CN103788321A - Short carbon chain fluorine polyurethane compound and water and oil repellent agent containing same - Google Patents
Short carbon chain fluorine polyurethane compound and water and oil repellent agent containing same Download PDFInfo
- Publication number
- CN103788321A CN103788321A CN201310463376.1A CN201310463376A CN103788321A CN 103788321 A CN103788321 A CN 103788321A CN 201310463376 A CN201310463376 A CN 201310463376A CN 103788321 A CN103788321 A CN 103788321A
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- China
- Prior art keywords
- alkyl
- urethanes
- group
- chemical formula
- compositions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 95
- 239000011737 fluorine Substances 0.000 title claims abstract description 79
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 79
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000005871 repellent Substances 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 title claims abstract description 10
- 239000004814 polyurethane Substances 0.000 title claims abstract 5
- 229920002635 polyurethane Polymers 0.000 title claims abstract 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 11
- 230000002940 repellent Effects 0.000 title abstract 5
- 239000000126 substance Substances 0.000 claims abstract description 77
- -1 carbonyl acid amide Chemical class 0.000 claims description 77
- 239000000203 mixture Substances 0.000 claims description 48
- 150000003673 urethanes Chemical class 0.000 claims description 48
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000003809 water extraction Methods 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000004744 fabric Substances 0.000 claims description 18
- 230000009257 reactivity Effects 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 15
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 15
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 15
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 10
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims description 10
- 239000010985 leather Substances 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 125000005120 alkyl cycloalkyl alkyl group Chemical group 0.000 claims description 6
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 5
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 claims description 5
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 claims description 5
- 235000005513 chalcones Nutrition 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 229960002725 isoflurane Drugs 0.000 claims description 5
- 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 5
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- LTMRRSWNXVJMBA-UHFFFAOYSA-N 2,2-diethylpropanedioic acid Chemical compound CCC(CC)(C(O)=O)C(O)=O LTMRRSWNXVJMBA-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229940022682 acetone Drugs 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- JROKZHBPSPIGMO-UHFFFAOYSA-N butanoic acid;propan-2-one Chemical compound CC(C)=O.CCCC(O)=O JROKZHBPSPIGMO-UHFFFAOYSA-N 0.000 claims description 3
- 229940043232 butyl acetate Drugs 0.000 claims description 3
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical compound CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 claims description 3
- 229940093499 ethyl acetate Drugs 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 229940032007 methylethyl ketone Drugs 0.000 claims description 3
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 3
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 10
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims 2
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 claims 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 claims 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 claims 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- 235000001508 sulfur Nutrition 0.000 claims 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 abstract description 11
- 230000036541 health Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 61
- 238000012360 testing method Methods 0.000 description 29
- 239000007788 liquid Substances 0.000 description 17
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 8
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000004815 dispersion polymer Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- HTRXGEPDTFSKLI-UHFFFAOYSA-N butanoic acid;ethyl acetate Chemical compound CCCC(O)=O.CCOC(C)=O HTRXGEPDTFSKLI-UHFFFAOYSA-N 0.000 description 3
- BRDOFYPYQFDHOQ-UHFFFAOYSA-N butyl acetate;hexanoic acid Chemical compound CCCCCC(O)=O.CCCCOC(C)=O BRDOFYPYQFDHOQ-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical compound C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 description 2
- QTBJZHMMQRGGKR-UHFFFAOYSA-N 3,5-dimethyl-1H-pyrazole Chemical compound CC1=NNC(=C1)C.CC1=NNC(=C1)C QTBJZHMMQRGGKR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920004935 Trevira® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- JUWXSPFZUDXNDX-UHFFFAOYSA-N azepan-2-one Chemical compound O=C1CCCCCN1.O=C1CCCCCN1 JUWXSPFZUDXNDX-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LQXLPMKDXWURTK-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound C(CCCCC)(O)(O)O.C(CCCCC)(O)(O)O LQXLPMKDXWURTK-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- VGLAWSIZPSWVEI-UHFFFAOYSA-N C(=C)OC=CC.[O] Chemical group C(=C)OC=CC.[O] VGLAWSIZPSWVEI-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 244000174681 Michelia champaca Species 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/8087—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8096—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with two or more compounds 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
- D06M15/37—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
- D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
Abstract
The invention provides a short carbon chain fluorine polyurethane compound and a water and oil repellent agent containing the same. The fluorine polyurethane compound has a structure shown in the following chemical formula: rf-Rx-O-[(O=C)-HN-Ry-NH-(C=O)]q-ORz. The water and oil repellent agent of the invention takes the fluorine polyurethane compound as a main component, and the PFOA (perfluorooctanoic acid) component contained in the existing water and oil repellent agent is greatly reduced, so the water and oil repellent agent has the advantages of environmental friendliness and health of users.
Description
Technical field
The present invention is about a kind of fluorine element urethanes and containing its water extraction oil extracticn agent, espespecially a kind of water extraction oil extracticn agent of low PFOA composition.
Background technology
Solvent-borne type oil extracticn agent (as the TaiWan, China patent No.: as shown in TWI289599) there is preferably the physical property of product and stability compared with aqueous dispersions type oil extracticn agent, and there is the advantage such as water-wash resistance and applied range.But existing solvent-borne type oil extracticn agent generally contains PFOA(Perfluoro Octanoic acid; Perfluorocaprylic Acid).This class material is difficult for decomposing in the Nature, and transformation period in human body reaches 4 years.Therefore, life-time service contains the solvent-borne type oil extracticn agent of PFOA to environment and HUMAN HEALTH, all may bring injury.
In today that environmental consciousness comes back and user day by day payes attention to its health, in this area, be badly in need of a kind of water extraction oil extracticn agent of novelty, its content by PFOA in product is down to minimum, can take into account again product usefulness simultaneously.
Summary of the invention
So one object of the present invention is for providing to prepare a kind of composition of fluorine element urethanes, described fluorine element urethanes can be used as the main component of water extraction oil extracticn agent, PFOA content can be down to minimum.
Another object of the present invention is for providing water extraction oil extracticn agent of a kind of low PFOA composition novelty and preparation method thereof, can exempt the doubt that environment and user's health are worked the mischief.
For achieving the above object, the invention provides a kind of fluorine element urethanes, it has the structure shown in following Chemical formula 1:
R
f-R
x-O-[(O=C)-HN-R
y-NH-(C=O)]
q-OR
z (1)；
Wherein, q is selected from 1 to 10 integer;
Wherein, R
ffor C
3～C
6perfluoroalkyl; R
xbe selected from C
1～C
10alkyl, C
1～C
10hydroxyalkyl, ester group alkyl, sulfonic acid amido, carbonyl acid amide base and oxygen base phenyl; Wherein, R
ybe selected from the C that is substituted or is unsubstituted
1～C
10alkyl, cycloalkyl, phenyl, naphthyl, alkyl phenyl, alkyl-cycloalkyl, alkyl phenyl alkyl and alkyl-cycloalkyl-alkyl; Wherein, R
zbe selected from ROH, R (EO)
mh, R-(EO)
m(PO)
nh, C
1～C
3thiol group, thiophenol base, ketoxime base, C
1～C
10acidic group, diketo, amide group, pyrazolyl and phenolic group; Wherein, described R
zto borrow the OH group in its structure to be binding in described Chemical formula 1; Wherein, R is C
8～C
20straight or branched alkyl; EO is oxyethane; PO is propylene oxide; M is 3～50 integer; N is 3～50 integer.
Preferably, described sulfonic acid amido has the structure shown in following Chemical formula 2-a :-SO
2-N (R
1) R
2-(2-a);
Wherein, R
1for hydrogen or C
1～C
10alkyl; Wherein, R
2for C
1～C
10alkylidene group.
Preferably, described carbonyl acid amide base has the structure shown in following Chemical formula 2-b :-CO-N (R
1) R
2-(2-b);
Wherein, R
1for hydrogen or C
1～C
10alkyl; Wherein, R
2for C
1～C
10alkylidene group.
Preferably, described ester group alkyl has the structure shown in following Chemical formula 2-c :-CH
2-CH (OCOR
3) CH
2-(2-c);
Wherein R
3for hydrogen or methyl.
Preferably, described oxygen base phenyl has the structure shown in following Chemical formula 2-d :-O-Ar-(2-d);
Wherein, Ar is Ben Ji Huo Benzyl base.
Preferably, described R
ybe selected from through 1-3 C
1～C
3the C that alkyl replaces
1～C
10alkyl, cycloalkyl, phenyl, naphthyl, alkyl phenyl, alkyl-cycloalkyl, alkyl phenyl alkyl and alkyl-cycloalkyl-alkyl.
Preferably, described R
ybe selected from aminomethyl phenyl, phenylmethylene phenyl, naphthyl, methylene-benzene methylene, hexyl, cyclohexyl, cyclohexylmethylene cyclohexyl, different fluorine that ketone group and tetramethylphenyl.
The present invention provides again a kind of composition of preparing fluorine element urethanes, and it comprises: the fluorine alcohol compound of 0.2～1.0 gram equivalent; The fat alcohol compound of 0.2～1.0 gram equivalent; The vulcabond of 0.8～2.0 gram equivalent or its polymkeric substance; The bridging agent of 0.1～0.5 gram equivalent; And the blockade agent of 0.1～0.5 gram equivalent.
Preferably, described fluorine alcohol compound is perfluoroalkyl alkylol cpd.
Preferably, described perfluoroalkyl alkylol cpd has the structure shown in following Chemical formula 2: R
f-R
x-OH (2);
Wherein, R
ffor C
3～C
6perfluoroalkyl;
Wherein, R
xfor C
1～C
10alkyl, C
1～C
10hydroxyalkyl, ester group alkyl, sulfonic acid amido, carbonyl acid amide base or oxygen base phenyl.
Preferably, described sulfonic acid amido has the structure shown in following Chemical formula 2-a :-SO
2-N (R
1) R
2-(2-a);
Wherein, R
1for hydrogen or C
1～C
10alkyl;
Wherein, R
2for C
1～C
10alkylidene group.
Preferably, described carbonyl acid amide base has the structure shown in following Chemical formula 2-b :-CO-N (R
1) R
2-(2-b);
Wherein, R
1for hydrogen or C
1～C
10alkyl;
Wherein, R
2for C
1～C
10alkylidene group.
Preferably, described ester group alkyl has the structure shown in following Chemical formula 2-c :-CH
2-CH (OCOR
3) CH
2-(2-c);
Wherein R
3for hydrogen or methyl.
Preferably, described oxygen base phenyl has the structure shown in following Chemical formula 2-d :-O-Ar-(2-d);
Wherein, Ar is Ben Ji Huo Benzyl base.
Preferably, described fluorine alcohol compound is selected from least one in following compound: CF
3(CF
2)
6(CH
2)
1oH; CF
3(CF
2)
6(CH
2)
2oH; CF
3(CF
2)
5(CH
2)
1oH; CF
3(CF
2)
5(CH
2)
2oH; CF
3(CF
2)
4(CH
2)
1oH; CF
3(CF
2)
4(CH
2)
2oH; And C
6f
13-O-Ar-OH; Wherein, Ar is Ben Ji Huo Benzyl base.
Preferably, described vulcabond is fragrant family vulcabond, fatty family vulcabond or its combination.Preferably, described fragrant family vulcabond comprises: tolylene diisocyanate (TDI), ditan-4,4`-vulcabond (MDI), naphthalene-1,5-vulcabond (NDI), xylylene diisocyanate (XDI) or its mixing.Preferably, described fatty family vulcabond comprises: hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (H
12mDI), isoflurane chalcone diisocyanate (IPDI), cyclohexyl diisocyanate (CHDI), tetramethylxylylene diisocyanate (TMXDI) or its mixing.
Preferably, described fat alcohol compound has at least one of structure shown in following chemical formula 3-a, chemical formula 3-b, chemical formula 3-c:
R-OH (3-a)；
R-(EO)
m-H (3-b)；
R-(EO)
m(PO)
n-H (3-c)；
Wherein, R is C
8～C
20straight or branched alkyl; Wherein, EO is oxyethane; Wherein, PO is propylene oxide; Wherein, the integer that m is 3～50; And wherein, the integer that n is 3～50.
Preferably, described bridging agent comprises three alkylol cpds.
Preferably, described three alkylol cpds comprise polyoxyethyl propyl triol (Poly (oxy propylene) triol), polyoxyethyl propyl polyoxy ethyl triol (Poly (oxy propylene ethylene) triol), trihydroxymethyl propane (TMP), glycerine (glycerol), hexanetriol (hexanetriol) or its mixture.
Preferably, described blockade agent comprises methyl alcohol (ethanol), ethanol (ethanol), sulfur alcohol (ethyl mercaptan), β-thiophenol (β-thionaphthol), methyl ethyl ketoxime (methyl ethyl ketone oxime), acetoxime (acetoxime), cyclohexanone-oxime (cyclohexanone oxime), Diacetylmonoxime (butanone oxime), diethyl malonic acid (diethylmalonate), methyl ethyl diketone (acetylacetone), acetone ethyl acetic acid (acetoethylacetate), ε-caprolactam (ε-caprolactam), 3, 5-dimethyl pyrazole (3, 5-Dimethylpyrazole), phenol (phenol), or its mixture.
Preferably, described composition further comprises the solvent of 50～80 weight percents, and wherein said weight percent is take the gross weight of described composition as basis.
Preferably, described solvent comprises ethyl acetate (ethyl acetate), butylacetate (butyl acetate), acetone (acetone), methylethylketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc), toluene (toluene) or its mixture.
Preferably, described fluorine element urethanes is a heat reactivity fluorine element urethanes.
The present invention provides a kind of solvent-borne type short carbon chain oil extracticn agent again, and it comprises: the heat reactivity fluorine element urethanes of 20～50 weight percents; And the solvent of 50～80 weight percents; Wherein, described weight percent is take the gross weight of described solvent-borne type short carbon chain oil extracticn agent as basis; Wherein, described heat reactivity fluorine element urethanes comprises described fluorine element urethanes, the prepared fluorine element urethanes of described composition or its combination.
Preferably, described heat reactivity fluorine element urethanes has C
3～C
6perfluoroalkyl.
Preferably, described solvent comprises ethyl acetate, butylacetate, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), dimethyl formamide, N,N-DIMETHYLACETAMIDE, toluene or its mixture.
The present invention separately provides a kind of method of described solvent-borne type short carbon chain oil extracticn agent, and it comprises following steps: a. make the vulcabond of the fluorine alcohol compound of 0.2～1.0 gram equivalent and 0.8～2.0 gram equivalent or its polymer reaction raw one first polymkeric substance; B. make the bridging agent of described the first polymkeric substance and the fat alcohol compound of 0.2～1.0 gram equivalent and 0.1～0.5 gram equivalent react raw one second polymkeric substance; And c. makes described the second polymkeric substance react raw a heat reactivity fluorine element urethanes with the blockade agent of 0.1～0.5 gram equivalent; Wherein, described step a, step b and/or step c account in the solvent of 50～80 weight percents and carry out in one; Wherein, described weight percent is take the gross weight of all reactants in the reaction of described step a, step b or step c as basis.
Preferably, in described step a, further comprise: measure the weight percent of the NCO group of the end of described the first polymkeric substance, when the weight percent of described NCO group reaches after 7～11 weight percents, start to carry out described step b; The weight percent of wherein said NCO group is take the gross weight of described the first polymkeric substance as basis.
Preferably, in described step b, further comprise: measure the weight percent of the NCO group of the end of described the second polymkeric substance, when the weight percent of described NCO group reaches after 0.5～2.0 weight percent, start to carry out described step c; The weight percent of wherein said NCO group is take the gross weight of described the second polymkeric substance as basis.
Preferably, described step a, described step b and/or described step c carry out in 40 ℃ to 120 ℃.
Preferably, the reaction times of described step a is 1 to 5 hours.
Preferably, the reaction times of described step b is 6 to 24 hours.
Preferably, the reaction times of described step c is 0.5 to 4 hours.
The present invention also provides a kind of article of tool water-repellent oil-repellent, and at least one surface-coated of wherein said article has described water extraction oil extracticn agent.
Preferably, described article are fabric or leather.
In sum, the present invention is about a kind of fluorine element urethanes, and prepares a kind of composition of fluorine element urethanes.Described fluorine element urethanes can be in order to prepare water extraction oil extracticn agent, and prepared water extraction oil extracticn agent has low PFOA composition, can reduce the doubt that environment and user's health is worked the mischief.
Embodiment
Fluorine element urethanes of the present invention
In one embodiment, the present invention is about a kind of fluorine element urethanes.Preferably, described fluorine element urethanes is a heat reactivity fluorine element urethanes.Preferably, described fluorine element urethanes has the structure shown in following Chemical formula 1:
R
f-R
x-O-[(O=C)-HN-R
y-NH-(C=O)]
q-OR
z (1)
Wherein, q is selected from 1 to 10 integer.
Described " R
f-R
x-O-" structure can come from a short carbon chain fluorine alcohol compound; Wherein, R
ffor C
3～C
6perfluoroalkyl; R
xbe selected from C
1～C
10alkyl, C
1～C
10hydroxyalkyl, ester group alkyl, sulfonic acid amido, carbonyl acid amide base and oxygen base phenyl.Described short carbon chain fluorine alcohol compound at least has a hydrogen-oxygen group, in the time of bond, and the Sauerstoffatom on hydrogen-oxygen group and described vulcabond (O=C=N-R
y-N=C=O) the carbon atom bond of isocyanide carbonyl acid (N=C=O) group in compound structure, nitrogen-atoms catches again sloughs hydrogen atom.
Described " R
f-R
x-O-" in structure, described R
xthe group that is selected from following chemical formula representative:
2-a-SO
2-N (R
1) R
2-; Wherein, R
1for hydrogen or C
1～C
10alkyl; R
2for C
1～C
10alkylidene group.
2-b-CO-N (R
1) R
2-; Wherein, R
1for hydrogen or C
1～C
10alkyl; R
2for C
1～C
10alkylidene group.
2-c-CH
2-CH (OCOR
3) CH
2-; Wherein R
3for hydrogen or methyl.
2-d-O-Ar-; Wherein, Ar is Ben Ji Huo Benzyl base.
In a preferred embodiments, described " R
f-R
x-O-" structure is at least one being selected from following compound: CF
3(CF
2)
6(CH
2)
1oH; CF
3(CF
2)
6(CH
2)
2oH; CF
3(CF
2)
5(CH
2)
1oH; CF
3(CF
2)
5(CH
2)
2oH; CF
3(CF
2)
4(CH
2)
1oH; CF
3(CF
2)
4(CH
2)
2oH; And C
6f
13-O-Ar-OH; Wherein, Ar is Ben Ji Huo Benzyl base.
Described " (O=C)-HN-R
y-NH-(C=O)-" can come from a vulcabond or its polymkeric substance; Wherein R
ybe selected from the C that is substituted or is unsubstituted
1～C
10alkyl, cycloalkyl, phenyl, naphthyl, alkyl phenyl, alkyl-cycloalkyl, alkyl phenyl alkyl and alkyl-cycloalkyl-alkyl.Feasible ground, described R
ybe selected from through 1-3 C
1～C
3the C that alkyl replaces
1～C
10alkyl, cycloalkyl, phenyl, naphthyl, alkyl phenyl, alkyl-cycloalkyl, alkyl phenyl alkyl and alkyl-cycloalkyl-alkyl.
Described " R
z" can come from an aliphatic alcohols compound, a bridging agent or a blockade agent.Feasible ground, R
zbe selected from ROH, R (EO)
mh, R-(EO)
m(PO)
nh, C
1～C
3thiol group, thiophenol base, ketoxime base, C
1～C
10acidic group, diketo, amide group, pyrazolyl and phenolic group; Wherein, R is C
8～C
20straight or branched alkyl; EO is oxyethane; PO is propylene oxide; M is 3～50 integer; N is 3～50 integer.Described aliphatic alcohols compound, described bridging agent and described blockade agent all at least have a hydrogen-oxygen group, in the time of bond, slough described hydrogen-oxygen group hydrogen atom and with described " (O=C)-HN-R
y-NH-(C=O)-" the carbon atom bond of carbonyl acid groups in structure.
Composition of the present invention
In another embodiment, the present invention about a kind of in order to prepare the composition of fluorine element urethanes.Described composition comprises: the fluorine alcohol compound of 0.2～1.0 gram equivalent; The fat alcohol compound of 0.2～1.0 gram equivalent; The vulcabond of 0.8～2.0 gram equivalent or its polymkeric substance; The bridging agent of 0.1～0.5 gram equivalent; And the blockade agent of 0.1～0.5 gram equivalent.
Preferably, described fluorine alcohol compound is a short carbon chain fluorine alcohol compound.Preferably, described fluorine alcohol compound is a short carbon chain perfluoroalkyl alkylol cpd.
Feasible ground, described fluorine alcohol compound has structure shown in following Chemical formula 2: R
f-R
x-OH (2);
Wherein, R
ffor C
3～C
6perfluoroalkyl; Wherein, R
xfor C
1～C
10alkyl, C
1～C
10hydroxyalkyl, ester group alkyl, sulfonic acid amido, carbonyl acid amide base or oxygen base phenyl.Feasible ground, R
xbe selected from the group (please refer to above-mentioned paragraph) of following Chemical formula 2-a, 2-b, 2-c or 2-d representative.
Preferably, described fluorine alcohol compound is selected from:
Wherein, R
ffor C
3～C
6perfluoroalkyl; R
1for hydrogen or C
1～C
10alkyl; R
2for C
1～C
10alkylidene group;
R
3for hydrogen or methyl; Ar is Ben Ji Huo Benzyl base
Preferably, described fluorine alcohol compound is selected from least one in following compound: CF
3(CF
2)
6(CH
2)
1oH; CF
3(CF
2)
6(CH
2)
2oH; CF
3(CF
2)
5(CH
2)
1oH; CF
3(CF
2)
5(CH
2)
2oH; CF
3(CF
2)
4(CH
2)
1oH; CF
3(CF
2)
4(CH
2)
2oH; And C
6f
13-O-Ar-OH; Wherein, Ar is Ben Ji Huo Benzyl base.
Preferably, described vulcabond is fragrant family vulcabond, fatty family vulcabond or its combination.Preferably, described fragrant family vulcabond comprises: tolylene diisocyanate (TDI), ditan-4,4`-vulcabond (MDI), naphthalene-1,5-vulcabond (NDI), xylylene diisocyanate (XDI) or its mixing.Preferably, described fatty family vulcabond comprises: hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (H
12mDI), isoflurane chalcone diisocyanate (IPDI), cyclohexyl diisocyanate (CHDI), tetramethylxylylene diisocyanate (TMXDI) or its mixing.
Preferably, described fat alcohol compound comprises fatty alcohol, fatty alcohol-polyoxyethylene ether or poly alkyl alcohol (oxygen ethene-oxypropylene) ether.Preferably, described fat alcohol compound has at least one of structure shown in following chemical formula 3-a, chemical formula 3-b, chemical formula 3-c:
R-OH (3-a)；
R-(EO)
m-H (3-b)；
R-(EO)
m(PO)
n-H (3-c)；
Wherein, R is C
8～C
20straight or branched alkyl; Wherein, EO is oxyethane; Wherein, PO is propylene oxide; Wherein, the integer that m is 3～50; And wherein, the integer that n is 3～50.
Preferably, described bridging agent comprises three alkylol cpds.Preferably, described three alkylol cpds comprise polyoxyethyl propyl triol (Poly (oxy propylene) triol), polyoxyethyl propyl polyoxy ethyl triol (Poly (oxy propylene ethylene) triol), trihydroxymethyl propane (TMP), glycerine (glycerol), hexanetriol (hexanetriol) or its mixture.
Preferably, described blockade agent comprises methyl alcohol (ethanol), ethanol (ethanol), sulfur alcohol (ethyl mercaptan), β-thiophenol (β-thionaphthol), methyl ethyl ketoxime (methyl ethyl ketone oxime), acetoxime (acetoxime), cyclohexanone-oxime (cyclohexanone oxime), Diacetylmonoxime (butanone oxime), diethyl malonic acid (diethylmalonate), methyl ethyl diketone (acetylacetone), acetone ethyl acetic acid (acetoethylacetate), ε-caprolactam (ε-caprolactam), 3, 5-dimethyl pyrazole (3, 5-Dimethylpyrazole), phenol (phenol), or its mixture.
Composition of the present invention can comprise the solvent of 50～80 weight percents, and wherein said weight percent is take the gross weight of described composition as basis.Described solvent includes, but are not limited to: ethyl acetate (ethyl acetate), butylacetate (butyl acetate), acetone (acetone), methylethylketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc), toluene (toluene) or its mixture.
Solvent-borne type short carbon chain oil extracticn agent of the present invention
In another embodiment, the present invention is about a kind of solvent-borne type short carbon chain oil extracticn agent and preparation method thereof.The heat reactivity fluorine element urethanes that described solvent-borne type short carbon chain oil extracticn agent comprises 20～50 weight percents; And the solvent of 50～80 weight percents; Wherein, described weight percent is take the gross weight of described solvent-borne type short carbon chain oil extracticn agent as basis; Wherein, described heat reactivity fluorine element urethanes comprises fluorine element urethanes of the present invention.
Described solvent includes, but are not limited to: ethyl acetate (ethyl acetate), butylacetate (butyl acetate), acetone (acetone), methylethylketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc), toluene (toluene) or its mixture.
The preparation method of solvent-borne type short carbon chain oil extracticn agent of the present invention can carry out with described composition of the present invention.Described preparation method is contained in the solvent of 50～80 weight percents and carries out following steps, wherein, the shared weight percent of described solvent be gross weight take all reactants in each reactions steps as basis:
A. make fluorine alcohol compound and vulcabond or its polymer reaction raw one first polymkeric substance.
Described step a makes the described fluorine alcohol compound of suitable equivalent ratio react with described vulcabond or its polymkeric substance.In reaction, carbon atom bond in (N=C=O) group of the Sauerstoffatom of the hydrogen-oxygen group of described fluorine alcohol compound and described vulcabond or its polymkeric substance forms ester group intermediate, and nitrogen-atoms catches hydrogen atom unnecessary on hydrogen-oxygen group again and forms carboxylic acid amide esters compound.Preferably, in the reaction of step a, measure the weight percent of the NCO group of the end of described the first polymkeric substance, when the weight percent of described NCO group reaches after 7～11 weight percents, start to carry out described step b.The weight percent of described NCO group is take the gross weight of described the first polymkeric substance as basis.
Preferably, the weight percent of described NCO group can be by adjusting reaction equivalent number, the reaction times of step a and/or the controlling reaction temperature of step a of described fluorine alcohol compound and described vulcabond or its polymkeric substance.
Preferably, step a be make the vulcabond of the fluorine alcohol compound of 0.2～1.0 gram equivalent and 0.8～2.0 gram equivalent or its polymer reaction raw one first polymkeric substance.Preferably, the reaction times of described step a is 1 to 5 hours.Preferably, the temperature of reaction of described step a is 40 ℃ to 120 ℃.
B. make described the first polymkeric substance react raw one second polymkeric substance with fat alcohol compound and bridging agent.
Step b reacts fat alcohol compound and the bridging agent of the first polymkeric substance and suitable equivalents.In reaction, the carbon atom bond of (N=C=O) group of the Sauerstoffatom of the hydrogen-oxygen group of described fat alcohol compound and described bridging agent and described vulcabond or its polymkeric substance forms ester group intermediate, and nitrogen-atoms catches hydrogen atom unnecessary on hydrogen-oxygen group again and forms carboxylic acid amide esters compound.Preferably, in the reaction of step b, measure the weight percent of the NCO group of the end of described the second polymkeric substance, when the weight percent of described NCO group reaches after 0.5～2.0 weight percent, start to carry out described step c.The weight percent of described NCO group is take the gross weight of described the second polymkeric substance as basis.
Preferably, the weight percent of described NCO group can be by adjusting reaction equivalent number, the reaction times of step b and/or the controlling reaction temperature of step b of described fat alcohol compound and described bridging agent.
Preferably, step b makes the bridging agent of described the first polymkeric substance and the fat alcohol compound of 0.2～1.0 gram equivalent and 0.1～0.5 gram equivalent react raw one second polymkeric substance.Preferably, the reaction times of described step b is 6 to 24 hours.Preferably, the temperature of reaction of described step b is 40 ℃ to 120 ℃.
C. make described the second polymkeric substance and block agent and react the plain urethanes of raw a heat reactivity fluorine.
Step c makes the second polymkeric substance react with the blockade agent of suitable equivalents.In reaction, the carbon atom bond of (N=C=O) group of the Sauerstoffatom of the hydrogen-oxygen group of described blockade agent and described vulcabond or its polymkeric substance forms ester group intermediate, and nitrogen-atoms catches hydrogen atom unnecessary on hydrogen-oxygen group again and forms carboxylic acid amide esters compound.
Preferably, after described step c has reacted, will no longer there is the NCO group that can react in described the second polymkeric substance.Described " can react " refer to carbon atom in the carbonyl group of this NCO group still can with another state from the oxonium ion bond of the hydrogen-oxygen group of described fluorine alcohol compound, described fat alcohol compound, described bridging agent or described blockade agent.Otherwise, the neither state in described " can react " of carbon atom in the carbonyl group of the NCO group in the structure of so-called " no longer having the NCO group that can react " all described vulcabond of intention or its polymkeric substance.
Preferably, can control in reaction, whether also to there is the NCO group that can react by adjusting described blockade agent reaction equivalent, the temperature of reaction of step c and/or the reaction times of step c.
Preferably, step c makes described the second polymkeric substance react raw a heat reactivity fluorine element urethanes with the blockade agent of 0.1～0.5 gram equivalent.Preferably, the reaction times of described step c is 0.5 to 4 hours.Preferably, the temperature of reaction of described step c is 40 ℃ to 120 ℃.
The article of tool water-repellent oil-repellent of the present invention
In another embodiment, the present invention is about a kind of article of tool water-repellent oil-repellent.At least one surface-coated of described article has described water extraction oil extracticn agent.Described article include but not limited to fabric or leather.Described fabric includes, but are not limited to: nylon Ta Futa (taffeta), trevira or cotton furniture cloth.Described leather includes, but are not limited to: coated split leather or pigskin.Preferably, can be first content take solvent cut water extraction oil extracticn agent of the present invention to heat reactivity fluorine element urethanes wherein as 0.5 to 2wt%, then be coated on the surface of described article.
Described coating method need not limit, and for instance, described water extraction oil extracticn agent can be packed into spray bottle, then be sprayed on uniformly via nozzle on the surface of described article; Or, also can be poured on the surface of described article by direct described water extraction oil extracticn agent, then make it evenly coat the surface of described article; Or, described article can be immersed to described water extraction oil extracticn agent, and being soaked, described water extraction oil extracticn agent moistens described article.
After applying described water extraction oil extracticn agent, can make again described article via dry air or be heating and curing, can make the surface of described article there is drying, dial oil and wash resistant characteristic.Feasiblely, described in, the program of being heating and curing is that the described article that are coated with described water extraction oil extracticn agent are heated 60 to 200 seconds at 100 ℃ to 190 ℃.
[preparation of solvent-borne type short carbon chain oil extracticn agent of the present invention]
Following paragraph will be recorded the example of several preparations water extraction oil extracticn agent of the present invention; only following contained example is preparation process and the correlation parameter for exemplary teaching water extraction oil extracticn agent of the present invention, not for limiting the claimed claim scope of the present invention.
Embodiment mono-
By the short carbon chain fluorine alcohol compound (CF of 0.5 gram equivalent
3(CF
2)
5(CH
2)
2oH) add in the 2L glass reaction container of equipping agitator, vacuum motor, thermometer and condenser etc.The air of extracting out in described glass reaction container enters after vacuum state it, continues to vacuumize 30 minutes, then abolishes after vacuum with nitrogen, continues logical nitrogen, so that subsequent reactions carries out under nitrogen environment.
Then add the isoflurane chalcone diisocyanate (IPDI) of 1.17 gram equivalents, and heating makes described glass reaction container be maintained at 85～90 ℃ 2 hours.Then measure the weight percent of NCO group.In the time that reaching 9-11wt%, the weight percent of NCO group adds the trihydroxymethyl propane (TMP) of 0.21 gram equivalent and the stearyl alcohol (CH of 0.32 gram equivalent
3(CH
2)
17, and make temperature be maintained at 85 ± 3 ℃ more than 12 hours OH).In the time that the weight percent of NCO group reaches 1-1.5%, be cooled to 50 ± 3 ℃, and add the methyl ethyl ketoxime (methyl ethyl ketone oxime) of 0.15 gram equivalent, then holding temperature 1 hour.Thereafter, then add 584.4 grams N,N-DIMETHYLACETAMIDE (DMAc) stir 30 minutes.Described polyreaction produces 1021 grams of weight, the polymer dispersion liquid that solid content is 39.6%, i.e. the solvent-borne type short carbon chain oil extracticn agent of the present embodiment.
Embodiment bis-
By the short carbon chain fluorine alcohol compound (CF of 0.5 gram equivalent
3(CF
2)
5(CH
2)
2oH) add in the 2L glass reaction container of equipping agitator, vacuum motor, thermometer and condenser etc.The air of extracting out in described glass reaction container enters after vacuum state it, continues to vacuumize 30 minutes, then abolishes after vacuum with nitrogen, continues logical nitrogen, so that subsequent reactions carries out under nitrogen environment.
Then add the isoflurane chalcone diisocyanate (IPDI) of 0.87 gram equivalent and the dicyclohexyl methane diisocyanate (H of 0.3 gram equivalent
12mDI), and heating make described glass reaction container be maintained at 90～95 ℃ 2 hours.Then measure the weight percent of NCO group.
In the time that reaching 9-11wt%, the weight percent of NCO group adds the trihydroxymethyl propane (TMP) of 0.21 gram equivalent and the stearyl alcohol (CH of 0.32 gram equivalent
3(CH
2)
17, and make temperature be maintained at 85 ± 3 ℃ more than 12 hours OH).
In the time that the weight percent of NCO group reaches 1-1.5wt%, be cooled to 50 ± 3 ℃, and add the methyl ethyl ketoxime (methyl ethyl ketone oxime) of 0.15 gram equivalent, then holding temperature 1 hour.Thereafter, then add the methylethylketone (MEK) of the N,N-DIMETHYLACETAMIDE (DMAc) of 500 grams and 98.5 grams to stir 30 minutes.Described polyreaction produces 1041 grams of weight, the polymer dispersion liquid that solid content is 39.4%, i.e. the solvent-borne type short carbon chain oil extracticn agent of the present embodiment.
Embodiment tri-
Desired raw material, weight and polymerization process are identical with embodiment mono-, but change the raw material stearyl alcohol (CH of subordinate phase polyreaction
3(CH
2)
17oH) for mixing the stearyl alcohol (CH of 0.22 gram equivalent
3(CH
2)
17oH) with the lauryl alcohol (CH3 (CH2) 11OH) of 0.1 gram equivalent, and make temperature be maintained at 85 ± 3 ℃ more than 12 hours.
In the time that the weight percent of NCO group reaches 1-1.5wt%, be cooled to 50 ± 3 ℃, and add the methyl ethyl ketoxime (methyl ethyl ketone oxime) of 0.15 gram equivalent, then holding temperature 1 hour.Thereafter, then add 584.4 grams toluene (toluene) stir 30 minutes; Described polyreaction produces 1012.6 grams of weight, the polymer dispersion liquid that solid content is 39.1%, i.e. the solvent-borne type short carbon chain oil extracticn agent of the present embodiment.
Embodiment tetra-
Desired raw material, weight and polymerization process are identical with embodiment bis-, but change the raw material stearyl alcohol (CH of subordinate phase polyreaction
3(CH
2)
17oH) for mixing the stearyl alcohol (CH of 0.22 gram equivalent
3(CH
2)
17oH) with the lauryl alcohol (CH of 0.1 gram equivalent
3(CH
2)
11, and make temperature be maintained at 85 ± 3 ℃ more than 12 hours OH).
In the time that the weight percent of NCO group reaches 1-1.5wt%, be cooled to 50 ± 3 ℃, and add the methyl ethyl ketoxime (methyl ethyl ketone oxime) of 0.15 gram equivalent, then holding temperature 1 hour.Thereafter, then add the methylethylketone (MEK) of the toluene (toluene) of 600 grams and 98.5 grams to stir 30 minutes; Described polyreaction produces 1132.6 grams of weight, the polymer dispersion liquid that solid content is 35.7%, i.e. the solvent-borne type short carbon chain oil extracticn agent of the present embodiment.Embodiment five
Desired raw material, weight and polymerization process are identical with embodiment bis-, but change the raw material stearyl alcohol (CH of subordinate phase polyreaction
3(CH
2)
17oH) weight is 0.3 gram equivalent, and the raw material methyl ethyl ketoxime (methyl ethyl ketone oxime) that separately changes phase III polyreaction is 0.17 gram equivalent.Add again the N,N-DIMETHYLACETAMIDE (DMAc) of 500 grams and the methylethylketone (MEK) of 98.5 grams to stir after 30 minutes, polyreaction produces 1037 grams of weight, solid content is 39.1% polymer dispersion liquid, i.e. the solvent-borne type short carbon chain oil extracticn agent of the present embodiment.
[effect detection of water extraction oil extracticn agent of the present invention]
Following paragraph, by the characteristic of the prepared water extraction oil extracticn agent of the described embodiment of test, is understood the practice effect of water extraction oil extracticn agent of the present invention in order to one of ordinary skill in the art.
Embodiment six: fabric treating
Dilute the prepared solvent-borne type short carbon chain oil extracticn agent of described embodiment mono-to five to the element of heat reactivity fluorine wherein urethanes content as 0.5wt% take butanone.Then, with soak the mode of moistening by described diluted water extraction oil extracticn agent be applied to fabric to be tested (trevira) upper after, press and inhale (pressing suction rate (Pick Up) is 60～70%) via roll, then dry 2 minutes with 120 ℃.And then carry out follow-up test.
In the present embodiment, separately test with the same manner with commercially available water-based oil extracticn agent PYMAGARD C-63N (YMAG-CURTIN, S.A.), with (comparative example one) as a comparison.
[water-repellancy check]
Check the water-repellancy (reference table 1) of the fabric sample of processing with AATCC standard test method No.22.
Table 1: water-repellancy inspecting standard
| Water-repellancy progression | State description |
| 100 | Surface is moistening without adhering to |
| 90 | Surface shows that trace is moistening |
| 80 | Display section, surface is moistening |
| 70 | Surface shows moistening |
| 50 | The all demonstrations in surface are moistening |
| 0 | The all demonstrations in table the inside are moistening |
In this check, the water of 250 milliliters is fallen on the fabric to be tested of upholding on 6 inch diameter plastic ferrules from 27 degree angles in thread mode.Until excessive moisture after 6 inch funnels on being suspended on fabric to be tested flow down, the standard of reference table 1 with visual assessment fine thing to be tested.Experimental result is as shown in table 3.
[dialling oiliness check]
Check group oiliness (reference table 2) of the fabric sample of processing with AATCC standard test method No.118.
Table 2: dial oiliness inspecting standard
| Dial oiliness progression | Testing liquid |
| 8 | Normal heptane |
| 7 | Octane |
| 6 | N-decane |
| 5 | N-dodecane |
| 4 | Positive 14 alkane |
| 3 | N-hexadecane |
| 2 | 35% n-hexadecane and 65%Nujol |
| 1 | 65%Nujol |
| 0 | Too late 1 |
From the testing liquid of lowest number, testing liquid is added drop-wise on fabric to be tested on three positions of separating at least 5 millimeters (0.05 millimeter of 5 millimeters of diameters or volume).Observe 30 seconds of this drop.If while end at this moment, there is in three the shape of two still, the testing liquid of next higher number to be complied with to identical inspecting standard and test and observe while thering is no moisten fabric sample to semisphere and drop periphery for spherical.This program lasts till to have has two can not be maintained spherical till semisphere or moistening phenomenon occurs in three an of testing liquid.The oiliness of dialling of fabric is commented etc. to be and in its three, is had two to drop in and in 30 seconds, keep spherical to semisphere and there is no the highest numbering test solution of moistening phenomenon.Experimental result is as shown in table 3.
[discolouration check]
Color has three attributes, i.e. form and aspect, chroma and lightness.Form and aspect have different color names to represent, as red, yellow, blue, green (white, black, ash belongs to without form and aspect).Chroma is the saturation ratio of color form and aspect, and lightness is the lightness that represents color, namely the glossiness of object.
Utilize X-Rite948 color difference meter measure fabric to be tested through the color-values before and after water extraction oil extracticn agent is processed (L, a, b) after, calculate total color difference (△ E, Total color difference) with following formula.△ E value is larger, represents that discolouration is larger.More discolouration represents that water extraction oil extracticn agent used can adversely cause the colourity that applies fabric to change.Experimental result is as shown in table 3.
△E＝[（△L）
2＋（△a）
2＋（△b）
2]
1/2
△ L: black and white lightness difference; △ a: red green difference; △ b: champac value of chromatism
The cloth testing result of table 3: embodiment six
| Drying progression | Dial oily progression | Discolouration | |
| Embodiment mono- | 100 | 5 | 0.38 |
| Embodiment bis- | 100 | 5 | 0.46 |
| Embodiment tri- | 100 | 4 | 0.36 |
| Embodiment tetra- | 100 | 4 | 0.33 |
| Embodiment five | 100 | 5 | 0.49 |
| Comparative example one | 90 | 3 | 0.85 |
As shown in Table 3, compared to the water-based water extraction oil extracticn agent of peddling on the market, solvent-borne type short carbon chain oil extracticn agent of the present invention uses to be had more outstanding drying and dials oily characteristic on textile article, and is difficult for causing fabric face variable color.
Embodiment seven: leather processing
Dilute the prepared solvent-borne type short carbon chain oil extracticn agent of described embodiment mono-to five to the element of heat reactivity fluorine wherein urethanes content as 5wt% take vinyl acetic monomer.Then, use spray gun with spraying method, the water extraction oil extracticn agent after described dilution to be imposed on after coated split leather product surface, first 80 ℃ of oven for drying 3 minutes, then be placed in 25 ℃ of environment 24 hours.And then carry out follow-up test.
The present embodiment is separately with commercially available solvent-borne type oil extracticn agent
lPA (Du Pont) tests in this way, with (comparative example two) as a comparison.
[test of water droplet progression]
The listed standard test liquid of this test following table 4 is tested.First test with the lowest class experimental liquid.Drip upper 3 standard test liquid in leather surface different positions place, and observed for 10 seconds.If drip experimental liquid and can moistening surface do not get higher one-level experimental liquid and test, until experimental liquid drop in 10 seconds can obvious moistening surface, be the water droplet progression (drying progression) of this surface.Test-results is as listed in table 6.
Table 4: drying progression standard
| Water-repellancy progression | Experimental liquid: aqueous isopropanol (%v/v) |
| 1 | 2 |
| 2 | 5 |
| 3 | 10 |
| 4 | 20 |
| 5 | 30 |
[test of oil droplet progression]
The listed standard test oil of this test following table 5 is tested.First test with the lowest class test oil.Drip upper 3 standard test oil in leather surface different positions place, and observed for 30 seconds.If drip test oil and can moistening surface do not get higher one-level test oil and test, until test oil droplet can obvious moistening surface in 30 seconds, be the water droplet progression (dialling oily progression) of this surface.Test-results is as listed in table 6.
Table 5: dial oily progression standard
| Dial oiliness progression | Test oil |
| 1 | Mineral oil viscosity: 140dynes/cm |
| 2 | 65:35 mineral oil: n-hexadecane |
| 3 | N-hexadecane |
| 4 | N-tetradecane |
| 5 | N-dodecane |
The leather test-results of table 6: embodiment seven
| Drying progression | Dial oily progression | |
| Embodiment mono- | 6 | 4 |
| Embodiment bis- | 6 | 3 |
| Embodiment tri- | 6 | 4 |
| Embodiment tetra- | 6 | 4 |
| Embodiment five | 6 | 3 |
| Comparative example two | 5 | 2 |
As shown in Table 6, solvent-borne type short carbon chain oil extracticn agent of the present invention uses on leatherware, has more outstanding drying and dials oily characteristic compared to the water extraction oil extracticn agent of peddling on the market.
One of ordinary skill in the art is worked as and can be understood, under spirit of the present invention, and the various variations that can carry out according to embodiment of the present invention.Therefore, obvious listed embodiment is not in order to limit the present invention, but attempt is under the definition of institute's claim, is covered by the modification of making in spirit of the present invention and category.
Claims (38)
1. a fluorine element urethanes, it has structure shown in following Chemical formula 1:
R
f-R
x-O-[(O=C)-HN-R
y-NH-(C=O)]
q-OR
z (1)；
Wherein, q is selected from 1 to 10 integer;
Wherein, R
ffor C
3～C
6perfluoroalkyl; R
xbe selected from C
1～C
10alkyl, C
1～C
10hydroxyalkyl, ester group alkyl, sulfonic acid amido, carbonyl acid amide base and oxygen base phenyl;
Wherein, R
ybe selected from the C that is substituted or is unsubstituted
1～C
10alkyl, cycloalkyl, phenyl, naphthyl, alkyl phenyl, alkyl-cycloalkyl, alkyl phenyl alkyl and alkyl-cycloalkyl-alkyl;
Wherein, R
zbe selected from ROH, R (EO)
mh, R-(EO)
m(PO)
nh, C
1～C
10alkyl alcohol radical, polyoxyethyl propyl alcohol radical, polyoxyethyl propyl polyoxy ethyl alcohol radical, C
1～C
3thiol group, thiophenol base, ketoxime base, C
1～C
10acidic group, diketo, amide group, pyrazolyl and phenolic group; Wherein, described R
zbe borrow OH group in its structure be binding on (C=O) in described Chemical formula 1-carbon atom;
Wherein, R is C
8～C
20straight or branched alkyl; EO is oxyethane; PO is propylene oxide; M is 3～50 integer; N is 3～50 integer.
2. fluorine element urethanes as claimed in claim 1, wherein, described sulfonic acid amido has structure shown in following Chemical formula 2-a:
-SO
2-N(R
1)R
2- (2-a)；
Wherein, R
1for hydrogen or C
1～C
10alkyl;
Wherein, R
2for C
1～C
10alkylidene group.
3. fluorine element urethanes as claimed in claim 1, wherein, described carbonyl acid amide base has structure shown in following Chemical formula 2-b:
-CO-N(R
1)R
2- (2-b)；
Wherein, R
1for hydrogen or C
1～C
10alkyl;
Wherein, R
2for C
1～C
10alkylidene group.
4. fluorine element urethanes as claimed in claim 1, wherein, described ester group alkyl has structure shown in following Chemical formula 2-c:
-CH
2-CH(OCOR
3)CH
2- (2-c)；
Wherein R
3for hydrogen or methyl.
5. fluorine element urethanes as claimed in claim 1, wherein, described oxygen base phenyl has structure shown in following Chemical formula 2-d:
-O-Ar- (2-d)；
Wherein, Ar is Ben Ji Huo Benzyl base.
6. fluorine element urethanes as claimed in claim 1, wherein, described R
ybe selected from through 1-3 C
1～C
3the C that alkyl replaces
1～C
10alkyl, cycloalkyl, phenyl, naphthyl, alkyl phenyl, alkyl-cycloalkyl, alkyl phenyl alkyl and alkyl-cycloalkyl-alkyl.
7. fluorine element urethanes as claimed in claim 1, wherein, described R
ybe selected from aminomethyl phenyl, phenylmethylene phenyl, naphthyl, methylene-benzene methylene, hexyl, cyclohexyl, cyclohexylmethylene cyclohexyl, different fluorine that ketone group and tetramethylphenyl.
8. a composition of preparing fluorine element urethanes, it comprises:
The fluorine alcohol compound of 0.2～1.0 gram equivalent;
The fat alcohol compound of 0.2～1.0 gram equivalent;
The vulcabond of 0.8～2.0 gram equivalent or its polymkeric substance;
The bridging agent of 0.1～0.5 gram equivalent; And
The blockade agent of 0.1～0.5 gram equivalent.
9. composition as claimed in claim 8, wherein, described fluorine alcohol compound is perfluoroalkyl alkylol cpd.
10. composition as claimed in claim 9, wherein, described perfluoroalkyl alkylol cpd has structure shown in following Chemical formula 2:
R
f-R
x-OH (2)；
Wherein, R
ffor C
3～C
6perfluoroalkyl;
Wherein, R
xfor C
1～C
10alkyl, C
1～C
10hydroxyalkyl, ester group alkyl, sulfonic acid amido, carbonyl acid amide base or oxygen base phenyl.
11. compositions as claimed in claim 10, wherein, described sulfonic acid amido has structure shown in following Chemical formula 2-a:
-SO
2-N(R
1)R
2- (2-a)；
Wherein, R
1for hydrogen or C
1～C
10alkyl;
Wherein, R
2for C
1～C
10alkylidene group.
12. compositions as claimed in claim 10, wherein, described carbonyl acid amide base has structure shown in following Chemical formula 2-b:
-CO-N(R
1)R
2- (2-b)；
Wherein, R
1for hydrogen or C
1～C
10alkyl;
Wherein, R
2for C
1～C
10alkylidene group.
13. compositions as claimed in claim 10, wherein, described ester group alkyl has structure shown in following Chemical formula 2-c:
-CH
2-CH(OCOR
3)CH
2- (2-c)；
Wherein R
3for hydrogen or methyl.
14. compositions as claimed in claim 10, wherein, described oxygen base phenyl has structure shown in following Chemical formula 2-d:
-O-Ar- (2-d)；
Wherein, Ar is Ben Ji Huo Benzyl base.
15. compositions as claimed in claim 8, wherein, described fluorine alcohol compound is selected from least one in following compound:
CF
3(CF
2)
6(CH
2)
1OH；
CF
3(CF
2)
6(CH
2)
2OH；
CF
3(CF
2)
5(CH
2)
1OH；
CF
3(CF
2)
5(CH
2)
2OH；
CF
3(CF
2)
4(CH
2)
1OH；
CF
3(CF
2)
4(CH
2)
2oH; And
C
6F
13-O-Ar-OH；
Wherein, Ar is Ben Ji Huo Benzyl base.
16. compositions as claimed in claim 8, wherein, described vulcabond is fragrant family vulcabond, fatty family vulcabond or its combination.
17. compositions as claimed in claim 16, wherein, described fragrant family vulcabond comprises: tolylene diisocyanate, ditan-4,4`-vulcabond, naphthalene-1,5-vulcabond, xylylene diisocyanate or its mixing.
18. compositions as claimed in claim 16, wherein, described fatty family vulcabond comprises: hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, isoflurane chalcone diisocyanate, cyclohexyl diisocyanate, tetramethylxylylene diisocyanate or its mixing.
19. compositions as claimed in claim 8, wherein, described fat alcohol compound has at least one of structure shown in following chemical formula 3-a, chemical formula 3-b, chemical formula 3-c:
R-OH (3-a)；
R-(EO)
m-H (3-b)；
R-(EO)
m(PO)
n-H (3-c)；
Wherein, R is C
8～C
20straight or branched alkyl;
Wherein, EO is oxyethane;
Wherein, PO is propylene oxide;
Wherein, the integer that m is 3～50; And
Wherein, the integer that n is 3～50.
20. compositions as claimed in claim 8, wherein, described bridging agent comprises three alkylol cpds.
21. compositions as claimed in claim 20, wherein, described three alkylol cpds comprise polyoxyethyl propyl triol, polyoxyethyl propyl polyoxy ethyl triol, trihydroxymethyl propane, glycerine, hexanetriol or its mixture.
22. compositions as claimed in claim 8, wherein, described blockade agent comprises methyl alcohol, ethanol, sulfur alcohol, β-thiophenol, methyl ethyl ketoxime, acetoxime, cyclohexanone-oxime, Diacetylmonoxime, diethyl malonic acid, methyl ethyl diketone, acetone ethyl acetic acid, ε-caprolactam, 3，5-dimethylpyrazole, phenol or its mixture.
23. compositions as claimed in claim 8, it further comprises the solvent of 50～80 weight percents, and wherein said weight percent is take the gross weight of described composition as basis.
24. compositions as claimed in claim 16, wherein, described solvent comprises ethyl acetate, butylacetate, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), dimethyl formamide, N,N-DIMETHYLACETAMIDE, toluene or its mixture.
25. compositions as claimed in claim 8, wherein, described fluorine element urethanes is a heat reactivity fluorine element urethanes.
26. compositions as claimed in claim 8, wherein, described fluorine element urethanes comprises fluorine element urethanes claimed in claim 1.
27. 1 kinds of solvent-borne type short carbon chain oil extracticn agents, it comprises:
The heat reactivity fluorine element urethanes of 20～50 weight percents; And
The solvent of 50～80 weight percents;
Wherein, described weight percent is take the gross weight of described solvent-borne type short carbon chain oil extracticn agent as basis;
Wherein, described heat reactivity fluorine element urethanes comprises the fluorinated polyurethane compound as described in any one in claim 1 to 7, the prepared fluorine element urethanes of the composition as described in any one in claim 8 to 25 or its combination.
28. solvent-borne type short carbon chain oil extracticn agents as claimed in claim 27, wherein, described heat reactivity fluorine element urethanes has C
3～C
6perfluoroalkyl.
29. solvent-borne type short carbon chain oil extracticn agents as claimed in claim 27, wherein, described solvent comprises ethyl acetate, butylacetate, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), dimethyl formamide, N,N-DIMETHYLACETAMIDE, toluene or its mixture.
Prepare the method for the solvent-borne type short carbon chain oil extracticn agent described in claim 27 for 30. 1 kinds, it comprises following steps:
A, the vulcabond that makes the fluorine alcohol compound of 0.2～1.0 gram equivalent and 0.8～2.0 gram equivalent or its polymer reaction raw one first polymkeric substance;
B, make the bridging agent of described the first polymkeric substance and the fat alcohol compound of 0.2～1.0 gram equivalent and 0.1～0.5 gram equivalent react raw one second polymkeric substance; And
C, make described the second polymkeric substance react raw a heat reactivity fluorine element urethanes with the blockade agent of 0.1～0.5 gram equivalent;
Wherein, described step a, step b and/or step c account in the solvent of 50～80 weight percents and carry out in one; Wherein, described weight percent is take the gross weight of all reactants in the reaction of described step a, step b or step c as basis.
31. methods as claimed in claim 30, wherein, in described step a, further comprise: measure the weight percent of the NCO group of the end of described the first polymkeric substance, when the weight percent of described NCO group reaches after 7～11 weight percents, start to carry out described step b; The weight percent of wherein said NCO group is take the gross weight of described the first polymkeric substance as basis.
32. methods as claimed in claim 30, wherein, in described step b, further comprise: measure the weight percent of the NCO group of the end of described the second polymkeric substance, when the weight percent of described NCO group reaches after 0.5～2.0 weight percent, start to carry out described step c; The weight percent of wherein said NCO group is take the gross weight of described the second polymkeric substance as basis.
33. methods as claimed in claim 30, wherein, described step a, described step b and/or described step c carry out in 40 ℃ to 120 ℃.
34. methods as claimed in claim 30, wherein, the reaction times of described step a is 1 to 5 hours.
35. methods as claimed in claim 30, wherein, the reaction times of described step b is 6 to 24 hours.
36. methods as claimed in claim 30, wherein, the reaction times of described step c is 0.5 to 4 hours.
The article of 37. 1 kinds of tool water-repellent oil-repellents, wherein, at least one surface-coated of described article has water extraction oil extracticn agent as claimed in claim 27.
38. article as claimed in claim 37, wherein, described article are fabric or leather.
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|---|---|---|---|
| TW101140257 | 2012-10-31 | ||
| TW101140257A TWI449777B (en) | 2012-10-31 | 2012-10-31 | Short chain fluorinated polyurethane compound and water-repellent and oil-repellent agent containing the same |
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|---|---|
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| CN112239956A (en) * | 2019-07-16 | 2021-01-19 | 漳州丰笙新材料有限公司 | Composition of fluorine polyurethane for water and oil repellent and preparation method thereof |
| CN110698630A (en) * | 2019-10-10 | 2020-01-17 | 江苏华大新材料有限公司 | Solvent type polyurethane resin, preparation method thereof and waterproof umbrella with lotus leaf effect |
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| TW201416429A (en) | 2014-05-01 |
| TWI449777B (en) | 2014-08-21 |
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