CN116377721A - 聚氨酯无氟易去污整理剂及制备方法 - Google Patents
聚氨酯无氟易去污整理剂及制备方法 Download PDFInfo
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- CN116377721A CN116377721A CN202310392463.6A CN202310392463A CN116377721A CN 116377721 A CN116377721 A CN 116377721A CN 202310392463 A CN202310392463 A CN 202310392463A CN 116377721 A CN116377721 A CN 116377721A
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- Prior art keywords
- polyurethane
- compound
- fluorine
- linear
- soil release
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 49
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 49
- 239000002689 soil Substances 0.000 title claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- -1 alcohol compound Chemical class 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 238000006482 condensation reaction Methods 0.000 claims abstract description 7
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 7
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 5
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims 1
- 230000003670 easy-to-clean Effects 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 26
- 230000036571 hydration Effects 0.000 abstract description 9
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- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 6
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- 230000002940 repellent Effects 0.000 abstract description 6
- 239000005871 repellent Substances 0.000 abstract description 6
- 238000005202 decontamination Methods 0.000 abstract description 4
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- 230000035515 penetration Effects 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 21
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 18
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- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
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- 238000003756 stirring Methods 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 6
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical class CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 4
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 4
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 3
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
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- 229940071160 cocoate Drugs 0.000 description 2
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- JIZCYLOUIAIZHQ-UHFFFAOYSA-N ethyl docosenyl Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC JIZCYLOUIAIZHQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- XIRNKXNNONJFQO-UHFFFAOYSA-N ethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC XIRNKXNNONJFQO-UHFFFAOYSA-N 0.000 description 2
- MMXKVMNBHPAILY-UHFFFAOYSA-N ethyl laurate Chemical compound CCCCCCCCCCCC(=O)OCC MMXKVMNBHPAILY-UHFFFAOYSA-N 0.000 description 2
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- 150000002191 fatty alcohols Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- QSQLTHHMFHEFIY-UHFFFAOYSA-N methyl behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OC QSQLTHHMFHEFIY-UHFFFAOYSA-N 0.000 description 2
- 238000003541 multi-stage reaction Methods 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
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- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
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- 238000004078 waterproofing Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
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- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
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- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
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- OFIDNKMQBYGNIW-UHFFFAOYSA-N arachidonic acid methyl ester Natural products CCCCCC=CCC=CCC=CCC=CCCCC(=O)OC OFIDNKMQBYGNIW-UHFFFAOYSA-N 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
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- 230000001186 cumulative effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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Abstract
本发明公开了一种聚氨酯无氟易去污整理剂及制备方法,所述聚氨酯无氟易去污整理剂是由二元醇化合物、多异氰酸酯、功能单体以及亲水单体经过缩聚反应生成聚氨酯聚合物,再经乳化后获得。本发明通过聚氨酯的缩合反应,将低表面能的无氟拒水基团和亲水性的聚醚等基团有机结合起来,在干态下,低表面能的拒水基团占据了纤维表面,降低了纤维的表面张力,防止污物吸附并能阻止水和污物在接触织物时发生渗透达到防污目的。在水中,高表面能的亲水聚醚链段翻转迁移到纤维表面,通过水合作用变在纤维表面定向排列形成一层水化层,降低了水‑纤维界面张力,从而达到易去污的效能。
Description
技术领域
本发明属于高分子领域和纺织助剂领域,具体涉及一种聚氨酯无氟易去污整理剂的组成,还涉及该聚氨酯无氟易去污整理剂的制备方法。本发明应用于纺织纤维面料的易去污整理。
背景技术
易去污整理剂作为一种功能型助剂被广泛使用。当沾污织物在洗涤过程中,油性污物、织物和水相处于平衡状态,通过降低水相与纤维相之间的界面张力或提高油相与纤维之间的界面张力,污物容易从织物上呈卷珠状脱落进入洗液中,从而实现有效的易去污效果。
目前,现有的易去污整理剂通常由疏水的长链含氟丙烯酸酯单体和带有亲水长链聚氧乙烯结构的单体通过共聚合实现。在此结构中,低表面能的氟碳链段在空气中自动迁移到纤维表面以降低纤维-空气表面张力,达到防污效果;在水洗时,高表面能的亲水聚氧乙烯链段会翻转迁移到纤维表面,通过水合作用,聚氧乙烯链段卷曲状态变成舒展伸长状态,从而在纤维表面定向排列形成一层水化层。纤维表面亲水性水化层的存在使水-纤维界面的界面张力降低,纤维表面的污渍得以分散到水中达到去污效果。
由于全含氟化合物的低生物降解性和累积效应所引发的环境生态问题引发全球关注,因此降低氟化物的用量或用非氟类产品替代,已经成为趋势和必然。
发明内容
本发明的第一个目的在于提供一种制备方法简单、易去污效果好、环保的聚氨酯无氟易去污整理剂。
本发明的第一个目的通过以下的技术措施来实现:一种聚氨酯无氟易去污整理剂,其特征在于,它是由二元醇化合物、多异氰酸酯、功能单体以及亲水单体经过缩聚反应生成聚氨酯聚合物,再经乳化后获得。
本发明通过聚氨酯的缩合反应,将低表面能的无氟拒水基团和亲水性的聚醚等基团有机结合起来,在干态下,低表面能的拒水基团占据了纤维表面,降低了纤维的表面张力,防止污物吸附并能阻止水和污物在接触织物时发生渗透达到防污目的。在水中,高表面能的亲水聚醚链段翻转迁移到纤维表面,通过水合作用变在纤维表面定向排列形成一层水化层,降低了水-纤维界面张力,从而达到易去污的效能。
本发明所述二元醇化合物的结构式为:
R1:碳数为6~30的饱和或不饱和的直链或支链长碳链烷基基团,优选饱和直链的烷基基团,其中,烷基碳链数10~22的直链饱和烷基效果最佳。R1包括但不限于辛基、癸基、月桂基、十四烷基、十六烷基、二十烷基等。
R2:碳数为2~8的直链或支链烷基基团,最佳碳链数为2~4,或是带两个羰基的直链或支链烷基基团;
R3:碳数为1~6的直链或支链烷基基团,包括但不限于甲基,乙基,丙基,丁基等基团。
本发明所述二元醇化合物由以下第一化合物(式I)通过催化还原得到,适合的催化剂包括硼氢化钠,氢化铝锂等:
R1:碳数为6~30的饱和或不饱和的直链或支链长碳链烷基基团;
R2:碳数为2~8的直链或支链烷基基团,或是带两个羰基的直链或支链烷基基团;
R3:碳数为1~6的直链或支链烷基基团。
本发明所述的第一化合物(式I)通过依次由以下第二化合物(式II)和第三化合物(式III)通过缩合反应后,再进一步与第四化合物(式IV)加成后得到:
R0:独立地为氢原子;
R1:碳数为6~30的饱和或不饱和的直链或支链长碳链烷基基团;
R2:碳数为2~8的直链或支链烷基基团;
R4:碳数为1~6的饱和或不饱和碳链基团;
R5:碳数为2~8的直链、支链或环状烷烃基基团;
X:同时为卤素原子或者为α,β-不饱和羰基基团。
本发明所述第二化合物为甲酸酯的系列衍生物。包括但不限于甲酸甲酯、甲酸乙酯或甲酸丁酯等。
本发明所述第三化合物为长链烷基酯的系列物中一种或两种以上组合。包括但不限于月桂酸甲酯、月桂酸乙酯、椰油酸甲酯、椰油酸乙酯、棕榈酸甲酯、棕榈酸乙酯、硬脂酸甲酯、硬脂酸乙酯、油酸甲酯、油酸丁酯、油酸乙酯、花生酸甲酯、花生酸乙酯、二十二烷酸甲酯和二十二烷酸乙酯等中一种或两种以上组合。
本发明所述第四化合物为卤素原子取代的双卤代烃或α素原子不饱和羰基基团。包括但不限于1,2-二氯乙烷,1,2-二溴乙烷,1,4-二氯丁烷,1,4-二溴丁烷,乙二醇二(甲基)丙烯酸酯,二乙二醇二(甲基)丙烯酸酯,丙二醇二(甲基)丙烯酸酯,二丙二醇二(甲基)丙烯酸酯,三丙二醇二(甲基)丙烯酸酯,1,3-丁二醇二(甲基)丙烯酸酯,1,4-丁二醇二(甲基)丙烯酸酯和1,6-己二醇二(甲基)丙烯酸酯中一种或两种以上组合。
本发明所述的第一化合物(式I)通过由第二化合物(式II)和第三化合物(式III)和第四化合物(式IV)通过分步反应制得,其摩尔比为第二化合物(式II):第三化合物(式III):第四化合物(式IV)=1~1.5:1:1~1.5。具体为第二化合物(式II)和第三化合物(式III)进行第一步缩合反应,反应温度为0~50℃,反应时间1~24h,反应催化剂包括但不限于氢化钠,甲醇钠,乙醇钠,叔丁醇钾等,催化剂的用量与第二化合物(式II)的摩尔比例为2~1:1。
本发明所述第一化合物(式I)通过由第二化合物(式II)和第三化合物(式III)和第四化合物(式IV)通过分步反应制得,具体为第二化合物(式II)和第三化合物(式III)缩合反应与第四化合物(式IV)进行第二步反应,反应催化剂包括但不限于氢化钠、甲醇钠、乙醇钠、叔丁醇钾等,反应催化剂的用量与第四化合物(式IV)的摩尔比例为2~1:1,反应温度为0~50℃,反应时间1~24h。
本发明所述多异氰酸酯是带有两个或两个以上异氰酸酯基团物质的一种或两种以上组合。包括但不限于芳香族或脂肪族异氰酸酯中的甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(H12MDI)、苯二亚甲基二异氰酸酯(XDI)、四甲基间苯二亚甲基二异氰酸酯(TMXDI)和三甲基-1,6-六亚甲基二异氰酸酯(TMHDI)中一种或两种以上组合,以及前述二异氰酸酯的二聚体、三聚体、缩二脲、碳化二亚胺改性,与丙二醇反应产物,与三羟甲基丙烷反应产物等衍生物中一种或两种以上组合。优选二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)及衍生物中的一种或两种以上组合。
本发明所述功能单体是具有活泼氢的小分子化合物,即是具有两个或两个以上羟基的多元醇或者酚类,或者具有两个或两个以上氨基的多元胺,或者具有单活泼氢官能团的化合物如酰胺、肟、咪唑等化合物中一种或两种以上组合。包括但不限于1,4-丁二醇,乙二醇,一缩二乙二醇,1,6-己二醇,丙三醇、三羟甲基丙烷,双三羟甲基丙烷,二羟甲基丙酸、二羟甲基丁酸、酒石酸、二乙醇胺、三乙醇胺、甲基二乙醇胺等多羟基化合物,或乙二胺,己二胺,异佛尔酮二胺,二胺,二乙烯三胺,或酚类、己内酰胺、乙酰乙酸乙酯、丙二酸二乙酯、丙酮肟、甲乙酮肟、3,5-二甲基吡唑等含单活泼氢原子的化合物的一种或两种以上组合。
本发明所述亲水单体的结构式是:
R6:独立地为氢或者甲基;
Y:独立地为羟基,伯胺基,或者仲胺基;
x,y,z:为0~100数值,且x,y,z不能同时为零。
本发明所述亲水单体是各种聚乙二醇、聚丙二醇、或聚乙二醇/聚丙二醇的嵌段聚合物或各种聚醚胺等等。亲水单体优选的分子量是1000~6000。可以采用商品化的产品如美国DOW公司的VORANOL系列以及美国HUNTSMAN公司的JEFFAMINE系列。
本发明的第二个目的在于提供一种上述聚氨酯无氟易去污整理剂的制备方法。
本发明的第二个目的通过以下的技术措施来实现:一种上述聚氨酯无氟易去污整理剂的制备方法,其特征在于,将二元醇化合物、功能单体、亲水单体和多异氰酸酯在溶剂中进行缩聚反应生成聚氨酯聚合物,反应温度50~100℃,反应时间2~8h,亲水单体重量百分比20~80%,溶剂为丙酮、丁酮、甲基异丁基酮、苯、甲苯、乙酸乙酯或乙酸丁酯;再将聚氨酯聚合物与乳化剂、去离子水混合后,经均质乳化制得聚氨酯无氟易去污整理剂,其中乳化剂的用量为聚氨酯聚合物的10~20%。
本发明所述乳化剂是直链脂肪醇聚氧乙烯醚、异构脂肪醇聚氧乙烯醚、失水山梨醇脂肪酸酯、聚氧乙烯失水山梨醇脂肪酸酯、脂肪酸甘油酯、脂肪酸聚甘油酯或烷基糖苷,或者烷基胺、烷基季铵盐、烷基酯基季铵盐、烷基酰基季铵盐和聚氧乙烯烷基季铵盐中一种或两种以上组合。
与现有技术相比,本发明具有如下显著的效果:
本发明通过聚氨酯的缩合反应,将低表面能的无氟拒水基团和亲水性的聚醚等基团有机结合起来,纤维经过本发明产品整理后,在干态下,低表面能的拒水基团占据了纤维表面,降低了纤维的表面张力,防止污物吸附并能阻止水和污物在接触织物时发生渗透达到防污目的。在水中,高表面能的亲水聚醚链段翻转迁移到纤维表面,通过水合作用变在纤维表面定向排列形成一层水化层,降低了水-纤维界面张力,从而达到易去污的效能。
具体实施方式
实施例1
在装有搅拌、回流冷凝管的三口烧瓶中,加入51.2g甲酸甲酯,213g月桂酸甲酯,55.3g甲醇钠的甲醇溶液,于30~40℃反应8h,反应完毕后向烧瓶中加入50%的乙酸溶液调节整个体系pH为弱酸性,加入等体积饱和氯化钠溶液用力震荡,分离有机层,水层再用15mL甲苯萃取,将萃取液和有机相合并后用无水硫酸钠干燥,将干燥过的有机层移入旋转蒸发器中,减压蒸馏得中间体产物。
然后取上述产物192g,加入22.7g甲醇钠的甲醇溶液,在0~5℃滴加1,4-二溴丁烷35.2g,0~5℃反应5h,加入硼氢化钠甲醇溶液22g,0~5℃反应4h,蒸出部分甲醇,加水分液,将有机相用水洗至中性后用无水硫酸钠干燥,然后移入旋转蒸发器中,减压蒸馏得到蜡状物中间体。
取上述中间体63.6g,加入甲基异丁基酮72g,六亚甲基二异氰酸酯(HDI)46.6g,N-甲基乙醇胺13.3g,聚乙二醇PEG2000(分子量2000)222.3g,二月桂酸二丁基锡0.04g,在70℃下反应6h,用二正丁胺法测定体系无残留异氰酸根后,反应结束,减压蒸馏脱除溶剂,得到聚氨酯聚合物产品。
取上述聚氨酯聚合物产品32g,TWEEN 80 0.16g(英国Croda公司),异构十三醇聚氧乙烯10醚0.18g,醋酸0.5g,水66g,高速剪切乳化,得到聚氨酯易去污整理剂产品。
实施例2
在装有搅拌、回流冷凝管的三口烧瓶中,加入63.2g甲酸乙酯,276.7g棕榈酸甲酯,54.3g甲醇钠的甲醇溶液,于30~40℃反应8h,反应完毕后向烧瓶中加入50%的乙酸溶液调节整个体系pH为弱酸性,加入等体积饱和氯化钠溶液用力震荡,分离有机层,水层再用15mL甲苯萃取,将萃取液和有机相合并后用无水硫酸钠干燥,将干燥过的有机层移入旋转蒸发器中,减压蒸馏得中间体产物。
然后取上述产物231.2g,加入26.7g甲醇钠的甲醇溶液,在0~5℃滴加1,4-二溴丁烷36g,0~5℃反应5h,加入硼氢化钠甲醇溶液19g,0~5℃反应4h,蒸出部分甲醇,加水分液,将有机相用水洗至中性后用无水硫酸钠干燥,然后移入旋转蒸发器中,减压蒸馏得到蜡状物中间体。
取上述中间体61.5g,加入甲基异丁基酮70g,六亚甲基二异氰酸酯(HDI)37.7g,N-甲基乙醇胺11.3g,聚氧乙烯聚氧丙烯醚(分子量3000)297g,二月桂酸二丁基锡0.05g,在70℃下反应6h,用二正丁胺法测定体系无残留异氰酸根后,反应结束,减压蒸馏脱除溶剂,得到聚氨酯聚合物产品。
取上述聚氨酯聚合物产品32g,十八烷基聚氧乙烯基氯化铵1.2g(Ethoquat O/12,AkzoNobel公司),异构十三醇聚氧乙烯10醚1.1g,醋酸0.5g,水65g,高速剪切乳化,得到聚氨酯易去污整理剂产品。
实施例3
在装有搅拌、回流冷凝管的三口烧瓶中,加入68.2g甲酸甲酯,219.3g月桂酸甲酯,56.3g甲醇钠的甲醇溶液,于30~40℃反应8h,反应完毕后向烧瓶中加入50%的乙酸溶液调节整个体系pH为弱酸性,加入等体积饱和氯化钠溶液用力震荡,分离有机层,水层再用15mL甲苯萃取,将萃取液和有机相合并后用无水硫酸钠干燥,将干燥过的有机层移入旋转蒸发器中,减压蒸馏得中间体产物。
然后取上述产物202g,加入22.7g甲醇钠的甲醇溶液,在30℃滴加1,6-己二醇二丙烯酸酯58.9g,30℃反应5h,然后加入硼氢化钠甲醇溶液21g,降温至0~5℃反应4h,加入50%的乙酸溶液调节整个体系为弱酸性,加水分液,将有机相用水洗至中性后用无水硫酸钠干燥,然后移入旋转蒸发器中,减压蒸馏得到蜡状物中间体。
取上述中间体83.2g,加入甲基异丁基酮94.5g,二羟甲基丙酸12.4g,JEFFAMINED2000(HUNTSMAN公司)254g,二月桂酸二丁基锡0.04g,滴加甲苯二异氰酸酯(TDI)47.8g,在70℃下反应6h,用二正丁胺法测定体系无残留异氰酸根后,反应结束,减压蒸馏脱除溶剂,得到聚氨酯聚合物产品。
取上述聚氨酯聚合物产品32g,TWEEN 80 1.2g,蓖麻油聚氧乙烯醚0.78g,三乙胺0.5g,水64g,高速剪切乳化,得到聚氨酯易去污整理剂产品。
实施例4
在装有搅拌、回流冷凝管的三口烧瓶中,加入63.2g甲酸乙酯,303.3g棕榈甲酯,67g乙醇钠的乙醇溶液,于30~40℃反应8h,反应完毕后向烧瓶中加入50%的乙酸溶液调节整个体系pH为弱酸性,加入等体积饱和氯化钠溶液用力震荡,分离有机层,水层再用15mL甲苯萃取,将萃取液和有机相合并后用无水硫酸钠干燥,将干燥过的有机层移入旋转蒸发器中,减压蒸馏得中间体产物。
然后取上述产物237.1g,加入28.5g甲醇钠的甲醇溶液,在30℃滴加1,6-己二醇二丙烯酸酯63.1g,30℃反应5h,然后加入硼氢化钠甲醇溶液18.3g,降温至0~5℃反应4h,加入50%的乙酸溶液调节整个体系为弱酸性,加水分液,将有机相用水洗至中性后用无水硫酸钠干燥,然后移入旋转蒸发器中,减压蒸馏得到蜡状物中间体。
取上述中间体96g,加入甲基异丁基酮109g,JEFFAMINE ED2003(HUNTSMAN公司)192g,二羟甲基丙酸14.4g,二月桂酸二丁基锡0.05g,滴加异佛尔酮二异氰酸酯(IPDI)57.7g,在70℃下反应6h,用二正丁胺法测定体系无残留异氰酸根后,反应结束,减压蒸馏脱除溶剂,得到聚氨酯聚合物产品。
取上述聚氨酯疏水化合物产品32g,异构十三醇聚氧乙烯10醚0.8g,月桂醇聚氧乙烯7醚1.25g,水64g,高速剪切乳化,得到聚氨酯易去污整理剂产品。
比较例1
在装有搅拌、回流冷凝管的三口烧瓶中,加入聚氧乙烯聚氧丙烯醚(分子量3000)199.5g,甲苯二异氰酸酯(TDI)13.9g,N-甲基乙醇胺1.8g,甲乙酮肟1.5g,二月桂酸二丁基锡0.06g,在70℃下反应6h,用二正丁胺法测定体系无残留异氰酸根后,反应结束,减压蒸馏脱除溶剂,得到聚氨酯化合物产品。
取上述聚氨酯疏水化合物产品32g,醋酸0.5g,水67.5g,搅拌得到外观均一产品。
比较例2
在装有搅拌、回流冷凝管的三口烧瓶中,加入JEFFAMINE ED2003(HUNTSMAN公司)204.8g,N-甲基乙醇胺3.1g,甲乙酮肟2.5g,二月桂酸二丁基锡0.06g,滴加甲苯二异氰酸酯(TDI)21g,在70℃下反应5h,用二正丁胺法测定体系无残留异氰酸根后,反应结束,减压蒸馏脱除溶剂,得到聚氨酯化合物产品。
取上述聚氨酯疏水化合物产品32g,醋酸0.5g,水67.5g,搅拌得到外观均一产品。
测试方法和结果
将实施例1 4的无氟防水剂和比较例1、2的产品用去离子水稀释成浓度50g/L,采用一浸一轧工艺,110℃烘干,170℃热处理定型60秒,按照AATCC 130-2018作为测试方法标准进行测试,测定初始和10次家庭洗涤(10HL)循环后防水的效果。结果下表所示:
(表1)
以上所述仅是本公开的具体实施方式,使本领域技术人员能够理解或实现本公开。对这些实施例的多种修改对本领域的技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本公开的精神或范围的情况下,在其它实施例中实现。因此,本公开将不会被限制于本文所述的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (8)
1.一种聚氨酯无氟易去污整理剂,其特征在于:它是由二元醇化合物、多异氰酸酯、功能单体和亲水单体经过缩聚反应生成聚氨酯聚合物,再经乳化后获得。
5.根据权利要求1所述的聚氨酯无氟易去污整理剂,其特征在于:所述多异氰酸酯是带有两个或两个以上异氰酸酯基团物质的一种或两种以上组合。
6.根据权利要求1所述的聚氨酯无氟易去污整理剂,其特征在于:所述功能单体是具有活泼氢的小分子化合物,即是具有两个或两个以上羟基的多元醇或者酚类,或者具有两个或两个以上氨基的多元胺,或者具有单活泼氢官能团的化合物中一种或两种以上组合。
8.一种权利要求1~7任一项所述聚氨酯无氟易去污整理剂的制备方法,其特征在于:将二元醇化合物、功能单体、亲水单体和多异氰酸酯进行缩聚反应生成聚氨酯聚合物,再将聚氨酯聚合物与乳化剂、去离子水混合后,经乳化制得聚氨酯无氟易去污整理剂。
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