CN114773535A - Fluorine-free carbamate waterproof emulsion and preparation and application thereof - Google Patents
Fluorine-free carbamate waterproof emulsion and preparation and application thereof Download PDFInfo
- Publication number
- CN114773535A CN114773535A CN202210350431.5A CN202210350431A CN114773535A CN 114773535 A CN114773535 A CN 114773535A CN 202210350431 A CN202210350431 A CN 202210350431A CN 114773535 A CN114773535 A CN 114773535A
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- Prior art keywords
- emulsion
- water
- waterproof
- reaction
- surfactant
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- 239000000839 emulsion Substances 0.000 title claims abstract description 62
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 9
- 150000003077 polyols Chemical class 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 7
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000002981 blocking agent Substances 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- 239000004753 textile Substances 0.000 claims description 32
- 239000004814 polyurethane Substances 0.000 claims description 26
- 229920002635 polyurethane Polymers 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- -1 sorbitan fatty acid ester Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000005871 repellent Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004156 Azodicarbonamide Substances 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical class OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 2
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- 238000006467 substitution reaction Methods 0.000 claims 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004078 waterproofing Methods 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 20
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 23
- 239000007787 solid Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 238000005507 spraying Methods 0.000 description 12
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 8
- 230000002940 repellent Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 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 description 4
- 238000004448 titration Methods 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- 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 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 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 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- VXZBYIWNGKSFOJ-UHFFFAOYSA-N 2-[4-[5-(2,3-dihydro-1H-inden-2-ylamino)pyrazin-2-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC=1N=CC(=NC=1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 VXZBYIWNGKSFOJ-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 235000011078 sorbitan tristearate Nutrition 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
-
- 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
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/01—Stain or soil resistance
-
- 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
Abstract
The invention relates to a fluoride-free carbamate waterproof emulsion and a preparation method thereof, wherein the fluoride-free carbamate waterproof emulsion is prepared from the following raw materials in percentage by weight: 16-24% of polyol, 0.07-0.09% of catalyst, 4-6% of polyisocyanate, 1-2% of surfactant, 1-2% of blocking agent, 2-4% of hydrophobic monomer, 0.015-0.03% of initiator and the balance of water. The water-based waterproof emulsion provided by the invention has better waterproof performance and mechanical property, and the fabric treated by the emulsion also has certain surface detergency and good texture, so that the emulsion can be widely applied to the fields and products such as clothes, protective clothing, carpets, furniture decorative materials, clothes and accessories, and the like, and further improves the application value of the waterproof coating.
Description
Technical Field
The invention relates to a fluorine-free carbamate waterproof emulsion and a preparation method thereof, which can be used for preparing a waterborne polyurethane composition for endowing textiles with durable water resistance and stain removal performance and belongs to the field of waterproof materials in the textile industry.
Background
The fluorocarbon-containing water repellent is the most advanced chemical water repellent at present, but the water repellent contains perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), fluorotelomer ethanol (FTOH) and the like. A great deal of research confirms that PFOA and PFOS are one of the most difficult organic pollutants to degrade in the world at present, have lasting environmental stability and high biological accumulation and have strong environmental migration capacity, and the United nations lists them in POPs for banning. Therefore, the development of environment-friendly fluorine-free waterproof agent is in line with the demand of the development of the times.
The water-based polyurethane waterproof paint is a novel high-molecular waterproof paint developed in Europe, America and Japan in the 60 th century. The research of polyurethane waterproof paint in China starts in the 70s, and develops rapidly in the 90 s and is widely popularized and popularized.
The water-based polyurethane has the advantages of environmental protection, low energy consumption and the like, the water-based polyurethane with the water-resistant performance can form a durable water-repellent film on the surface of a fabric so as to achieve the water-resistant function, but the water-based polyurethane has a serious defect, water is used as a dispersing agent, hydrophilic groups such as-COOH or-OH and the like are inevitably introduced into a molecular structure, and the water resistance of the water-based polyurethane is much poorer than that of a solvent-based polyurethane coating due to the addition of hydrophilic monomers and the hydrophilicity of carbamate, urea bonds and the like, so that the application range of the water-based polyurethane is limited. In order to overcome a series of problems of poor water resistance, poor hand feeling of processed fabrics and the like of common waterborne polyurethane waterproof coatings, the invention introduces polyol with long carbon chains and polyisocyanate with a ring structure, and invents the fluorine-free carbamate waterproof emulsion capable of providing higher water resistance and stain removal performance for textile substrates.
Disclosure of Invention
The invention provides a fluorine-free carbamate waterproof emulsion and a preparation method thereof.
The invention is realized by the following technical scheme:
a fluorine-free carbamate waterproof emulsion and a preparation method thereof are specifically implemented according to the following steps:
step 1, weighing the following raw materials in percentage by mass:
16-24% (preferably 19.5-23.5%) of polyol, 0.07-0.09% (preferably 0.08-0.09%) of catalyst, 4-6% (preferably 4.5-6%) of isocyanate and/or polyisocyanate, 1-2% (preferably 1.2-1.8%) of surfactant, 1-2% (preferably 1.4-1.6%) of blocking agent, 2-4% (preferably 2.6-3.4%) of hydrophobic monomer, 0.015-0.03% (preferably 0.02-0.03%) of initiator and the balance of water;
step 2, pre-mixing the polyhydric alcohol weighed in the step 1 with acetone subjected to reflux dehydration and drying treatment, introducing nitrogen, heating and uniformly stirring to obtain an alcohol solution mixture;
step 3, adding the isocyanate and/or polyisocyanate weighed in the step 1 into the alcohol mixture in the step 2, adding a solvent with the mass of 1:1 of that of the polyol to reduce the viscosity of the system, continuously keeping the nitrogen atmosphere, adding a catalyst after the temperature is raised to a certain temperature, stirring and reacting in an oil bath, and cooling after the-NCO content reaches 3-3.5% to obtain a carbamate prepolymer;
step 4, adding the end-capping reagent into the prepolymer for reaction, and cooling the mixture when the-NCO content is lower than 0.1-0.3%; adding the hydrophobic monomer into the solution, continuously mixing and stirring for 30-40min, and cooling;
step 5, slowly adding deionized water into the solution obtained in the step 4, and simultaneously dispersing uniformly at a high speed under the condition of gauge pressure of 300-500KPa to obtain a waterborne polyurethane crude emulsion;
and step 6, adding the initiator into the crude emulsion obtained in the step 5, raising the temperature for reaction, continuously dispersing the mixture uniformly at a high speed under the condition of the gauge pressure of 300-500Kpa after the reaction is finished, then carrying out reduced pressure distillation to remove the solvent, and cooling to obtain the waterborne polyurethane emulsion.
The invention is also characterized in that:
the polyhydric alcohol is selected from sorbitan fatty acid ester. The sorbitan fatty acid ester is preferably selected from any one or a mixture of more than two of sorbitan fatty acid esters obtained by mono-substituted, di-substituted or tri-substituted alcoholic hydroxyl groups of fatty acid; the sorbitan fatty acid ester is formed by esterification reaction of dehydrated sorbitol and fatty acid containing chain alkyl group having 7 to 21 carbons. The initiator is selected from one or more of inorganic peroxides (such as one or more of potassium persulfate, ammonium persulfate and benzoyl peroxide) or azo compounds (such as one or more of 2, 2-Azobisisobutyronitrile (AIBN), 4-azobis (4-cyanovaleric acid) and azodicarbonamide).
The surfactant is a mixture of a nonionic surfactant and a cationic surfactant, preferably a mixture of cetyl trimethyl ammonium bromide and one or more of fatty alcohol-polyoxyethylene ether or polyethylene glycol trimethyl nonyl ether, and the mixing mass ratio of the nonionic surfactant to the cationic surfactant is 1: 1-3.
The end capping agent is any one of 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate and hydroxyethyl acrylate.
The hydrophobic monomer is any one or more of methyl methacrylate, ethyl methacrylate and butyl methacrylate.
The catalyst is any one or more of zinc isooctanoate, tin isooctanoate and bismuth isooctanoate.
In the step 2, the temperature of the polyol reflux water removal oil bath is controlled at 110 ℃ of 105-.
In the step 3, the oil bath reaction temperature is controlled to be 80-90 ℃, the mixing and stirring time is 0.5-1h, the reaction time is 2-3h, and the rotating speed is 400-; the temperature of the oil bath is controlled at 70-75 ℃, and the rotation speed is 300-450 r/min.
In the steps 4 and 5, the end-capping temperature is controlled to be 70-75 ℃, deionized water needs to be slowly added, and high-speed shearing dispersion is carried out at the same time, the emulsifying dispersion temperature is controlled to be 45-50 ℃, the emulsifying dispersion time is 0.3-0.5h, and the rotating speed is 900-1200 r/min.
In the step 6, the initiation temperature is controlled at 70-80 ℃, the reaction time is 3-4h, the rotation speed is 900-1200r/min, the suction filtration vacuum degree is controlled at 0.01-0.02Mpa, the suction filtration time is 0.3-0.5h, and the suction filtration temperature is 75-85 ℃.
The water-based waterproof emulsion provided by the invention has better waterproof performance and mechanical property, and the fabric treated by the emulsion also has certain surface detergency and good texture, so that the emulsion can be widely applied to the fields and products such as clothes, protective clothing, carpets, furniture decorative materials, clothes and accessories, and the like, and further improves the application value of the waterproof coating.
Detailed Description
Example 1
Weighing 23g of sorbitan trilaurate ester, refluxing for 120min AT an oil bath temperature of 105 ℃, continuously introducing nitrogen, purging for 15min by using nitrogen AT a flow rate of 25mL/min after refluxing is finished to remove water in the sorbitan trilaurate ester, drying 5g of Acetone (AT) placed in a closed container for 24h by using a 10g4A molecular sieve, removing water in the acetone, placing the acetone and the sorbitan trilaurate ester into a three-neck flask equipped with an overhead stirrer, introducing N into a reaction system, and removing water in the acetone2Protecting, strictly controlling the water and oxygen free of the system, heating the system to 50 ℃, controlling the rotating speed of a stirring rod to be 400r/min, and continuously stirring for 0.2h until the alcohol solid is fullPartially melting;
weighing 6g of IPDI trimer (IDT 70S) and properly adding butyl acetate (BuAc,23g) as a solvent, stirring and mixing the solution, adding the solution (the adding time is 2-5S) into a flask, observing the viscosity of the system, mixing and stirring the solution for 1h, then adding a mixture (0.08g, the mass ratio is 1: 1) of zinc isooctanoate and tin isooctanoate as catalysts, raising the temperature of the system to 85 ℃, continuously introducing nitrogen, and reacting for 3 h; detecting the content of NCO (isocyanate group) by a di-n-butylamine method, wherein the mass fraction of NCO is 3.24%, and judging that the reaction is finished;
the experimental procedure of the di-n-butylamine method is as follows: accurately weighing 5g of carbamate prepolymer into a dry 250ml triangular flask, measuring 20ml of toluene into the triangular flask by using a 20ml measuring cylinder, accurately transferring 20ml of di-n-butylamine solution into the triangular flask by using a 20ml big tripe pipette, fully oscillating, standing for 20min, measuring 100ml of isopropanol into the triangular flask by using a 100ml measuring cylinder, oscillating, adding 2-3 drops of bromocresol green indicator, and titrating by using 1mol/L hydrochloric acid standard solution until the sample solution is changed from blue to yellow green.
Calculating the formula:
V0blank titration consumes volume (mL) of hydrochloric acid standard solution; v1Volume of hydrochloric acid standard solution consumed (mL) by sample titration; m is the sample mass (g), W is the isocyanate mass fraction, c is the molar concentration (mol/L) of the standard hydrochloric acid solution, and blank titration refers to titration performed without urethane prepolymer.
Cooling the system to 75 ℃, adding an end-capping reagent 2-hydroxyethyl acrylate (1.6g), detecting the content of NCO by a di-n-butylamine method, judging that the mass fraction of NCO is less than 0.1%, cooling the system to 45 ℃, adding hydrophobic monomers of methyl methacrylate (0.9g) and butyl methacrylate (2.0g), properly increasing the rotating speed of a stirring rod to 450r/min, and continuously mixing and stirring for 35min to obtain a prepolymer solution.
Weighing deionized water (65g) and placing the deionized water into a beaker, dissolving fatty alcohol-polyoxyethylene ether (AEO-9, 0.6g) and cetyl trimethyl ammonium bromide (CTAB,0.9g) into the deionized water, slowly dropping the deionized water into an emulsifying machine, and carrying out high-speed shearing emulsification for 20min at 1000r/min under the pressure of 400KPa gauge pressure;
transferring the prepared emulsion solution from an emulsifying machine to a three-neck flask, adding potassium persulfate (KPS, 0.02g), reacting at the temperature of 80 ℃ for 3 hours, transferring the crude emulsion into the emulsifying machine, and continuously emulsifying and dispersing at a high speed for 0.5 hour at the rotating speed of 1000r/min and the pressure of 400KPa under the pressure of gauge pressure;
and finally, keeping the temperature of 80 ℃ under the condition of 0.01Mpa vacuum degree for distillation for 30min, removing solvents of butyl acetate and acetone, and cooling to obtain the waterborne polyurethane emulsion with the solid content of about 33%. The obtained emulsion is uniformly sprayed on the surface of the textile by a spraying mode, the treated textile is firstly pre-dried for 1min at 100 ℃, then dried for 5min at 130 ℃ and flattened for standby, and the wettability test is carried out according to the ISO 4920-.
Example 2
Example 2 the procedure was the same as in example 1 except that the starting sorbitan trilaurate ester was changed to sorbitan tristearate and the NCO: OH value was maintained. To obtain the waterborne polyurethane emulsion with the solid content of 34 percent. The obtained emulsion is uniformly sprayed on the surface of the textile by a spraying mode, the treated textile is pre-dried for 1min at 100 ℃, then dried for 5min at 130 ℃ and flattened for standby, and the wettability test is carried out according to the ISO 4920-1981 standard.
Example 3
Example 3 the procedure is the same as in example 1, except that the starting sorbitan trilaurate ester is replaced by sorbitan trioleate, the NCO: OH value being maintained. Obtaining the aqueous polyurethane emulsion with the solid content of 32 percent. The obtained emulsion is uniformly sprayed on the surface of the textile by a spraying mode, the treated textile is firstly pre-dried for 1min at 100 ℃, then dried for 5min at 130 ℃ and flattened for standby, and the wettability test is carried out according to the ISO 4920-.
Example 4
Example 4 the procedure was the same as in example 1 except that the amount of sorbitan trilaurate was increased to 24 g. To obtain the waterborne polyurethane emulsion with the solid content of 33 percent. The obtained emulsion is uniformly sprayed on the surface of the textile by a spraying mode, the treated textile is pre-dried for 1min at 100 ℃, then dried for 5min at 130 ℃ and flattened for standby, and the wettability test is carried out according to the ISO 4920-1981 standard.
Example 5
Example 5 the procedure was the same as in example 1 except that the amount of sorbitan trilaurate was reduced to 16 g. To obtain the waterborne polyurethane emulsion with the solid content of 33 percent. The obtained emulsion is uniformly sprayed on the surface of the textile by a spraying mode, the treated textile is pre-dried for 1min at 100 ℃, then dried for 5min at 130 ℃ and flattened for standby, and the wettability test is carried out according to the ISO 4920-1981 standard.
Example 6
Example 6 the procedure was the same as in example 1 except that the amount of hydrophobic monomer methyl methacrylate was increased to 1.5g and the amount of butyl methacrylate was increased to 3.2 g. To obtain the waterborne polyurethane emulsion with the solid content of 33 percent. The obtained emulsion is uniformly sprayed on the surface of the textile by a spraying mode, the treated textile is pre-dried for 1min at 100 ℃, then dried for 5min at 130 ℃ and flattened for standby, and the wettability test is carried out according to the ISO 4920-1981 standard.
Example 7
Example 7 the procedure was the same as that of example 1 except that the amount of hydrophobic monomers methyl methacrylate was reduced to 0.5g and the amount of butyl methacrylate was reduced to 1.5 g. Obtaining the aqueous polyurethane emulsion with the solid content of 31 percent. The obtained emulsion is uniformly sprayed on the surface of the textile by a spraying mode, the treated textile is firstly pre-dried for 1min at 100 ℃, then dried for 5min at 130 ℃ and flattened for standby, and the wettability test is carried out according to the ISO 4920-.
Example 8
Example 8 the synthesis procedure is the same as in example 1, except that the amount of IPDI trimer is increased to 6.5 g. To obtain the aqueous polyurethane emulsion with the solid content of 36 percent. The obtained emulsion is uniformly sprayed on the surface of the textile by a spraying mode, the treated textile is firstly pre-dried for 1min at 100 ℃, then dried for 5min at 130 ℃ and flattened for standby, and the wettability test is carried out according to the ISO 4920-.
Example 9
Example 9 the synthesis procedure is the same as in example 1, except that the amount of IPDI trimer is reduced to 4 g. To obtain the aqueous polyurethane emulsion with the solid content of 30 percent. The obtained emulsion is uniformly sprayed on the surface of the textile by a spraying mode, the treated textile is pre-dried for 1min at 100 ℃, then dried for 5min at 130 ℃ and flattened for standby, and the wettability test is carried out according to the ISO 4920-1981 standard.
Example 10
Example 10 the synthesis procedure was the same as in example 1, except that an aqueous prepolymer was prepared without (without) adding an isocyanate compound, and emulsified with a surfactant solution to obtain an aqueous polyurethane emulsion. The prepared emulsion was applied to textiles after dilution and tested for wettability according to ISO 4920-1981. The obtained emulsion is uniformly sprayed on the surface of the textile by a spraying mode, the treated textile is firstly pre-dried for 1min at 100 ℃, then dried for 5min at 130 ℃ and flattened for standby, and the wettability test is carried out according to the ISO 4920-.
Example 11
Example 11 the procedure of synthesis is the same as example 1 except that an aqueous prepolymer is prepared without (without) addition of an alcohol and emulsified with a surfactant solution to obtain an aqueous polyurethane emulsion. The obtained emulsion is uniformly sprayed on the surface of the textile by a spraying mode, the treated textile is firstly pre-dried for 1min at 100 ℃, then dried for 5min at 130 ℃ and flattened for standby, and the wettability test is carried out according to the ISO 4920-.
Example 12 is a blank control, and the synthesis procedure is the same as in example 1, except that the aqueous prepolymer is prepared without (without) the addition of isocyanate compounds and alcohol, and only the surfactant solution is used. The surface active agent solution is evenly sprayed on the surface of the textile by a spraying way, the treated textile is firstly pre-dried for 1min at 100 ℃, then dried for 5min at 130 ℃ and flattened for standby, and the wettability test is carried out according to the ISO 4920-.
Table 1 shows the results of the wettability testing of examples 1 to 10
| Examples | Cotton | Polyester fiber | Chunzhan (a kind of yarn of China) |
| Example 1 | 100 | 100 | 100 |
| Example 2 | 90 | 100 | 100 |
| Example 3 | 100 | 100 | 90 |
| Example 4 | 90 | 100 | 100 |
| Example 5 | 90 | 90 | 90 |
| Example 6 | 90 | 100 | 90 |
| Example 7 | 90 | 90 | 100 |
| Example 8 | 90 | 80 | 90 |
| Example 9 | 80 | 90 | 80 |
| Example 10 | 50 | 70 | 60 |
| Example 11 | 50 | 50 | 50 |
| Example 12 | 0 | 0 | 0 |
Table 2 shows the results of the soil release performance tests of the cotton cloths of examples 1-12: the stain removal performance is evaluated according to GB/T30159.1-2013 part I detection and evaluation of stain resistance of textiles, namely stain resistance of textiles, and a liquid stain method is adopted.
Comparative example
Compared with the fluorine-free products which are commercially available and reported in patents at present, the fluorine-free carbamate waterproof emulsion synthesized in the specification has higher wetting performance and stain removal performance on cotton cloth, polyester fiber and pongee under the condition of treating the same fabric. The fluorine-free waterproof emulsion can achieve the waterproof effect of a commercially available fluorine-containing product, but compared with the fluorine-containing product, the fluorine-free waterproof emulsion has the advantages of safety, greenness and environmental friendliness, and the treated fabric has better hand feeling.
Comparative example 1
A commercially available fluorine-free waterproof agent HGST-1692S produced by Suzhou yellow Yongyuan chemical industry is purchased, the effective solid content is 30%, the purchased product is treated on the fabric by adopting the process which is the same as that of the invention, corresponding tests are carried out, and the test results are compared with the invention.
Comparative example 2
We purchased commercially available fluorine-free water repellent YZ-5505A manufactured by Suzhou Yi textile technology Co., Ltd with an effective solid content of 35%, treated the fabric using the same process as described above and tested accordingly, and compared the test results with the present invention.
Comparative example 3
According to the patent CN 107278221A, the fluorine-free waterproof agent is prepared, the solid content of the waterproof agent prepared by the method is 30%, but the reaction requirement is more complex, and a large amount of organic solvent is used, so that the fluorine-free waterproof agent is difficult to recover and pollutes the environment. The fabric is treated by the same process as the invention, and corresponding tests are carried out, and the test results are compared with the invention.
Comparative example 4
The fluorine-containing waterproof agent TG-5671 which is produced by Dajin company and sold on the market is purchased, the effective solid content is 30%, the purchased product is used for treating the fabric by adopting the process which is the same as the process of the invention, the corresponding test is carried out, and the test result is compared with the invention.
Comparative example 5
According to patent CN 103396510A, a fluorine-free water repellent is prepared, the solid content of the water repellent prepared by the method is 30%, and the preparation steps are complicated. We treated the fabric using the same process as described above in the present invention and tested accordingly, the results of which are compared with the present invention in comparative example 6
Comparative example 6 the synthesis procedure was the same as in example 1 except that the amount of sorbitan trilaurate was increased to 30 g. To obtain the aqueous polyurethane emulsion with the solid content of 36 percent. The fabric is treated by the same process as the invention, and corresponding tests are carried out, and the test results are compared with the invention.
Comparative example 7
Comparative example 7 the synthesis procedure was the same as in example 1 except that the amount of the hydrophobic monomer methyl methacrylate was increased to 5.0g to obtain an aqueous polyurethane emulsion having a solid content of 38%. The fabric is treated by the same process as the invention, and corresponding tests are carried out, and the test results are compared with the invention.
Comparative example 8
Comparative example 8 the synthesis procedure is the same as in example 1, except that the amount of IPDI trimer was increased to 5.0g. The fabric is treated by the same process as the invention, and corresponding tests are carried out, and the test results are compared with the invention.
The following are the results of comparing the performances of the product of the present invention (example 1) with those of the fluorine-free water repellent HGST-1692S, YZ-5505A, fluorine-containing water repellent TG-5671, product reported in patent CN 103396510A, patent CN 107278221A, comparative example 6, comparative example 7 and comparative example 8, and the cost thereof, respectively, on treated cotton cloth, as shown in Table 3, and the stain properties on treated cotton cloth, respectively, as shown in Table 4.
TABLE 3
TABLE 4
| Examples of the invention | Milk | Red ink | Corn oil | Soy sauce |
| The invention | 5 | 5 | 5 | 5 |
| Comparative example 1 | 4 | 4 | 4 | 4 |
| Comparative example 2 | 4 | 4 | 4 | 4 |
| Comparative example 3 | 3 | 3 | 3 | 4 |
| Comparative example 4 | 5 | 5 | 5 | 5 |
| Comparative example 5 | 4 | 3 | 4 | 3 |
| Comparative example 6 | 3 | 4 | 3 | 4 |
| Comparative example 7 | 3 | 4 | 4 | 3 |
| Comparative example 8 | 4 | 4 | 4 | 4 |
From the comparison results, it can be seen that: compared with the commercial fluorine-free waterproof agent, the product synthesized by similar patents and the emulsion prepared in non-preferred proportion, the fluorine-free carbamate waterproof emulsion prepared by the invention has higher wetting performance and dirt-removing performance on cotton cloth, polyester fiber and Chunza fabric under the condition of treating the same fabric, and can achieve the waterproof effect of the commercial fluorine-containing product.
Claims (10)
1. The fluorine-free carbamate waterproof emulsion is characterized by comprising the following raw materials in percentage by weight: 16-24% (preferably 19.5-23.5%) of polyol, 0.07-0.09% (preferably 0.08-0.09%) of catalyst, 4-6% (preferably 4.5-6%) of isocyanate and/or polyisocyanate, 1-2% (preferably 1.2-1.8%) of surfactant, 1-2% (preferably 1.4-1.6%) of blocking agent, 2-4% (preferably 2.6-3.4%) of hydrophobic monomer, 0.015-0.03% (preferably 0.02-0.03%) of initiator and the balance of water.
2. The water-resistant emulsion of claim 1 wherein the polyol is a sorbitan fatty acid ester;
the sorbitan fatty acid ester is preferably selected from any one or more than two mixtures of sorbitan fatty acid esters obtained by mono-substitution, di-substitution or tri-substitution of fatty acid; the sorbitan fatty acid ester is prepared by esterification reaction of dehydrated sorbitol and fatty acid containing chain alkyl group with 7-21 carbons;
the initiator is any one or more of inorganic peroxides (such as one or more of potassium persulfate, ammonium persulfate and benzoyl peroxide) or azo compounds (such as one or more of 2, 2-Azobisisobutyronitrile (AIBN), 4-azobis (4-cyanovaleric acid) and azodicarbonamide).
3. The waterproof emulsion according to claim 1, wherein the surfactant is a mixture of a nonionic surfactant and a cationic surfactant, preferably a mixture of cetyl trimethyl ammonium bromide and one or more of fatty alcohol-polyoxyethylene ether or polyethylene glycol trimethyl nonyl ether, and the mass ratio of the nonionic surfactant to the cationic surfactant is 1:1 to 1: 3.
4. The waterproof emulsion according to claim 1, wherein the end-capping agent is any one of 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and hydroxyethyl acrylate;
the hydrophobic monomer is any one or more than two of methyl methacrylate, ethyl methacrylate and butyl methacrylate;
the catalyst is any one or more than two of zinc isooctanoate, tin isooctanoate and bismuth isooctanoate.
5. A process for preparing a water-resistant emulsion according to any one of claims 1 to 4, comprising the steps of:
step 1, premixing acetone after refluxing and dewatering the polyhydric alcohol and drying treatment, heating and uniformly stirring under the protection of nitrogen to obtain an alcohol solution mixture;
step 2, adding the isocyanate and/or the polyisocyanate into the alcohol mixture obtained in the step 1, adding a solvent with the mass ratio of 1:1-1:1.5 to the polyol to reduce the viscosity of the system, continuously keeping the nitrogen atmosphere, adding a catalyst after the reaction temperature is raised, stirring for reaction, and cooling after the-NCO content reaches 3-3.5% to obtain a carbamate prepolymer;
step 3, adding the end-capping reagent into the prepolymer for reaction, cooling after the-NCO content is less than 0.1-0.3%, adding the hydrophobic monomer into the solution, and continuously mixing and stirring for 30-40 min;
step 4, dissolving a surfactant in water, adding a water solution containing the surfactant into the solution in the step 3, and simultaneously dispersing the solution uniformly at a high speed under the condition of 300-500Kpa gauge pressure to obtain a waterborne polyurethane crude emulsion;
and 5, adding an initiator into the crude emulsion obtained in the step 4, raising the temperature for reaction, continuously dispersing uniformly at a high speed under the condition of 300-500Kpa gauge pressure after the reaction is finished, then carrying out reduced pressure distillation to remove redundant solvent and acetone, and cooling to obtain the waterborne polyurethane emulsion.
6. The method for preparing waterproof emulsion as claimed in claim 5, wherein in step 1, the temperature of refluxing and water removal of the polyol raw material is controlled at 110 ℃ and the refluxing time is 2-3h, and after the refluxing, nitrogen (with a nitrogen flow rate of 20-25mL/min) is introduced to purge for 0.1-0.3 h; the acetone used is kept stand in a molecular sieve for 24 to 36 hours for water removal treatment; the mixing temperature of the two is controlled between 45 ℃ and 55 ℃, the mixing and stirring time is 0.2h to 0.5h, and the rotating speed is 300-450 r/min.
7. The preparation method of the waterproof emulsion as claimed in claim 5, wherein in step 2, the time for adding the isocyanate and/or the polyisocyanate is 2-5s, the system is always kept in a nitrogen atmosphere, the reaction temperature is controlled at 80-90 ℃, the mixing and stirring time is 0.5-1h, the reaction time is 2-3h, and the rotation speed is 400-500 r/min; the temperature is controlled to be 70-75 ℃, and the rotating speed is 300-450 r/min; the solvent is one or more of butyl acetate, ethyl acetate, butanone and acetone.
8. The preparation method of the waterproof emulsion as claimed in claim 5, wherein in steps 3 and 4, the end-capping reaction temperature is controlled to be 70-75 ℃, the emulsifying and dispersing temperature after the hydrophobic monomer is added and added is controlled to be 45-50 ℃, the emulsifying and dispersing time is 0.3-0.5h, and the rotation speed is 900-.
9. The method for preparing waterproof emulsion as claimed in claim 5, wherein in step 5, the initiation reaction temperature is controlled to 70-80 ℃, the reaction time is 3-4h, the high speed dispersion rotation speed is 900-.
10. Use of a water-repellent emulsion according to any one of claims 1 to 4 in a process for waterproofing textiles.
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| KR20180136153A (en) * | 2017-06-14 | 2018-12-24 | ㈜대동켐텍 | Polyacrylic-based surface water repellent and water repellent textile product using the same |
| CN109988264A (en) * | 2017-12-29 | 2019-07-09 | 乳源东阳光氟有限公司 | A kind of no fluoro water proofing agent and its preparation method and application |
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