CN101768884B - Multi-quaternary ammonium group cation type polyurethane color fixing agent and preparation method thereof - Google Patents
Multi-quaternary ammonium group cation type polyurethane color fixing agent and preparation method thereof Download PDFInfo
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- CN101768884B CN101768884B CN201010013591A CN201010013591A CN101768884B CN 101768884 B CN101768884 B CN 101768884B CN 201010013591 A CN201010013591 A CN 201010013591A CN 201010013591 A CN201010013591 A CN 201010013591A CN 101768884 B CN101768884 B CN 101768884B
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 63
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 239000004814 polyurethane Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000004970 Chain extender Substances 0.000 claims abstract description 45
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 43
- 238000007789 sealing Methods 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 14
- -1 tertiary amine compounds Chemical class 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 68
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 67
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 50
- 238000001816 cooling Methods 0.000 claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 28
- 238000010992 reflux Methods 0.000 claims description 26
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 21
- 230000000903 blocking effect Effects 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- 229960000583 acetic acid Drugs 0.000 claims description 14
- 239000012362 glacial acetic acid Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 238000004945 emulsification Methods 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 150000002009 diols Chemical class 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 10
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 10
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- 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 7
- QCMHUGYTOGXZIW-UHFFFAOYSA-N 3-(dimethylamino)propane-1,2-diol Chemical compound CN(C)CC(O)CO QCMHUGYTOGXZIW-UHFFFAOYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 6
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 5
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 4
- 229940073608 benzyl chloride Drugs 0.000 claims description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 4
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 claims description 4
- 125000005189 alkyl hydroxy group Chemical group 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 claims description 2
- KMWHQYDMBYABKL-UHFFFAOYSA-N 1-iodohexadecane Chemical compound CCCCCCCCCCCCCCCCI KMWHQYDMBYABKL-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 23
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 12
- 239000004744 fabric Substances 0.000 abstract description 10
- 239000000975 dye Substances 0.000 abstract description 8
- 230000002152 alkylating effect Effects 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000005303 weighing Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 229920005906 polyester polyol Polymers 0.000 description 7
- 229920005862 polyol Polymers 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 6
- 239000004753 textile Substances 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 4
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 4
- 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 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 3
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 3
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 2
- HHRGNKUNRVABBN-UHFFFAOYSA-N 2-[2-hydroxyethyl(propan-2-yl)amino]ethanol Chemical compound OCCN(C(C)C)CCO HHRGNKUNRVABBN-UHFFFAOYSA-N 0.000 description 2
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 2
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 2
- 239000002535 acidifier Substances 0.000 description 2
- 150000001347 alkyl bromides Chemical class 0.000 description 2
- 150000001351 alkyl iodides Chemical class 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 2
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 2
- 239000000982 direct dye Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- VLSTXUUYLIALPB-UHFFFAOYSA-N n-propan-2-ylpropan-1-amine Chemical compound CCCNC(C)C VLSTXUUYLIALPB-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000985 reactive dye Substances 0.000 description 2
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- MBVGJZDLUQNERS-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound FC(F)(F)C1=NC(C#N)=C(C#N)N1 MBVGJZDLUQNERS-UHFFFAOYSA-N 0.000 description 1
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- MEBJLVMIIRFIJS-UHFFFAOYSA-N hexanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCC(O)=O MEBJLVMIIRFIJS-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a multi-quaternary ammonium group cation type polyurethane color fixing agent (see structural formula (I)), and a preparation method thereof. The preparation method comprises the following steps of: weighing 1.3-153.2 parts by weight of diisocyanate a, 3.7-365 parts by weight of diisocyanate b, 4.5-584 parts by weight of polyatomic alcohol, 0.02-1 part by weight of catalyst, 2-100 parts by weight of polyhydroxy tertiary amine compounds, 2-236 parts by weight of alkylating reagents, 1-38 parts by weight of sealers, 5-80 parts by weight of organic solvents a, 5-100 partsby weight of organic solvents b, 10-50 parts by weight of organic solvents c, 0.1-5 parts by weight of acidizing reagents and 20-800 parts by weight of deionized water in weight ratio; sequentially preparing a multi-quaternary ammonium group chain extender and a polyurethane prepolymer for chain-extension reaction, sealing reaction, removing solvent and emulsifying to obtain the color fixing agent. The color fixing agent prepared by the preparation method reduces the water solubility of dyes and improves the color fastness of the dyes, and fabrics have soft hand feeling after being fixed. In the formula, X is a sealing group, Y is a diisocyanate main group, Z is polyurethane soft section, R and R'are alkyl groups or hydroxyl groups, and n is equal to 1-15.
Description
Technical Field
The invention belongs to the technical field of textile dyeing and finishing, and particularly relates to a multi-quaternary ammonium group cationic polyurethane color fixing agent and a preparation method thereof.
Background
After the textile is dyed by anionic dyes such as direct dyes, acid dyes and the like, the wet processing color fastness of the textile is poor, and even if the textile dyed by the reactive dyes is dyed, the wet rubbing fastness of the textile is not enough to meet the quality requirement, so that various color fastness standards of wearing and using can be achieved generally by color fixing treatment. Fixing agents such as fixing agent Y, fixing agent M, and crosslinking agent DE have been banned because they contain free formaldehyde. At present, most of the used formaldehyde-free color fixing agents are polyamine high molecular compounds, such as color fixing agent DM-2518 of Guangzhou Demei chemical industry Co., Ltd, formaldehyde-free color fixing agent TF-233 of Zhejiang chemical group Co., Ltd and the like, and the color fixing agents have good color fixing effects when applied to direct dye and reactive dye dyeing of pure cotton, polyester cotton and polyester-viscose fabrics, but have very common color fixing effects on darker fabrics, silk, wool and other fabrics.
Disclosure of Invention
The invention aims to provide a multi-quaternary ammonium group cationic polyurethane color fixing agent, which solves the problem that the color fixing effect of the existing color fixing agent on darker fabrics and fabrics such as silk, wool and the like is poor.
The invention also aims to provide a preparation method of the multi-quaternary ammonium group cationic polyurethane color fixing agent.
The technical scheme adopted by the invention is that the multi-quaternary ammonium group cationic polyurethane color fixing agent has the molecular formula as follows:
wherein, X-is a blocking group; y-a diisocyanate backbone group; z-polyurethane soft segment;
r, R' -alkyl or alkylhydroxy; n is 1-15.
The invention adopts another technical scheme that a method for preparing the color fixing agent is implemented according to the following steps:
step 1: weighing 1.3-153.2 parts of diisocyanate a, 3.7-365 parts of diisocyanate b, 4.5-584 parts of polyol, 0.02-1 part of catalyst, 2-100 parts of polyhydroxy tertiary amine compound, 2-236 parts of alkylating reagent, 1-38 parts of sealing agent, 5-80 parts of organic solvent a, 5-100 parts of organic solvent b, 10-50 parts of organic solvent c, 10-100 parts of organic solvent d, 0.1-5 parts of acidifying reagent and 20-800 parts of deionized water according to the weight ratio;
step 2: preparing a multi-quaternary ammonium base chain extender:
adding the polyhydroxy tertiary amine compound weighed in the step 1 and an organic solvent a into a dry reactor, mixing to obtain a mixed solution, dropwise adding the diisocyanate a weighed in the step 1 into the mixed solution, reacting for 1-2 hours at the temperature of 3-10 ℃, then heating to 50-100 ℃, dropwise adding the alkylating reagent weighed in the step 1, and performing reflux reaction for 2-5 hours to obtain a multi-quaternary ammonium group chain extender;
preparing a polyurethane prepolymer:
adding diisocyanate b weighed in the step 1 and an organic solvent b into a dry reactor to obtain a mixed solution, dropwise adding polyalcohol weighed in the step 1 into the mixed solution, then adding a catalyst weighed in the step 1, and reacting for 2-4 hours at the temperature of 50-90 ℃ to obtain a polyurethane prepolymer;
and step 3: chain extension reaction
Adding the multi-quaternary ammonium group chain extender obtained in the step 2 into the polyurethane prepolymer, adding the organic solvent c weighed in the step 1, and reacting for 1.5-2 hours at the temperature of 40-90 ℃ to obtain a polyurethane polymer with an end group of isocyanate group;
and 4, step 4: blocking reaction
Cooling the polyurethane polymer obtained in the step 3 to 0-10 ℃, adding the organic solvent d weighed in the step 1, adding the sealing agent weighed in the step 1, and carrying out sealing reaction for 1-2 hours to obtain a polyurethane polymer emulsion with a sealed end group;
and 5: desolventizing and emulsifying
And (3) carrying out reduced pressure distillation on the polyurethane polymer emulsion obtained in the step (4), removing the organic solvent, adjusting the pH value to 5.5-6.5 by using the acidifying reagent weighed in the step (1), then adding the deionized water weighed in the step (1), and emulsifying for 0.5-1 hour to obtain the emulsion-like multi-quaternary ammonium group cationic polyurethane color fixing agent.
The present invention is also characterized in that,
wherein the diisocyanate is one of toluene diisocyanate, xylylene diisocyanate, naphthalene-1, 5-diisocyanate, diphenylmethane-4, 4' -diisocyanate, isophorone diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate or 1, 6-hexamethylene diisocyanate.
Wherein the polyester polyol adopts polyester polyol or polyether polyol, the polyester polyol adopts one of polyethylene glycol adipate glycol, 1, 4-butanediol adipate glycol, polyethylene glycol adipate-propylene glycol or 1, 6-hexanediol polycarbonate glycol, or the mixture of more than two of the polyester polyol and the polyethylene glycol adipate glycol; the polyether polyol is one of ethylene oxide glycol, polypropylene oxide glycol or polytetrahydrofuran glycol, or a mixture of two or more of the ethylene oxide glycol, the polypropylene oxide glycol and the polytetrahydrofuran glycol.
Wherein the catalyst is one of dibutyltin dilaurate, stannous octoate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate or tetraisobutyl titanate.
Wherein the polyhydroxy tertiary amine compound is one of triethanolamine, N-methyldiethanolamine, N-isopropyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine or 3-dimethylamino-1, 2-propanediol, or a mixture of more than two of the above.
Wherein the alkylating reagent is one of dimethyl sulfate, diethyl sulfate, dimethyl carbonate, diethyl carbonate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, benzyl chloride, benzyl bromide, alkyl bromide or alkyl iodide.
The blocking agent is one of N-methyl methylamine, N-ethyl ethylamine, N-isopropyl propylamine, N-methyl ethylamine, N-ethyl methylamine, N-methyl propylamine, N-methyl aniline, N-ethyl aniline, sodium bisulfite, methyl ethyl ketoxime, phenol or caprolactam.
Wherein the organic solvent is one of ethyl acetate, butyl acetate, acetone, butanone, 1, 2-dichloroethane, N-methylpyrrolidone, N-dimethylformamide, isopropanol, N-propanol, absolute ethyl alcohol or tetrahydrofuran.
Wherein the acidifying agent is glacial acetic acid.
The color fixing agent has the beneficial effects that the color fixing agent is used for the textile dyeing post-treatment, can improve the washing fastness and the dry and wet rubbing color fastness of various anionic dyes, and keeps the soft hand feeling of fabrics.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention discloses a multi-quaternary ammonium group cationic polyurethane color fixing agent, which has a representative chemical structural formula as follows:
in the formula,
x-a blocking group;
y-a diisocyanate backbone group;
z-polyurethane soft segment;
r, R' -alkyl, alkylhydroxy, etc.;
n＝1-15。
the preparation method of the multi-quaternary ammonium group cationic polyurethane color fixing agent is implemented according to the following steps:
step 1: weighing 1.3-153.2 parts of diisocyanate a, 3.7-365 parts of diisocyanate b, 4.5-584 parts of polyol, 0.02-1 part of catalyst, 2-100 parts of polyhydroxy tertiary amine compound, 2-236 parts of alkylating reagent, 1-38 parts of sealing agent, 5-80 parts of organic solvent a, 5-100 parts of organic solvent b, 10-50 parts of organic solvent c, 10-100 parts of organic solvent d, 0.1-5 parts of acidifying reagent and 20-800 parts of deionized water according to the weight ratio;
wherein the diisocyanate is one of Toluene Diisocyanate (TDI), Xylylene Diisocyanate (XDI), naphthalene-1, 5-diisocyanate (NDI), diphenylmethane-4, 4' -diisocyanate (MDI), isophorone diisocyanate (IPDI), methylcyclohexyl diisocyanate (HTDI), dicyclohexylmethane diisocyanate (HMDI), tetramethylxylylene diisocyanate (TMXDI) or 1, 6-Hexamethylene Diisocyanate (HDI);
wherein the polyester polyol is polyester polyol or polyether polyol, and the polyester polyol is one or a mixture of more than two of polyethylene glycol adipate glycol (PEA), polyethylene glycol adipate glycol (PDA), polyethylene-1, 4-butanediol adipate glycol (PBA), polyethylene-propylene glycol adipate glycol or polycarbonate-1, 6-hexanediol carbonate glycol (PHC); the polyether polyol is one or a mixture of more than two of ethylene oxide glycol (PEG), polypropylene oxide glycol (PPG) or polytetrahydrofuran glycol (PTMG);
wherein the catalyst is one of dibutyltin dilaurate (DBTDL), stannous octoate, lead octoate (24% Pb), cobalt octoate (6% Co), iron octoate (6% Fe), zinc naphthenate (14.5% Zn) or tetraisobutyl titanate;
wherein the polyhydroxy tertiary amine compound is one or a mixture of more than two of Triethanolamine (TEA), N-Methyldiethanolamine (MDEA), N-isopropyldiethanolamine, N-ethyldiethanolamine (EDEA), N-Butyldiethanolamine (BDEA) or 3-dimethylamino-1, 2-propanediol;
wherein the alkylating reagent adopts one of dimethyl sulfate, diethyl sulfate, dimethyl carbonate, diethyl carbonate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, benzyl chloride, benzyl bromide, alkyl bromide or alkyl iodide;
wherein the sealant is one of N-methyl methylamine (dimethylamine), N-ethyl ethylamine (diethylamine), N-isopropyl propylamine, N-methyl ethylamine, N-ethyl methylamine, N-methyl propylamine, N-methyl aniline, N-ethyl aniline, sodium bisulfite, methyl ethyl ketoxime, phenol or caprolactam;
wherein the organic solvent is one of ethyl acetate, butyl acetate, acetone, butanone, 1, 2-dichloroethane, N-methylpyrrolidone, N-Dimethylformamide (DMF), isopropanol, N-propanol, absolute ethyl alcohol or tetrahydrofuran;
wherein the acidifying agent is glacial acetic acid.
Step 2: preparing a multi-quaternary ammonium base chain extender:
adding the polyhydroxy tertiary amine compound weighed in the step 1 and an organic solvent a into a dry reactor, mixing to obtain a mixed solution, dropwise adding the diisocyanate a weighed in the step 1 into the mixed solution, reacting for 1-2 hours at the temperature of 3-10 ℃, then heating to 50-100 ℃, dropwise adding the alkylating reagent weighed in the step 1, and performing reflux reaction for 2-5 hours to obtain a multi-quaternary ammonium group chain extender;
preparing a polyurethane prepolymer:
adding diisocyanate b weighed in the step 1 and an organic solvent b into a dry reactor to obtain a mixed solution, dropwise adding the polyol weighed in the step 1 into the mixed solution by using a dropping funnel, then adding the catalyst weighed in the step 1, and reacting for 2-4 hours at the temperature of 50-90 ℃ to obtain a polyurethane prepolymer;
and step 3: chain extension reaction
Adding the multi-quaternary ammonium group chain extender obtained in the step 2 into the polyurethane prepolymer, adding the organic solvent c weighed in the step 1, and reacting for 1.5-2 hours at the temperature of 40-90 ℃ to obtain a polyurethane polymer with an end group of isocyanate group;
and 4, step 4: blocking reaction
Cooling the polyurethane polymer obtained in the step 3 to 0-10 ℃, adding the organic solvent d weighed in the step 1, adding the sealing agent weighed in the step 1, and carrying out sealing reaction for 1-2 hours to obtain a polyurethane polymer emulsion with a sealed end group;
and 5: desolventizing and emulsifying
And (3) carrying out reduced pressure distillation on the polyurethane polymer emulsion obtained in the step (4), removing the organic solvent, adjusting the pH value to 5.5-6.5 by using the acidifying reagent weighed in the step (1), then adding the deionized water weighed in the step (1), and emulsifying for 0.5-1 hour by using a high-speed emulsifying machine to obtain the emulsion-like multi-quaternary ammonium group cationic polyurethane color fixing agent.
According to the multi-quaternary ammonium group cationic polyurethane color fixing agent, a proper amount of quaternary ammonium group cationic groups are introduced into a polyurethane macromolecular chain, and can be combined with dye anionic groups on fibers through ionic bonds, so that the water solubility of the dye is reduced; meanwhile, under certain conditions, the blocking groups on the molecules of the color fixing agent can form covalent bond combination with the fibers and hydroxyl, amino, carboxyls and the like on the molecules of the dye after deblocking, so that the color fastness of the dye, especially the wet-processing color fastness, is improved. Because the polyurethane polymer has the characteristics of excellent elasticity, flexibility and the like, compared with other types of color fixing agents, the color fixing agent has soft hand feeling of the treated fabric.
Example 1
(1) Preparation of multi-quaternary ammonium group chain extender
To a dry reactor, 100 parts Triethanolamine (TEA) and 60 parts N-methylpyrrolidone were added, followed by 153.2 parts MDI, and the temperature was maintained at 10 ℃ for 2 hours. Gradually heating to 95 ℃, adding 236.4 parts of iodohexadecane, and refluxing for 2 hours to obtain the multi-quaternary ammonium group chain extender. Cooling to room temperature, charging nitrogen gas, and sealing.
Preparation of polyurethane prepolymer
Distilling a mixture of 24 parts of PEG600 and 60 parts of PPG1500 at 100 ℃ under reduced pressure for 2 hours, cooling to 50 ℃, adding 25 parts of acetone, and sealing for later use. Adding 41 parts of MDI into a dry reactor, introducing nitrogen for protection, dropwise adding a mixture of the two polyether diols into a dropping funnel, adding 0.03 part of DBTDL, controlling the temperature at 55 ℃, and carrying out heat preservation reaction for 2 hours to obtain a polyurethane prepolymer;
(2) chain extension reaction
Adding 35 parts of acetone into the polyurethane prepolymer prepared in the step (1), then dropwise adding the multi-quaternary ammonium group chain extender prepared in the step (1), controlling the temperature to be 70 ℃, and carrying out reflux reaction for 2 hours under the protection of nitrogen.
(3) Blocking reaction
And cooling the polymer obtained after the reaction to 5 ℃, adding 35 parts of absolute ethyl alcohol, adding 2 parts of N-methyl methylamine, and carrying out closed reaction for 1.5 hours.
(4) Removing solvent
And (3) distilling under reduced pressure to remove the solvent to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent.
(5) Emulsification
And adding 5 parts of glacial acetic acid to adjust the pH value to 5.5, adding 600 parts of deionized water, and emulsifying on a high-speed emulsifying machine for 0.8 hour to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent emulsion.
Example 2
(1) Preparation of multi-quaternary ammonium group chain extender
To the dried reactor, 2 parts of N-ethyldiethanolamine (MDEA) and 5 parts of N-methylpyrrolidone were added, followed by 1.3 parts of HDI, and the reaction was carried out for 2 hours while maintaining the temperature at 15 ℃. Gradually heating to 90 ℃, adding 2.1 parts of benzyl chloride, and refluxing for 2 hours to obtain the multi-quaternary ammonium group chain extender. Cooling to room temperature, filling nitrogen and sealing for later use to obtain the multi-quaternary ammonium group chain extender.
Preparation of polyurethane prepolymer
Distilling 4.5 parts of PEG600 at 100 ℃ under reduced pressure for 2 hours, cooling to 55 ℃, adding 5 parts of acetone, and sealing for later use. Adding 3.7 parts of IPDI (isophorone diisocyanate) into a dry reactor, filling nitrogen for protection, dropwise adding the PEG600 into a dropping funnel, adding 0.2 part of stannous octoate, controlling the temperature at 50 ℃, and carrying out heat preservation reaction for 2 hours to obtain a polyurethane prepolymer;
(2) chain extension reaction
And (2) adding 10 parts of acetone into the polyurethane prepolymer prepared in the step (1), then dropwise adding the multi-quaternary ammonium group chain extender prepared in the step (1), controlling the temperature to be 75 ℃, and carrying out reflux reaction for 2 hours under the protection of nitrogen.
(3) Blocking reaction
And cooling the polymer obtained after the reaction to 0 ℃, adding 10 parts of isopropanol, adding 1 part of sodium bisulfite, and carrying out closed reaction for 1 hour.
(4) Removing solvent
And (3) distilling under reduced pressure to remove the solvent to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent.
(5) Emulsification
And adding 0.1 part of glacial acetic acid to adjust the pH value to 6.5, adding 20 parts of deionized water, and emulsifying on a high-speed emulsifying machine for 1 hour to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent emulsion.
Example 3
(1) Preparation of multi-quaternary ammonium group chain extender
To a dry reactor, 10.7 parts of 3-dimethylamino-1, 2-propanediol, 13.4 parts Triethanolamine (TEA), 66 parts N-Methyldiethanolamine (MDEA) and 80 parts N-methylpyrrolidone were added, and then 91 parts MDI was added and the temperature was maintained at 10 ℃ for 2 hours. Gradually heating to 100 ℃, adding 125 parts of benzyl bromide, and refluxing for 2 hours to obtain the multi-quaternary ammonium base chain extender. Cooling to room temperature, charging nitrogen gas, and sealing.
Preparation of polyurethane prepolymer
And (3) distilling 584 parts of PEG800 at 100 ℃ under reduced pressure for 2 hours, cooling to 60 ℃, adding 100 parts of acetone, and sealing for later use. 365 parts of MDI is added into a dry reactor, nitrogen is filled for protection, the PEG800 and 1 part of stannous octoate are added into a dropping funnel dropwise, the temperature is controlled at 60 ℃, and the heat preservation reaction is carried out for 2.5 hours, so as to prepare a polyurethane prepolymer;
(2) chain extension reaction
And (2) adding 50 parts of acetone into the polyurethane prepolymer prepared in the step (1), then dropwise adding the multi-quaternary ammonium group chain extender prepared in the step (1), controlling the temperature to be 90 ℃, and carrying out reflux reaction for 2 hours under the protection of nitrogen.
(3) Blocking reaction
And cooling the polymer obtained after the reaction to 10 ℃, adding 100 parts of absolute ethyl alcohol, adding 38 parts of sodium bisulfite, and carrying out closed reaction for 2 hours.
(4) Removing solvent
And (3) distilling under reduced pressure to remove the solvent to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent.
(5) Emulsification
And 4.5 parts of glacial acetic acid is added to adjust the pH value to 6, and 800 parts of deionized water is added to emulsify for 0.5 hour under high-speed shearing force, so that the multi-quaternary ammonium group cationic polyurethane color fixing agent emulsion is obtained.
Example 4
(1) Preparation of multi-quaternary ammonium group chain extender
To a dry reactor were added 42.9 parts of N-Methyldiethanolamine (MDEA), 53.7 parts of Triethanolamine (TEA) and 80 parts of N-methylpyrrolidone, and then 94.0 parts of TDI was added, and the temperature was maintained at 3 ℃ for 2 hours. Gradually heating to 60 ℃, adding 61.5 parts of benzyl bromide, and refluxing for 2 hours to obtain the multi-quaternary ammonium base chain extender. Cooling to room temperature, charging nitrogen gas, and sealing.
Preparation of polyurethane prepolymer
Distilling 180 parts of PTMG1000 at 100 ℃ under reduced pressure for 2 hours, cooling to 55 ℃, adding 30 parts of acetone, and sealing for later use. Adding 90 parts of MDI into a dry reactor, introducing nitrogen for protection, dropwise adding polyether glycol into a dropping funnel, adding 0.1 part of lead octoate (24% Pb), controlling the temperature at 90 ℃, and carrying out heat preservation reaction for 4 hours to obtain a polyurethane prepolymer;
(2) chain extension reaction
Adding 60 parts of acetone into the polyurethane prepolymer prepared in the step (1), then dropwise adding the multi-quaternary ammonium group chain extender prepared in the step (1), controlling the temperature to be 40 ℃, and carrying out reflux reaction for 1.5 hours under the protection of nitrogen.
(3) Blocking reaction
The polymer obtained after the reaction is cooled to 5 ℃, 55 parts of isopropanol and 9.87 parts of N-ethyl ethylamine are added, and the reaction is sealed for 1.5 hours.
(4) Removing solvent
And (3) distilling under reduced pressure to remove the solvent to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent.
(5) Emulsification
Adding 4.8 parts of glacial acetic acid to adjust the pH value to 6, and adding 596 parts of deionized water to emulsify for 1 hour under high-speed shearing force to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent emulsion.
Example 5
(1) Preparation of polyquaternary ammonium base chain extender
42.8 parts of 3-dimethylamino-1, 2-propanediol and 60 parts of N-methylpyrrolidone are charged into a dry reactor, and then 23.4 parts of TDI is added and the reaction is carried out for 1 hour while maintaining the temperature at 8 ℃. Gradually heating to 50 ℃, adding 110 parts of bromohexadecane, and refluxing for 5 hours to obtain the multi-quaternary ammonium base chain extender. Cooling to room temperature, charging nitrogen gas, and sealing.
Preparation of polyurethane prepolymer
And distilling a mixture of 60 parts of PTMG800, 36 parts of PEG800 and 90 parts of PPG1500 at 100 ℃ under reduced pressure for 2 hours, cooling to 55 ℃, adding 30 parts of acetone, and sealing for later use. Adding 80 parts of IPDI (isophorone diisocyanate) into a dry reactor, filling nitrogen for protection, dropwise adding a mixture of three polyether diols into a dropping funnel, adding 0.6 part of DBTDL, controlling the temperature at 60 ℃, and carrying out heat preservation reaction for 2.5 hours to obtain a polyurethane prepolymer;
(2) chain extension reaction
Adding 35 parts of acetone into the polyurethane prepolymer prepared in the step (1), then dropwise adding the multi-quaternary ammonium group chain extender prepared in the step (1), controlling the temperature to be 80 ℃, and carrying out reflux reaction for 2 hours under the protection of nitrogen.
(3) Blocking reaction
The polymer obtained after the reaction is cooled to 5 ℃, 50 parts of isopropanol are added, 9.87 parts of N-ethyl ethylamine are added, and the closed reaction is carried out for 1.5 hours.
(4) Removing solvent
And (3) distilling under reduced pressure to remove the solvent to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent.
(5) Emulsification
Adding 2.1 parts of glacial acetic acid to adjust the pH value to 6.5, and adding 450 parts of deionized water to emulsify for 1 hour under high-speed shearing force to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent emulsion.
Example 6
(1) Preparation of multi-quaternary ammonium group chain extender
To a dry reactor, 26.9 parts of Triethanolamine (TEA) and 80 parts of N-methylpyrrolidone were added, followed by 15.1 parts of HDI, and the reaction was carried out for 1.5 hours while maintaining the temperature at 10 ℃. Gradually heating to 75 ℃, adding 22.8 parts of dimethyl sulfate, and refluxing for 3 hours to obtain the multi-quaternary ammonium base chain extender. Cooling to room temperature, charging nitrogen gas, and sealing.
Preparation of polyurethane prepolymer
Distilling 180 parts of PTMG1500 and 48 parts of PPG800 at 100 ℃ under reduced pressure for 2 hours, cooling to 65 ℃, adding 35 parts of acetone, and sealing for later use. Adding 80 parts of IPDI (isophorone diisocyanate) into a dry reactor, filling nitrogen for protection, dropwise adding a mixture of two polyether diols into a dropping funnel, controlling the temperature at 65 ℃, and carrying out heat preservation reaction for 2.5 hours to obtain a polyurethane prepolymer;
(2) chain extension reaction
Adding 35 parts of acetone into the polyurethane prepolymer prepared in the step (1), then dropwise adding the multi-quaternary ammonium group chain extender prepared in the step (1), controlling the temperature to be 70 ℃, and carrying out reflux reaction for 2 hours under the protection of nitrogen.
(3) Blocking reaction
The polymer obtained after the above reaction was cooled to 5 ℃, 50 parts of isopropyl alcohol, 6.6 parts of N-ethyl ethylamine and 6.8 parts of N-methylpropylamine were added, and a sealing reaction was carried out for 1.5 hours.
(4) Removing solvent
And (3) distilling under reduced pressure to remove the solvent to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent.
(5) Emulsification
And adding 1.3 parts of glacial acetic acid to adjust the pH value to 6, and adding 360 parts of deionized water to emulsify for 1 hour under high-speed shearing force to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent emulsion.
Table 1 comparison of the results of the invention with other fixing agents
| Variety of color fixing agent | Dry/wet crocking fastness (grade) | Soaping color fastness (grade) | Hand feeling | Formaldehyde (I) |
| Color fixing agent DM-2518 | 3-4/2-3 | 3-4 | Is harder | Is free of |
| Color fixing agent TF-233 | 3-4/2-3 | 3-4 | Is harder | Is free of |
| Inventive example 1 | 4/3-4 | 4 | Softness | Is free of |
| Inventive example 2 | 4/3-4 | 4 | Softness | Is free of |
| Hair brushEXAMPLES example 3 | 4/3 | 4 | Softness | Is free of |
| Inventive example 4 | 4/3-4 | 4 | Softness | Is free of |
| Inventive example 5 | 4/3-4 | 4 | Softness | Is free of |
| Inventive example 6 | 4/3-4 | 4 | Softness | Is free of |
Note: 1. dry and wet rubbing fastness: GB/T3920-1997
2. Soaping fastness: GB/T3921.1-1997
3. Formaldehyde: GB/T2912.1-1998 first part water extraction method
As can be seen from Table 1, the multi-quaternary ammonium group cationic polyurethane color fixing agent disclosed by the invention has the advantages that due to the softness and elasticity of the soft polyurethane segment, the fabric after finishing is soft in hand feeling, and the dry and wet rubbing fastness and washing fastness of the dyed fabric are excellent.
Claims (2)
1. The multi-quaternary ammonium group cationic polyurethane color fixing agent is characterized by having a molecular formula as follows:
wherein, X-is a blocking group; a Y-diisocyanate host group; a Z-polyurethane soft segment;
r, R' -alkyl or alkylhydroxy; n is 1-15.
2. A method for preparing the fixing agent according to claim 1, which is carried out by the following steps:
step 1: preparation of multi-quaternary ammonium group chain extender
Adding 100 parts of triethanolamine and 60 parts of N-methylpyrrolidone into a dry reactor, then adding 153.2 parts of diphenylmethane-4, 4' -diisocyanate, keeping the temperature at 10 ℃ for reacting for 2 hours, gradually heating to 95 ℃, adding 236.4 parts of iodohexadecane, refluxing for 2 hours to obtain a multi-quaternary ammonium group chain extender, cooling to room temperature, filling nitrogen, and sealing for later use;
preparation of polyurethane prepolymer
Distilling a mixture of 24 parts of ethylene oxide glycol 600 and 60 parts of polyoxypropylene glycol 1500 at 100 ℃ under reduced pressure for 2 hours, cooling to 50 ℃, adding 25 parts of acetone, sealing for later use, adding 41 parts of diphenylmethane-4, 4' -diisocyanate into a dry reactor, introducing nitrogen for protection, dropwise adding a mixture of the two polyether diols into a dropping funnel, adding 0.03 part of dibutyltin dilaurate, controlling the temperature to be 55 ℃, and carrying out heat preservation reaction for 2 hours to obtain a polyurethane prepolymer;
step 2: chain extension reaction
Adding 35 parts of acetone into the polyurethane prepolymer prepared in the step 1, then dropwise adding the multi-quaternary ammonium group chain extender prepared in the step 1, controlling the temperature to be 70 ℃, and carrying out reflux reaction for 2 hours under the protection of nitrogen;
and step 3: blocking reaction
Cooling the polymer obtained after the reaction in the step 2 to 5 ℃, adding 35 parts of absolute ethyl alcohol, then adding 2 parts of N-methyl methylamine, and carrying out closed reaction for 1.5 hours;
and 4, step 4: removing solvent
Distilling under reduced pressure to remove the solvent to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent;
and 5: emulsification
Adding 5 parts of glacial acetic acid to adjust the pH value to 5.5, adding 600 parts of deionized water, and emulsifying on a high-speed emulsifying machine for 0.8 hour to obtain multi-quaternary ammonium group cationic polyurethane color fixing agent emulsion;
or,
step 1: preparation of multi-quaternary ammonium group chain extender
Adding 2 parts of N-ethyldiethanolamine and 5 parts of N-methylpyrrolidone into a dried reactor, then adding 1.3 parts of 1, 6-hexamethylene diisocyanate, keeping the temperature at 15 ℃ for reacting for 2 hours, gradually heating to 90 ℃, adding 2.1 parts of benzyl chloride, refluxing for 2 hours to obtain a multi-quaternary ammonium base chain extender, cooling to room temperature, filling nitrogen, and sealing for later use to obtain the multi-quaternary ammonium base chain extender;
preparation of polyurethane prepolymer
Distilling 4.5 parts of ethylene oxide glycol 600 at 100 ℃ under reduced pressure for 2 hours, cooling to 55 ℃, adding 5 parts of acetone, sealing for later use, adding 3.7 parts of isophorone diisocyanate into a dry reactor, introducing nitrogen for protection, dropwise adding the ethylene oxide glycol 600 by using a dropping funnel, adding 0.2 part of stannous octoate, controlling the temperature at 50 ℃, and carrying out heat preservation reaction for 2 hours to obtain a polyurethane prepolymer;
step 2: chain extension reaction
Adding 10 parts of acetone into the polyurethane prepolymer prepared in the step 1, then dropwise adding the multi-quaternary ammonium group chain extender prepared in the step 1, controlling the temperature to be 75 ℃, and carrying out reflux reaction for 2 hours under the protection of nitrogen;
and step 3: blocking reaction
Cooling the polymer obtained after the reaction in the step 2 to 0 ℃, adding 10 parts of isopropanol, adding 1 part of sodium bisulfite, and carrying out closed reaction for 1 hour;
and 4, step 4: removing solvent
Distilling under reduced pressure to remove the solvent to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent;
and 5: emulsification
Adding 0.1 part of glacial acetic acid to adjust the pH value to 6.5, adding 20 parts of deionized water, and emulsifying on a high-speed emulsifying machine for 1 hour to obtain multi-quaternary ammonium group cationic polyurethane color fixing agent emulsion;
or,
step 1: preparation of multi-quaternary ammonium group chain extender
Adding 10.7 parts of 3-dimethylamino-1, 2-propanediol, 13.4 parts of triethanolamine, 66 parts of N-methyldiethanolamine and 80 parts of N-methylpyrrolidone into a dry reactor, then adding 91 parts of diphenylmethane-4, 4' -diisocyanate, keeping the temperature at 10 ℃ for reacting for 2 hours, gradually heating to 100 ℃, adding 125 parts of benzyl bromide, refluxing for 2 hours to obtain a multi-quaternary ammonium base chain extender, cooling to room temperature, filling nitrogen, and sealing for later use;
preparation of polyurethane prepolymer
Distilling 584 parts of ethylene oxide glycol 800 at 100 ℃ for 2 hours under reduced pressure, cooling to 60 ℃, adding 100 parts of acetone, sealing for later use, adding 365 parts of diphenylmethane-4, 4' -diisocyanate into a dry reactor, introducing nitrogen for protection, dropwise adding the ethylene oxide glycol 800 by using a dropping funnel, adding 1 part of stannous octoate, controlling the temperature at 60 ℃, and carrying out heat preservation reaction for 2.5 hours to obtain a polyurethane prepolymer;
step 2: chain extension reaction
Adding 50 parts of acetone into the polyurethane prepolymer prepared in the step 1, and then dropwise adding the acetone
Controlling the temperature of the multi-quaternary ammonium group chain extender prepared in the step 1 to be 90 ℃, and carrying out reflux reaction for 2 hours under the protection of nitrogen;
and step 3: blocking reaction
Cooling the polymer obtained after the reaction in the step 2 to 10 ℃, adding 100 parts of absolute ethyl alcohol, adding 38 parts of sodium bisulfite, and carrying out closed reaction for 2 hours;
and 4, step 4: removing solvent
Distilling under reduced pressure to remove the solvent to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent;
and 5: emulsification
Adding 4.5 parts of glacial acetic acid to adjust the pH value to 6, and adding 800 parts of deionized water to emulsify for 0.5 hour under high-speed shearing force to obtain multi-quaternary ammonium group cationic polyurethane color fixing agent emulsion;
or,
step 1: preparation of multi-quaternary ammonium group chain extender
Adding 42.9 parts of N-methyldiethanolamine, 53.7 parts of triethanolamine and 80 parts of N-methylpyrrolidone into a dry reactor, then adding 94.0 parts of toluene diisocyanate, keeping the temperature at 3 ℃ for reaction for 2 hours, gradually heating to 60 ℃, adding 61.5 parts of benzyl bromide, refluxing for 2 hours to obtain a multi-quaternary ammonium base chain extender, cooling to room temperature, filling nitrogen, and sealing for later use;
preparation of polyurethane prepolymer
Distilling 180 parts of polytetrahydrofuran diol 1000 at 100 ℃ under reduced pressure for 2 hours, cooling to 55 ℃, adding 30 parts of acetone, sealing for later use, adding 90 parts of diphenylmethane-4, 4' -diisocyanate into a dry reactor, introducing nitrogen for protection, dropwise adding polyether glycol by using a dropping funnel, adding 0.1 part of lead octoate, controlling the temperature to be 90 ℃, and carrying out heat preservation reaction for 4 hours to obtain a polyurethane prepolymer;
step 2: chain extension reaction
Adding 60 parts of acetone into the polyurethane prepolymer prepared in the step 1, then dropwise adding the multi-quaternary ammonium group chain extender prepared in the step 1, controlling the temperature to be 40 ℃, and carrying out reflux reaction for 1.5 hours under the protection of nitrogen;
and step 3: blocking reaction
Cooling the polymer obtained after the reaction in the step 2 to 5 ℃, adding 55 parts of isopropanol, then adding 9.87 parts of N-ethyl ethylamine, and carrying out closed reaction for 1.5 hours;
and 4, step 4: removing solvent
Distilling under reduced pressure to remove the solvent to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent;
and 5: emulsification
Adding 4.8 parts of glacial acetic acid to adjust the pH value to 6, and adding 596 parts of deionized water to emulsify for 1 hour under high-speed shearing force to obtain multi-quaternary ammonium group cationic polyurethane color fixing agent emulsion;
or,
step 1: preparation of polyquaternary ammonium base chain extender
Adding 42.8 parts of 3-dimethylamino-1, 2-propanediol and 60 parts of N-methylpyrrolidone into a dry reactor, then adding 23.4 parts of toluene diisocyanate, keeping the temperature at 8 ℃ for reacting for 1 hour, gradually heating to 50 ℃, adding 110 parts of bromohexadecane, refluxing for 5 hours to obtain a multi-quaternary ammonium group chain extender, cooling to room temperature, filling nitrogen, and sealing for later use;
preparation of polyurethane prepolymer
Distilling a mixture of 60 parts of polytetrahydrofuran diol 800, 36 parts of ethylene oxide diol 800 and 90 parts of polyoxypropylene diol 1500 at 100 ℃ under reduced pressure for 2 hours, cooling to 55 ℃, adding 30 parts of acetone, sealing for later use, adding 80 parts of isophorone diisocyanate into a dry reactor, filling nitrogen for protection, dropwise adding a mixture of three polyether diols into a dropping funnel, adding 0.6 part of dibutyltin dilaurate, controlling the temperature at 60 ℃, and carrying out heat preservation reaction for 2.5 hours to obtain a polyurethane prepolymer;
step 2: chain extension reaction
Adding 35 parts of acetone into the polyurethane prepolymer prepared in the step 1, then dropwise adding the multi-quaternary ammonium group chain extender prepared in the step 1, controlling the temperature to be 80 ℃, and carrying out reflux reaction for 2 hours under the protection of nitrogen;
and step 3: blocking reaction
Cooling the polymer obtained after the reaction in the step 2 to 5 ℃, adding 50 parts of isopropanol, adding 9.87 parts of N-ethyl ethylamine, and carrying out closed reaction for 1.5 hours;
and 4, step 4: removing solvent
Distilling under reduced pressure to remove the solvent to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent;
and 5: emulsification
Adding 2.1 parts of glacial acetic acid to adjust the pH value to 6.5, and adding 450 parts of deionized water to emulsify for 1 hour under high-speed shearing force to obtain multi-quaternary ammonium group cationic polyurethane color fixing agent emulsion;
or,
step 1: preparation of multi-quaternary ammonium group chain extender
Adding 26.9 parts of triethanolamine and 80 parts of N-methylpyrrolidone into a dry reactor, then adding 15.1 parts of 1, 6-hexamethylene diisocyanate, keeping the temperature at 10 ℃ for reacting for 1.5 hours, gradually heating to 75 ℃, adding 22.8 parts of dimethyl sulfate, refluxing for 3 hours to obtain a multi-quaternary ammonium group chain extender, cooling to room temperature, filling nitrogen, and sealing for later use;
preparation of polyurethane prepolymer
Distilling 180 parts of polytetrahydrofuran diol 1500 and 48 parts of polyoxypropylene diol 800 at 100 ℃ under reduced pressure for 2 hours, cooling to 65 ℃, adding 35 parts of acetone, sealing for later use, adding 80 parts of isophorone diisocyanate into a dry reactor, introducing nitrogen for protection, dropwise adding a mixture of two polyether diols by using a dropping funnel, controlling the temperature to 65 ℃, and carrying out heat preservation reaction for 2.5 hours to obtain a polyurethane prepolymer;
step 2: chain extension reaction
Adding 35 parts of acetone into the polyurethane prepolymer prepared in the step 1, then dropwise adding the multi-quaternary ammonium group chain extender prepared in the step 1, controlling the temperature to be 70 ℃, and carrying out reflux reaction for 2 hours under the protection of nitrogen;
and step 3: blocking reaction
Cooling the polymer obtained after the reaction in the step 2 to 5 ℃, adding 50 parts of isopropanol, then adding 6.6 parts of N-ethyl ethylamine and 6.8 parts of N-methylpropylamine, and carrying out a closed reaction for 1.5 hours;
and 4, step 4: removing solvent
Distilling under reduced pressure to remove the solvent to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent;
and 5: emulsification
And adding 1.3 parts of glacial acetic acid to adjust the pH value to 6, and adding 360 parts of deionized water to emulsify for 1 hour under high-speed shearing force to obtain the multi-quaternary ammonium group cationic polyurethane color fixing agent emulsion.
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| CN102127193B (en) * | 2011-01-30 | 2012-07-18 | 安徽大学 | Method for preparing cationic poly(urethane-dimethyldiallylammonium chloride) color fixing agent |
| CN102251416B (en) * | 2011-04-15 | 2013-06-26 | 西安工程大学 | Waterborne polyurethane graft-modified polyamine color fixing agent and preparation method thereof |
| CN103421158B (en) * | 2013-08-06 | 2015-07-29 | 陕西科技大学 | A kind of preparation method and application's method of the fixing and hyperchromicity agent for superfine fiber chemical leather dyeing |
| CN103614935A (en) * | 2013-11-21 | 2014-03-05 | 湖州厉华妤婕联合纺织有限公司 | Improved color fixative for textiles |
| WO2016099948A1 (en) | 2014-12-16 | 2016-06-23 | 3M Innovative Properties Company | Antistatic polymers and methods of making the same |
| US10308753B2 (en) | 2014-12-16 | 2019-06-04 | 3M Innovative Properties Company | Ionic diol, antistatic polyurethane, and method of making the same |
| WO2016099996A1 (en) | 2014-12-16 | 2016-06-23 | 3M Innovative Properties Company | Antistatic polymers and methods of making the same |
| CN105113255A (en) * | 2015-09-07 | 2015-12-02 | 杭州美高华颐化工有限公司 | Organosilicone modification polyurethane color fixing agent and preparation method thereof |
| CN105568723A (en) * | 2016-02-29 | 2016-05-11 | 苏州印丝特纺织数码科技有限公司 | Synthesis method for cationic waterborne polyurethane acid dye fixing agent |
| CN109537332B (en) * | 2017-04-10 | 2021-07-20 | 南通大学 | Special color fixing agent for one-bath dyeing of polyester-cotton blended fabric and with simplified process flow |
| CN107354776B (en) * | 2017-08-16 | 2020-02-11 | 纤化（上海）生物化工股份有限公司 | Cationic modifier for textile pretreatment and synthetic method thereof |
| TWI825116B (en) * | 2018-07-06 | 2023-12-11 | 英商萊卡英國有限公司 | Acid-dyeable spandex from cationic polyurethane |
| CN109667175A (en) * | 2018-12-21 | 2019-04-23 | 南通江天化学股份有限公司 | A kind of synthetic method of water-borne polyurethane color fixing agent |
| CN110563906B (en) * | 2019-08-15 | 2021-11-16 | 深圳大学 | Shape memory polyurethane and preparation method and application thereof |
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