节pH后,制成水性丙烯酸聚氨酯乳液,然后将上述乳液与乳化剂,按照乳化剂质量占乳液中多异氰酸酯、低聚多元醇和丙烯酸交联单体质量之和的0.5~4%、更优选1~3%的比例混合,进行后续处理。
其中,不同的引发剂所对应的反应温度和保温温度都不一样,如V50引发剂的反应温度在66℃,保温温度在72℃,VA044的反应温度为56℃,保温温度为60℃,因此加入引发剂后的反应温度、保温温度根据具体使用的引发剂进行设定。
其中,调节pH所用的有机酸可以是乙酸、柠檬酸、草酸、乙二胺四乙酸中的任意一种或多种。
扩链剂中,二乙烯三胺与环氧氯丙烷的加合物是一种单独使用的亲水性扩链剂。
具体实施方式
为了使本领域的技术人员更好地理解本申请中的技术方案,下面将对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本申请的一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本申请保护的范围。
实施例1
取真空脱水后的PEG-1500 75g,异佛尔酮二异氰酸酯12g加入玻璃烧瓶中,N2保护,加热至76~78℃,反应2h,加入扩链剂N-甲基二乙醇胺(溶于适量溶剂丁酮)1.5g,滴入几滴催化剂二丁基二月桂酸锡,反应0.5h后加入交联单体丙烯酸羟乙酯5.6g,反应1h出料,加入乙酸中和至pH值为7~8,最后在高剪切力作用下加去离子水230g制得水性丙烯酸聚氨酯乳液;
取上述水性丙烯酸聚氨酯乳液130g,加入十六烷基三甲基溴化铵0.86g,AEO-90.75g,1308 0.65g搅拌溶解,通氮气,升温至60℃,加入丙烯酸十二酯13g,丙烯酸丁酯21g,去离子水60g,快速搅拌,加入引发剂V50 0.3g,升温至66℃,反应3h,升温至72℃保温3h。降温至40~60℃过滤,即得无氟防水剂。
实施例2
取真空脱水后的PEG-1500 65g,1,6-己基二异氰酸酯10g加入玻璃烧瓶中,N2保护,加热至76~78℃,反应2h,加入扩链剂N-甲基二乙醇胺(溶于适量溶剂N-甲基吡咯烷酮)1.3g,滴入几滴催化剂二丁基二月桂酸锡,反应0.5h后加入交联单体丙烯酸羟乙酯5.6g,反应1h,出料,加入乙酸中和至pH值为7~8,最后在高剪切力作用下加去离子水230g制得水性丙烯酸聚氨酯乳液;
取上述水性丙烯酸聚氨酯乳液130g,加入十八烷基三甲基氯化铵0.91g,平平加O-15 0.80g,1305 0.65g搅拌溶解,通氮气,升温至60℃,加入丙烯酸异辛酯11g,丙烯酸甲酯19g,去离子水60g,快速搅拌,加入引发剂V50 0.3g,升温至66℃,反应3h,升温至72℃保温3h。降温至40~60℃过滤,即得无氟防水剂。
实施例3
取真空脱水后的PEG-1500 75g,异佛尔酮二异氰酸酯12g加入玻璃烧瓶中,N2保护,加热至76~78℃,反应2h,加入扩链剂N-甲基二乙醇胺(溶于适量溶剂丁酮)1.5g,滴入几滴催化剂二丁基二月桂酸锡,反应0.5h后加入交联单体甲基丙烯酸羟乙酯5.6g,反应1h,出料,加入乙酸中和至pH值为7~8,最后在高剪切力作用下加去离子水230g,制得水性丙烯酸聚氨酯乳液;
取上述水性丙烯酸聚氨酯乳液130g,加入双椰油烷基二甲基氯化铵1.0g,AEO-90.75g,1308 0.65g搅拌溶解,通氮气,升温至50℃,加入丙烯酸十二酯13g,丙烯酸丁酯18g,去离子水60g,快速搅拌,加入引发剂VA044 0.3g,升温至56℃,反应3h,升温至60℃保温3h。降温至40~60℃过滤,即得无氟防水剂。
实施例4
取真空脱水后的PEG-1500 65g,1,6-己基二异氰酸酯10g加入玻璃烧瓶中,N2保护,加热至76~78℃,反应2h,加入扩链剂N-甲基二乙醇胺(溶于适量溶剂丁酮)1.3g,滴入几滴催化剂二丁基二月桂酸锡,反应0.5h后加入交联单体丙烯酸羟丙酯6.3g,反应1h,出料,加入乙酸中和至pH值为7~8,最后在高剪切力作用下加去离子水230g制得水性丙烯酸聚氨酯乳液;
取上述的水性丙烯酸聚氨酯乳液130g,加入十六烷基三甲基溴化铵0.86g,TX-100.8g,吐温-80 0.74g搅拌溶解,通氮气,升温至60℃,加入丙烯酸十二酯5g,丙烯酸丁酯10g,去离子水60g,快速搅拌,加入引发剂V50 0.3g,升温至66℃,反应3h,升温至72℃保温3h。降温至40~60℃过滤,即得无氟防水剂。
实施例5
取真空脱水后的PEG-2000 81g,异佛尔酮二异氰酸酯12g,加入玻璃烧瓶中,N2保护,加热至76~78℃,反应2h,加入扩链剂N-甲基二乙醇胺(溶于适量溶剂N-甲基吡咯烷酮)1.3g,滴入几滴催化剂二丁基二月桂酸锡,反应0.5h后加入交联单体丙烯酸羟乙酯5.6g,反应1h,出料,加入乙酸中和至pH值为7~8,最后在高剪切力作用下加去离子水230g制得水性丙烯酸聚氨酯乳液;
取上述水性丙烯酸聚氨酯乳液130g,加入十六烷基三甲基溴化铵0.86g,AEO-90.75g,1308 0.65g搅拌溶解,通氮气,升温至60℃,加入丙烯酸十二酯10g,丙烯酸甲酯13g,去离子水60g,快速搅拌,加入引发剂V50 0.3g,升温至66℃,反应3h,升温至72℃保温3h。降温至40~60℃过滤,即得无氟防水剂。
对比例1
取真空脱水后的PEG-1500 75g,异佛尔酮二异氰酸酯12g加入玻璃烧瓶中,N2保护,加热至76~78℃,反应2h,加入扩链剂N-甲基二乙醇胺(溶于适量溶剂丁酮)1.3g,滴入几滴催化剂二丁基二月桂酸锡,反应0.5h后加入交联单体丙烯酸羟乙酯5.6g,反应1h,出料,加入乙酸中和至pH值为7~8,最后在高剪切力作用下加去离子水230g制得水性丙烯酸性聚氨酯乳液;
取上述水性丙烯酸聚氨酯乳液130g,加入十六烷基三甲基溴化铵0.86g,AEO-90.75g,1308 0.65g搅拌溶解,通氮气,升温至60℃,加入丙烯酸十二酯18g,丙烯酸丁酯13g,去离子水60g,加入引发剂V50 0.3g,升温至66℃,反应3h,升温至72℃保温3h。降温至40~60℃过滤,即得无氟防水剂。
对比例2
取真空脱水后的PEG-1500 75g,异佛尔酮二异氰酸酯12g加入玻璃烧瓶中,N2保护,加热至76~78℃,反应2h,加入扩链剂N-甲基二乙醇胺(溶于适量溶剂N-甲基吡咯烷酮)1.5g,滴入几滴催化剂二丁基二月桂酸锡,反应0.5h后加入交联单体丙烯酸羟乙酯5.6g,反应1h,出料,加入乙酸中和至pH值为7~8,最后在高剪切力作用下加去离子水230g制得水性丙烯酸性聚氨酯乳液;
取上述水性丙烯酸聚氨酯乳液130g,加入十八烷基三甲基氯化铵0.21g,平平加O-15 1.10g,1305 1.05g搅拌溶解,通氮气,升温至60℃,加入丙烯酸十八酯13g,丙烯酸甲酯18g,去离子水60g,快速搅拌,加入引发剂V50 0.3g,升温至66℃,反应3h,升温至72℃保温3h。降温至40~60℃过滤,即得无氟防水剂。
将实施例1~5和对比例1~2制备的防水剂用水稀释至30g/L,取春亚纺、涤塔夫、尼丝纺等布样,一浸一轧,100℃烘干,170℃定型热处理40秒,室温冷却回潮后测定防水效果,如下表所示:
表中:〇-优秀△-一般◇-差
其中,防水效果测试是按照AATCC-22的标准方法进行,评分细则如下:
储存稳定性实验的测试方法:将固含量30%的无氟防水剂于40℃条件下静置30日后,观察乳液沉淀情况。评判标准:〇:完全没有沉淀;△:有少量沉淀;×:有很多沉淀。
机械稳定性实验的测试方法:用水将无氟防水剂稀释到10g/L,用高速分散机以3000r/min搅拌30min后,用黑色滤纸过滤固体杂质。评判标准:〇:完全没有固体杂质;△:有少量固体杂质;×:有很多固体杂质。
从实施例和对比例的性能测试结果可以看出,对比例1由于单体A用量多于单体B,储存稳定性较差,防水性能与实施例1-5也存在差别。对比例2中阳离子表面活性剂十八烷基三甲基氯化铵在整个乳化剂(三种)中比例过小,只有8.9%,导致其储存稳定性、机械稳定性、黄变三个性能都较差,并且防水性能与实施例1-5存在较大差别。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (7)
1.一种无氟防水剂,其特征在于,由以下质量百分比的原料制成:
多异氰酸酯 1~5%;
低聚多元醇 5~20%;
扩链剂 0.05~1%;扩链剂为亲水性扩链剂,亲水性扩链剂溶于溶剂中使用,溶剂为N-甲基吡咯烷酮、丁酮或乙酸丁酯中的一种或多种;
丙烯酸交联单体 0.2~2%;丙烯酸交联单体为甲基丙烯酸羟乙酯、丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酸羟丙酯中的一种或多种;
乳化剂 0.1~2%;且乳化剂质量占乳液中多异氰酸酯、低聚多元醇和丙烯酸交联单体质量之和的0.5~4%;乳化剂中,离子型表面活性剂的质量分数为20~70%,余量为非离子表面活性剂;
单体A 1~10%;
单体B 2~15%;单体A丙烯酸十二酯、丙烯酸十八酯,丙烯酸异癸酯、丙烯酸异辛酯的一种或多种;单体B为丙烯酸丁酯、丙烯酸乙酯、丙烯酸甲酯中的一种或多种;且单体A和单体B的质量比为1:1~3;
引发剂 0.01~1%;
还包括用于调节pH的有机酸,所述有机酸具体为乙酸、柠檬酸、草酸、乙二胺四乙酸中的任意一种或多种;
余量为水;
制备方法如下:(1)水性丙烯酸聚氨酯乳液的制备:将真空脱水的多异氰酸酯与低聚多元醇混合,在氮气保护下,加热至75~85℃反应 2h,加入扩链剂,并在催化剂二丁基二月桂酸锡作用下,反应0.5h后加入丙烯酸交联单体再反应 1h,出料,加入有机酸调节pH值至7~8,在剪切力作用下加入多异氰酸酯、低聚多元醇和丙烯酸交联单体质量之和2~4倍质量的去离子水制得水性丙烯酸聚氨酯乳液;
(2)丙烯酸酯改性聚氨酯水分散体的制备:取上述乳液加入乳化剂,乳化剂质量占乳液中多异氰酸酯、低聚多元醇和丙烯酸交联单体质量之和的0.5~4%;然后在氮气保护下,升温至60℃,加入单体A和单体B混匀,加入单体A和单体B质量之和1~3倍质量的去离子水,缓慢加入引发剂,升温至引发剂反应温度反应3~4h,然后升温至引发剂保温温度保温 3h,降温至40~60℃过滤,即得无氟防水剂。
2.根据权利要求1所述的无氟防水剂,其特征在于,多异氰酸酯为异佛尔酮二异氰酸酯,1,6-己基二异氰酸酯,二环己基甲烷二异氰酸酯中的一种或几种;和/或,
低聚多元醇为聚乙二醇,聚乙二醇具体为PEG-800,PEG-1000,PEG-1500、PEG-2000中的一种或多种。
3.根据权利要求1-2中任一项所述的无氟防水剂,其特征在于,多异氰酸酯与低聚多元醇的摩尔比为1:1~2。
4.根据权利要求1所述的无氟防水剂,其特征在于,亲水性扩链剂具体为N-甲基二乙醇胺、二乙醇胺、三乙醇胺,或者二乙烯三胺与环氧氯丙烷的加合物中的一种或多种。
5.根据权利要求1所述的无氟防水剂,其特征在于,
离子型表面活性剂具体为阳离子表面活性剂、两性表面活性剂中的任意一种或多种;非离子型表面活性剂具体为异构醇聚氧乙烯醚、聚氧乙烯山梨醇脂肪酸酯、山梨醇酯、聚氧乙烯脂肪醇醚、烷基酚聚氧乙烯醚中的任意一种或多种。
6.根据权利要求5所述的无氟防水剂,其特征在于,阳离子表面活性剂为十二烷基三甲基氯化铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、十八烷基三甲基氯化铵、双十二烷基二甲基氯化铵、双十八烷基二甲基氯化铵、双椰油烷基二甲基氯化铵、十二烷基双羟乙基甲基氯化铵、酯基季胺盐tep-88中的任意一种或多种;
两性表面活性剂为烷基甜菜碱、烷基硫代甜菜碱、脂肪酸酰胺丙基甜菜碱中的一种或多种;
非离子型表面活性剂中,异构醇聚氧乙烯醚具体为1303、1305、1306、1308、1310中的一种或多种;聚氧乙烯山梨醇脂肪酸酯具体为吐温-20、吐温-40、吐温-60、吐温80中的一种或多种;山梨醇酯具体为司盘-20、司盘-40、司盘-60、司盘-80中的一种或多种;聚氧乙烯脂肪醇醚具体为平平加O-10、平平加O-15、平平加O-20、平平加O-25中的一种或多种;烷基酚聚氧乙烯醚具体为OP-10、TX-10或NP-10中的一种或多种。
7.根据权利要求1所述的无氟防水剂,其特征在于,引发剂为V50,VA044、VA-061、过硫酸铵中的一种。
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