CN107353671A - A kind of azo structure contained active cationic dye and preparation method thereof - Google Patents
A kind of azo structure contained active cationic dye and preparation method thereof Download PDFInfo
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- CN107353671A CN107353671A CN201710593412.4A CN201710593412A CN107353671A CN 107353671 A CN107353671 A CN 107353671A CN 201710593412 A CN201710593412 A CN 201710593412A CN 107353671 A CN107353671 A CN 107353671A
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- 125000002091 cationic group Chemical group 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000000975 dye Substances 0.000 claims abstract description 99
- 229920001427 mPEG Polymers 0.000 claims abstract description 57
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims abstract description 49
- -1 secondary amine compound Chemical class 0.000 claims abstract description 34
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 85
- VGKYEIFFSOPYEW-UHFFFAOYSA-N 2-methyl-4-[(4-phenyldiazenylphenyl)diazenyl]phenol Chemical compound Cc1cc(ccc1O)N=Nc1ccc(cc1)N=Nc1ccccc1 VGKYEIFFSOPYEW-UHFFFAOYSA-N 0.000 claims description 83
- TUXJTJITXCHUEL-UHFFFAOYSA-N disperse red 11 Chemical compound C1=CC=C2C(=O)C3=C(N)C(OC)=CC(N)=C3C(=O)C2=C1 TUXJTJITXCHUEL-UHFFFAOYSA-N 0.000 claims description 51
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 48
- ZLCUIOWQYBYEBG-UHFFFAOYSA-N 1-Amino-2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=C(N)C(C)=CC=C3C(=O)C2=C1 ZLCUIOWQYBYEBG-UHFFFAOYSA-N 0.000 claims description 40
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- LZKGFGLOQNSMBS-UHFFFAOYSA-N 4,5,6-trichlorotriazine Chemical compound ClC1=NN=NC(Cl)=C1Cl LZKGFGLOQNSMBS-UHFFFAOYSA-N 0.000 claims description 17
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- HVOYZOQVDYHUPF-UHFFFAOYSA-N n,n',n'-trimethylethane-1,2-diamine Chemical compound CNCCN(C)C HVOYZOQVDYHUPF-UHFFFAOYSA-N 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- VMKJWLXVLHBJNK-UHFFFAOYSA-N cyanuric fluoride Chemical compound FC1=NC(F)=NC(F)=N1 VMKJWLXVLHBJNK-UHFFFAOYSA-N 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- FEJPWLNPOFOBSP-UHFFFAOYSA-N 2-[4-[(2-chloro-4-nitrophenyl)diazenyl]-n-ethylanilino]ethanol Chemical compound C1=CC(N(CCO)CC)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1Cl FEJPWLNPOFOBSP-UHFFFAOYSA-N 0.000 claims description 9
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 7
- SORARJZLMNRBAQ-UHFFFAOYSA-N n,n',n'-trimethylpropane-1,3-diamine Chemical compound CNCCCN(C)C SORARJZLMNRBAQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 6
- HXXLWTPFYWMBSC-UHFFFAOYSA-N 2-[3-chloro-4-[(2,6-dichloro-4-nitrophenyl)diazenyl]-n-(2-hydroxyethyl)anilino]ethanol Chemical compound ClC1=CC(N(CCO)CCO)=CC=C1N=NC1=C(Cl)C=C([N+]([O-])=O)C=C1Cl HXXLWTPFYWMBSC-UHFFFAOYSA-N 0.000 claims description 5
- VIPATEVXXXQLLF-UHFFFAOYSA-N 2-[n-ethyl-3-methyl-4-[(4-nitrophenyl)diazenyl]anilino]ethanol Chemical compound CC1=CC(N(CCO)CC)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1 VIPATEVXXXQLLF-UHFFFAOYSA-N 0.000 claims description 5
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 claims description 5
- XCFGSTMILLZSFI-UHFFFAOYSA-N 4-hydroxy-3-phenyldiazenyl-1H-quinolin-2-one Chemical compound OC1=NC2=CC=CC=C2C(O)=C1N=NC1=CC=CC=C1 XCFGSTMILLZSFI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 5
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 5
- 229940073608 benzyl chloride Drugs 0.000 claims description 5
- DSSYKIVIOFKYAU-UHFFFAOYSA-N camphor Chemical compound C1CC2(C)C(=O)CC1C2(C)C DSSYKIVIOFKYAU-UHFFFAOYSA-N 0.000 claims description 5
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- QJGOOFISESXSNF-UHFFFAOYSA-N methyl 4-[(3-methyl-5-oxo-1-phenyl-4h-pyrazol-4-yl)diazenyl]benzoate Chemical compound C1=CC(C(=O)OC)=CC=C1N=NC1C(=O)N(C=2C=CC=CC=2)N=C1C QJGOOFISESXSNF-UHFFFAOYSA-N 0.000 claims description 5
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical class CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- MPIGKGDPQRWZLU-UHFFFAOYSA-N 2-[4-[(2,6-dichloro-4-nitrophenyl)diazenyl]-n-methylanilino]ethanol Chemical compound C1=CC(N(CCO)C)=CC=C1N=NC1=C(Cl)C=C([N+]([O-])=O)C=C1Cl MPIGKGDPQRWZLU-UHFFFAOYSA-N 0.000 claims description 4
- DQMYXIPCBKSDCB-UHFFFAOYSA-N 2-[[4-[(2-chloro-4,6-dinitrophenyl)diazenyl]naphthalen-1-yl]amino]ethanol Chemical compound C12=CC=CC=C2C(NCCO)=CC=C1N=NC1=C(Cl)C=C([N+]([O-])=O)C=C1[N+]([O-])=O DQMYXIPCBKSDCB-UHFFFAOYSA-N 0.000 claims description 4
- COCWIIAFGQLMGS-UHFFFAOYSA-N 3-[n-ethyl-3-methyl-4-[(5-nitro-1,3-thiazol-2-yl)diazenyl]anilino]propane-1,2-diol Chemical compound CC1=CC(N(CC(O)CO)CC)=CC=C1N=NC1=NC=C([N+]([O-])=O)S1 COCWIIAFGQLMGS-UHFFFAOYSA-N 0.000 claims description 4
- IMWICXCTLULCFP-UHFFFAOYSA-N 3-[n-ethyl-3-methyl-4-[(6-methylsulfonyl-1,3-benzothiazol-2-yl)diazenyl]anilino]propanenitrile Chemical compound CC1=CC(N(CCC#N)CC)=CC=C1N=NC1=NC2=CC=C(S(C)(=O)=O)C=C2S1 IMWICXCTLULCFP-UHFFFAOYSA-N 0.000 claims description 4
- FWTBRYBHCBCJEQ-UHFFFAOYSA-N 4-[(4-phenyldiazenylnaphthalen-1-yl)diazenyl]phenol Chemical compound C1=CC(O)=CC=C1N=NC(C1=CC=CC=C11)=CC=C1N=NC1=CC=CC=C1 FWTBRYBHCBCJEQ-UHFFFAOYSA-N 0.000 claims description 4
- XXSLVBDPACXUDO-UHFFFAOYSA-N 4-hydroxy-1-methyl-3-[(3-nitrophenyl)diazenyl]quinolin-2-one Chemical compound CN1C(=O)C(N=NC2=CC(=CC=C2)[N+]([O-])=O)=C(O)C2=CC=CC=C12 XXSLVBDPACXUDO-UHFFFAOYSA-N 0.000 claims description 4
- 235000009508 confectionery Nutrition 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 4
- MJEWVKATPDZNHU-UHFFFAOYSA-N n-[2-[(2-bromo-4,6-dinitrophenyl)diazenyl]-5-[2-cyanoethyl(2-hydroxyethyl)amino]-4-methoxyphenyl]acetamide Chemical compound C1=C(N(CCO)CCC#N)C(OC)=CC(N=NC=2C(=CC(=CC=2Br)[N+]([O-])=O)[N+]([O-])=O)=C1NC(C)=O MJEWVKATPDZNHU-UHFFFAOYSA-N 0.000 claims description 4
- OIXUJRCCNNHWFI-UHFFFAOYSA-N 1,2-dioxane Chemical compound C1CCOOC1 OIXUJRCCNNHWFI-UHFFFAOYSA-N 0.000 claims description 3
- WZYPIHOBHDXNJL-UHFFFAOYSA-N 2-[4-[(2-bromo-6-chloro-4-nitrophenyl)diazenyl]-3-chloro-n-(2-hydroxyethyl)anilino]ethanol Chemical compound ClC1=CC(N(CCO)CCO)=CC=C1N=NC1=C(Cl)C=C([N+]([O-])=O)C=C1Br WZYPIHOBHDXNJL-UHFFFAOYSA-N 0.000 claims description 3
- NBEXAEYARUBYDV-UHFFFAOYSA-N 2-[4-[(2-chloro-4-nitrophenyl)diazenyl]-n-(2-hydroxyethyl)-3-methylanilino]ethanol Chemical compound CC1=CC(N(CCO)CCO)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1Cl NBEXAEYARUBYDV-UHFFFAOYSA-N 0.000 claims description 3
- PBZAQXHQPHZWIF-UHFFFAOYSA-N 4-[(4-chloro-2-methylphenyl)diazenyl]-N-(2-ethoxyphenyl)-3-hydroxynaphthalene-2-carboxamide Chemical compound CCOc1ccccc1NC(=O)c1cc2ccccc2c(N=Nc2ccc(Cl)cc2C)c1O PBZAQXHQPHZWIF-UHFFFAOYSA-N 0.000 claims description 3
- RTZYVAQWQXPIAC-UHFFFAOYSA-N 4-[(4-phenyldiazenylphenyl)diazenyl]phenol Chemical compound C1=CC(O)=CC=C1N=NC1=CC=C(N=NC=2C=CC=CC=2)C=C1 RTZYVAQWQXPIAC-UHFFFAOYSA-N 0.000 claims description 3
- PTIVACHGVHIMMK-UHFFFAOYSA-N 4-[[2-methoxy-4-[(4-nitrophenyl)diazenyl]phenyl]diazenyl]phenol Chemical compound COC1=CC(N=NC=2C=CC(=CC=2)[N+]([O-])=O)=CC=C1N=NC1=CC=C(O)C=C1 PTIVACHGVHIMMK-UHFFFAOYSA-N 0.000 claims description 3
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 3
- MRQIXHXHHPWVIL-UHFFFAOYSA-N chembl1397023 Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC1=CC=CC=C1 MRQIXHXHHPWVIL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 6
- 230000035484 reaction time Effects 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 2
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims 1
- AGYKGLGUMGTNHK-UHFFFAOYSA-N C.[Br] Chemical compound C.[Br] AGYKGLGUMGTNHK-UHFFFAOYSA-N 0.000 claims 1
- PVQLYHIXPHMFDV-UHFFFAOYSA-N CC(C)=O.c1ncncn1 Chemical compound CC(C)=O.c1ncncn1 PVQLYHIXPHMFDV-UHFFFAOYSA-N 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 238000004043 dyeing Methods 0.000 abstract description 9
- 229920000570 polyether Polymers 0.000 abstract description 5
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 4
- 150000003512 tertiary amines Chemical class 0.000 abstract description 2
- 229920003043 Cellulose fiber Polymers 0.000 abstract 1
- 125000001475 halogen functional group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 132
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 230000006837 decompression Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000002955 isolation Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000986 disperse dye Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000985 reactive dye Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000011017 operating method Methods 0.000 description 4
- 235000011837 pasties Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 241001062009 Indigofera Species 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229940126678 chinese medicines Drugs 0.000 description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 description 2
- OMRXVBREYFZQHU-UHFFFAOYSA-N 2,4-dichloro-1,3,5-triazine Chemical compound ClC1=NC=NC(Cl)=N1 OMRXVBREYFZQHU-UHFFFAOYSA-N 0.000 description 2
- HTSVYUUXJSMGQC-UHFFFAOYSA-N 2-chloro-1,3,5-triazine Chemical class ClC1=NC=NC=N1 HTSVYUUXJSMGQC-UHFFFAOYSA-N 0.000 description 2
- UNBOSJFEZZJZLR-UHFFFAOYSA-N 4-(4-nitrophenylazo)aniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1 UNBOSJFEZZJZLR-UHFFFAOYSA-N 0.000 description 2
- 244000144730 Amygdalus persica Species 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
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- 229920002521 macromolecule Polymers 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical group C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- ONRREFWJTRBDRA-UHFFFAOYSA-N 2-chloroethanamine;hydron;chloride Chemical compound [Cl-].[NH3+]CCCl ONRREFWJTRBDRA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MCZQGJXPPZHLTG-UHFFFAOYSA-N C.[Cl] Chemical compound C.[Cl] MCZQGJXPPZHLTG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 241000238370 Sepia Species 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000000664 diazo group Chemical class [N-]=[N+]=[*] 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- INQOMBQAUSQDDS-BJUDXGSMSA-N iodomethane Chemical group I[11CH3] INQOMBQAUSQDDS-BJUDXGSMSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- PKAUVIXBZJUYRV-UHFFFAOYSA-N methane;hydroiodide Chemical compound C.I PKAUVIXBZJUYRV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical class CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/046—Specific dyes not provided for in group C09B62/06 - C09B62/10
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/085—Monoazo dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
The present invention provides a kind of azo structure contained active cationic dye as shown in figure (1) and preparation method thereof.Reacted first with secondary amine compound and methoxy poly (ethylene glycol) glycidol ether, prepare the methyl polyether-based substituted propyl tertiary amine compound of 2 hydroxyl 3, then itself and the azo dispersion dyes chromogen containing hydroxyl or amino are attached using halo s-triazine, it is finally again that the tertiary amine progress in product is quaternized, prepare azo structure contained active cationic dye.This active cationic dye chromatogram is complete, and water solubility is adjustable, direct to cellulose fibre high, can carry out salt-free dyeing, its preparation method is simple, and cost is low.
Description
Technical field
The invention belongs to dye chemical industry field, the cation activity for being related to a kind of azo structure contained disperse dyes chromogen contaminates
Material and preparation method thereof.
Technical background
In order to solve traditional activated dyestuff (containing anionic water soluble groups such as sulfonic group or carboxyls) to cellulosic fabric
The problem of electrolyte need to be added during dyeing, researchers have done substantial amounts of research.Mainly solve method be fabric cation graft,
Add several aspects such as dyeing assistant and active cationic dye.The research and development of wherein active cationic dye are always the heat of research
Point.
It is raw material that Zhao Tao, which describes one kind with N, N- dimethylaminopropylamines, 1- amino anthraquinones, Cyanuric Chloride, dithyl sulfate,
Quaternary ammonium salt cationic reactive dye and its dyeability (dyestuff and dyeing, 2009,46 (4) of synthesis：32-35)；Wang Lianjun is situated between
Continued a kind of cation activity using Isosorbide-5-Nitrae-diamino-anthraquinone, cyanuric chloride, 2-chloroethyl amine hydrochloride and pyridine as Material synthesis
Dyestuff, and use it for bafta salt-free dyeing (printing and dyeing, 2009,35 (7)：9-11)；Ma Hui describes one kind with polyethyleneimine
Amine (PEI) is macromolecular scaffold, and the chloro-1,3,5-triazines of 2- (1- anthraquinonyls amino) -4,6- bis- are dye matrix, are connect by chemistry
The high molecular dye of branch synthesis, then it is quaternized to the nitrogen-atoms progress on polyethyleneimine macromolecule, obtain macromolecule cation
Reactive dye (printing and dyeing assistant, 2011,28 (12)：25-28).
Patent CN200410078938.1 describes a series of bisazos " quaternary dyestuff ", still, because its dyestuff
Still contain 3-4 sulfonic group in structure as water soluble group, be not real " cation " reactive dye, it is impossible to realize
The salt-free dyeing of bafta；Patent CN103725036A describes a kind of orange red active cationic dye and its system respectively
Preparation Method, the transformation of the way Preparation Method be first to be reacted with Cyanuric Chloride using amino anthraquinones, prepare dichloro s-triazine intermediate, then this
Dichloro s-triazine intermediate with N, the reaction of N- dimethylated propyl diethylenetriamines, is then prepared with nicotinic acid, chloroethanes reaction again successively again；
The preparation method of the active cationic dye of a kind of segment containing polyetheramine is described in patent CN105694529.Its synthesis thinking
It is to be connected using polyetheramine with anthraquinone chromogen by a chloro-s-triazine, and quaternary ammonium salt structure is introduced in polyetheramine end.This
Class dyestuff solves the problems, such as the water-soluble poor of common active cationic dye.
The active cationic dye of dication bis-epoxy active group is described in patent CN105585875A.Its preparation side
Method is to utilize anthraquinone ring chromogen, obtained by connecting two quaternary ammonium salt structures containing epoxy radicals respectively by cyanuro；Patent
All describe a kind of preparation method of the reactive dye of result containing quaternary ammonium salt in WO9842785A1 and patent US5925745, but its
Still substantial amounts of sulfonate radical is contained in molecular structure, therefore it is not active cationic dye truly；Patent
A kind of dye of positive ion containing anthraquinone ring chromogen is described in US5520707, its coloring available for hair, but its
There is no response type group, therefore be not belonging to active cationic dye category yet.
The present invention relates to it is a kind of using containing the active cationic dye prepared by azo structure disperse dyes chromogen and
Its preparation method, design and prepare a kind of water-soluble preferable, the complete azo structure contained active cationic dye of chromatogram.
Anthraquinone ring dyestuff is selected as most common active cationic dye chromogen structure, still because its molecular weight is small
Anthraquinone ring dye species are less, have impact on the applicability of active cationic dye, meanwhile, anthraquinone dye production be exist compared with
Big pollution problem.And azo structure dyestuff chromogen usually contains multiple nitros, cyanogen because complicated in dye structure
The substituents such as base, chlorine, bromine, molecular weight is larger, poorly water-soluble, seldom is selected as active cationic dye chromogen structure.This
The common azo structure contained disperse dyes of patent of invention are modified as chromogen, draw body polyethers in the molecular structure
Segment is water-soluble to improve its, while introduces quaternary ammonium salt and halogen s-triazine structure, prepares containing polyether segment and azo structure
Active cationic dye.Such dyestuff preparation method is simple, and raw material are cheap, and cost is low, prepared active cationic dye
Good water solubility is good to bafta salt-free dyeing effect.
The content of the invention
It is an object of the invention to provide azo structure contained active cationic dye, shown in its structural formula following (1),
The preparation method of the active cationic dye as shown in figure (1) designed by the present invention mainly has following three step complete
Into：
The first step：Reacted using hydroxyl or the azo dispersion dyes chromogen of amino and three halogen s-triazine, prepare two
Halogen s-triazine azo dispersion dyes derivative, its reaction equation are as follows：
Second step：Reacted using secondary amine compound and methoxy poly (ethylene glycol) glycidol ether, prepare 2- hydroxyl -3- first
Base polyether-based substituted propyl tertiary amine compound：
3rd step：The 2- hydroxy-3-methyls polyether-based substituted propyl tertiary amine compound and the first step prepared using second step
After the prepared dihalo s-triazine azo dispersion dyes derivatives reaction of reaction, then it is quaternized through quaternizing agent, prepare
Azo structure contained active cationic dye：
In the first step, the azo dispersion dyes chromogen of selection is hydroxyl or the disperse dyes of amino；
Preferably, in the first step, the hydroxyl of selection or the azo dispersion dyes chromogen of amino are：Disperse yellow 3,
Disperse yellow 4, disperse yellow 5, disperse yellow 7, disperse yellow 10, disperse yellow 23, disperse yellow 50, disperse yellow 56, disperse yellow 60, disperse yellow
70th, disperse yellow 76, disperse yellow 79, disperse yellow 83, disperse yellow 97, disperse yellow 102, disperse yellow 103, disperse yellow 114, disperse yellow
119th, disperse yellow 199, disperse yellow 123, disperse yellow 126, disperse yellow 134, disperse yellow 165, DISPERSE Yellow 211, disperse yellow 221, point
Dissipate Huang 231, disperse yellow 241；Disperse orange 5, disperse orange 10, disperse orange 13, disperse orange 17, disperse orange 20, disperse orange 21, disperse orange
29th, disperse orange 38, disperse orange 42, disperse orange 66, disperse orange 74, disperse orange 121, disperse orange 138；Red-1 200, disperse red 2, divide
Dissipate red 220, disperse red 221, disperse red 5, disperse red 6, disperse red 8, Red-1 200 2, DISPERSE Red 13, Red-1 200 6, disperse red
17th, Red-1 200 9, disperse red 30, disperse red 32, disperse red 43, Disperse Blue 56, disperse red 58, disperse red 64, disperse red 88, point
Dissipate red 97, disperse red 98, Red-1 200 07, Red-1 200 09, dispersion red 11 8, Red-1 200 26, Red-1 200 28, Red-1 200 29,
DISPERSE Red 13 7, Red-1 200 41, Red-1 200 51, Red-1 200 56, Red-1 200 57, disperse red 200, disperse red 334；Disperse violet
7th, disperse violet 12, disperse violet 13, disperse violet 24, disperse violet 43；Disperse blue 15, disperse blue 38, disperse blue 82, disperse blue 85, point
Dissipate indigo plant 90, disperse blue 94, disperse blue 96, disperse blue 102, disperse blue 122, disperse blue 128, disperse blue 146, disperse blue 264, point
Dissipate indigo plant 344；Disperse brown 1：1st, disperse brown 4, disperse brown 5；Scattered black 4.
Preferably, the three halo s-triazine selected in the first step are trichloro-triazine or trifluoro s-triazine；
In the first step, the ratio between amount of substance of three selected halo s-triazine and azo dispersion dyes chromogen is 1:
1~4: 1；
Preferably, the secondary amine compound in the second step is dimethylamine, diethylamine, diphenylamines, dibenzylamine, N- methyl benzyls
Amine, methylphenylamine, N, N, N '-trimethyl ethylenediamine, N, N, N '-trimethyl -1,3- propane diamine；
The degree of polymerization of polyethylene glycol is in 2-50 in methoxy poly (ethylene glycol) glycidyl ether compound in the second step
Between；
Preferably, the methoxy poly (ethylene glycol) glycidyl ether compound in the second step is methoxy poly (ethylene glycol)
(400) glycidol ether, methoxy poly (ethylene glycol) (750) glycidol ether, methoxy poly (ethylene glycol) (1000) glycidol ether,
Methoxy poly (ethylene glycol) (1500) glycidol ether, methoxy poly (ethylene glycol) (2000) glycidol ether and methoxy poly (ethylene glycol)
(2500) glycidol ether；
In the second step, secondary amine compound and the ratio of the amount of the material of methoxy poly (ethylene glycol) glycidyl ether compound
For 1: 1~5: 1；
Preferably, the quaternizing agent in the 3rd step is dimethyl suflfate, dithyl sulfate, dimethyl carbonate, iodine
Methane, chloromethanes, bromomethane, chloroethanes, iodoethane, benzyl chloride, cylite.
The preparation method of the azo structure contained active cationic dye is：
(1) by azo dispersion dyes and three halo s-triazine in acetone, 1,2- dioxane, acetonitrile, tetrahydrofuran, diformazan
The in the mixed solvent of base formamide equal solvent or itself and water is sufficiently stirred, and is adjusted with sodium carbonate or potassium carbonate and is connect pH value of reaction system and be
4-6, after -5 DEG C~15 DEG C are reacted 4~9 hours, isolate product；
(2) by secondary amine compound and the abundant compound of methoxy poly (ethylene glycol) glycidol ether, 60~140 DEG C of fully reactions
3-8 hours, isolate product；
(3) amount of the materials such as the product that is reacted with (2) step of product that (1) step is reacted is mixed, with sodium carbonate, carbonic acid
Potassium, sodium hydroxide or potassium hydroxide regulation pH value of reaction system are 4-6, and after 30-65 DEG C is reacted 4~9 hours, separation is produced
Thing, the quaternizing agent of certain amount of substance is added, after 60-110 DEG C of reaction 2-8 hour, obtains the azo structure contained cation of product
Reactive dye.
Wherein, the total described azo dispersion dyes of step (1) be disperse yellow 3, disperse yellow 4, disperse yellow 5, disperse yellow 7, point
Dissipate Huang 10, disperse yellow 23, disperse yellow 50, disperse yellow 56, disperse yellow 60, disperse yellow 70, disperse yellow 76, disperse yellow 79, disperse yellow
83rd, disperse yellow 97, disperse yellow 102, disperse yellow 103, disperse yellow 114, disperse yellow 119, disperse yellow 123, disperse yellow 126, scattered
Huang 134, disperse yellow 165, disperse yellow 199, DISPERSE Yellow 211, disperse yellow 221, disperse yellow 231, disperse yellow 241；Disperse orange 5, divide
Dissipate orange 10, disperse orange 13, disperse orange 17, disperse orange 20, disperse orange 21, disperse orange 29, disperse orange 38, disperse orange 42, disperse orange
66th, disperse orange 74, disperse orange 121, disperse orange 138, Red-1 200, disperse red 2, disperse red 220, disperse red 221, disperse red 5,
Disperse red 6, disperse red 8, Red-1 200 2, DISPERSE Red 13, Red-1 200 6, Red-1 200 7, Red-1 200 9, disperse red 30, disperse red
32nd, disperse red 43, Disperse Blue 56, disperse red 58, disperse red 64, disperse red 88, disperse red 97, disperse red 98, Red-1 200 07,
Red-1 200 09, dispersion red 11 8, Red-1 200 26, Red-1 200 28, Red-1 200 29, DISPERSE Red 13 7, Red-1 200 41, disperse red
151st, Red-1 200 56, Red-1 200 57, disperse red 200, disperse red 334, disperse violet 7, disperse violet 12, disperse violet 13, disperse violet
24th, disperse violet 43；Disperse blue 15, disperse blue 38, disperse blue 82, disperse blue 85, disperse blue 90, disperse blue 94, disperse blue 96, point
Dissipate indigo plant 102, disperse blue 122, disperse blue 128, disperse blue 146, disperse blue 264, disperse blue 344；Disperse brown 1：1st, disperse brown 4,
Disperse brown 5, scattered black 4.Three described halo s-triazine are trichloro-triazine or trifluoro s-triazine；
Secondary amine compound described in step (2) is dimethylamine, diethylamine, diphenylamines, dibenzylamine, N- methylbenzylamines, N-
Methylaniline, N, N, N '-trimethyl ethylenediamine, N, N, N '-trimethyl -1,3- propane diamine.Described methoxy poly (ethylene glycol) contracting
Water glycerine ether compound be methoxy poly (ethylene glycol) (400) glycidol ether, methoxy poly (ethylene glycol) (750) glycidol ether,
Methoxy poly (ethylene glycol) (1000) glycidol ether, methoxy poly (ethylene glycol) (1500) glycidol ether, methoxy poly (ethylene glycol)
(2000) glycidol ether and methoxy poly (ethylene glycol) (2500) glycidol ether glycidol ether.
Quaternizing agent described in step (3) is dimethyl suflfate, dithyl sulfate, dimethyl carbonate, iodomethane, chlorine
Methane, bromomethane, chloroethanes, iodoethane, benzyl chloride, cylite.
Wherein, in the preparing raw material of the azo structure contained active cationic dye, azo dispersion dyes used are point
Huang 7 is dissipated, three halo s-triazine are trichloro-triazine, and secondary amine compound is dimethylamine, methoxy poly (ethylene glycol) glycidyl ether
Compound is methoxy poly (ethylene glycol) (750) glycidol ether, when quaternizing agent is dimethyl suflfate, utilizes above-mentioned raw material system
The reaction equation of standby azo structure contained active cationic dye is as follows：
(1) step
(2) step
(3) step
In the preparing raw material of the azo structure contained active cationic dye, azo dispersion dyes used are disperse red
98, three halo s-triazine are trifluoro s-triazine, and secondary amine compound is diphenylamines, methoxy poly (ethylene glycol) glycidyl ether compound
For methoxy poly (ethylene glycol) (1000) glycidol ether, when quaternizing agent is iodomethane, prepared using above-mentioned raw material containing even
The reaction equation of N structure active cationic dye is as follows：
(1) step
(2) step
(3) step
Brief description of the drawings
Scheme (1) azo structure contained active cationic dye structural representation,
Wherein：N is 2 to 50 natural number；X is F or Cl atoms；
D is azo structure dyestuff chromogen；
Q is the group containing quaternary ammonium salt structure, such as following formula (a), (b), (c), shown group：
And R1, R2, R3, R4, R5For methyl, ethyl, phenyl, benzyl.
Scheme (2) product P-1 structural formulas；
Scheme (3) product P-2 structural formulas；
Scheme (4) product P-3 structural formulas；
Scheme (5) product P-4 structural formulas；
Scheme (6) product P-5 structural formulas；
Scheme (7) product P-6 structural formulas；
Scheme (8) product P-7 structural formulas；
Scheme (9) product P-8 structural formulas；
Scheme (10) product P-9 structural formulas；
Scheme (11) product P-10 structural formulas；
Scheme (12) product P-11 structural formulas；
Scheme (13) product P-12 structural formulas；
Scheme (14-1) product P13a structural formulas；
Scheme (14-2) product P13b structural formulas；
Scheme (14) product P-13 structural formulas；
Scheme (15-1) product P-14b structural formulas；
Scheme (15) product P-14 structural formulas；
Scheme (16-1) product P-15a structural formulas；
Scheme (16-2) product P-15b structural formulas；
Scheme (16) product P-15 structural formulas；
Scheme (17) product P-16 structural formulas；
Scheme (18) product P-17 structural formulas；
Scheme (19) product P-18 structural formulas；
Scheme (20) product P-19 structural formulas；
Scheme (21) product P-20 structural formulas.
Embodiment
Following examples are the further explanations to the present invention, but the invention is not limited in this.
Azo dispersion dyes part is provided by DYE PRODUCTION producer in the following example, is partly made by oneself by laboratory, azo
Disperse dyes preparation method is very simple, is also well known；The mono methoxy polyethylene glycol glycidol ether of different molecular weight
Compound can also buy gained by market, can also utilize mono methoxy APEO and epoxychloropropane system by laboratory
Standby, its preparation method is shown in document (fine-chemical intermediate, 2005,35 (3)：45-47；Hubei Chemical, 1994, (1)：19-21；
Synthesis, 1985, (6)：649-651).
Involved organic chemical reactionses in the present invention, such as the hydroxyl in azo dispersion dyes or amino and halo s-triazine
Reaction, methoxy poly (ethylene glycol) glycidol ether and the active hydrogen reaction in secondary amine, tertiary amine and quaternizing agent reaction prepare season
Ammonium salt belongs to common chemical reaction, and product structure is very clear and definite, and accessory substance is few.
Embodiment 1
(1) by disperse yellow 3 (26.9g, 0.1mol, laboratory self-control, purity 99.5%) with trichloro-triazine (18.5g,
0.1mol, Chinese medicines group production) it is sufficiently stirred in 100ml acetone, it is 5-6 to connect pH value of reaction system with 10% sodium carbonate liquor,
After 5 DEG C are reacted 8 hours, it is standby to isolate product；By products therefrom with nuclear magnetic resonance (1H-NMR) method is characterized,1H-
NMR (DMSO) result：δ=8.12 (s, 1H)；δ=7.15~7.90 (d, 7H)；δ=2.35 (s, 3H)；δ=2.36 (s, 3H)；
(2) by dimethylamine (21.4g, 0.2mol) and methoxy poly (ethylene glycol) (750) glycidol ether (80g, 0.1mol,
Jiangsu Zhongshang Chemical Co., Ltd. produces) abundant compound, 80 DEG C of fully reactions 5 hours, vacuum rotary steam, separate unnecessary diformazan
Amine, collect product；
(3) by the product of product (33.2g, 0.08mol) and (2) step reaction of (1) step reaction (72.56g,
The amount mixing of material such as 0.08mol), it is 4-6 to adjust pH value of reaction system with sodium carbonate, after 65 DEG C of reactions 6 hours, uses acetone
Extract and separate goes out product, with anhydrous sodium sulfate drying to anhydrous, adds dimethyl suflfate (5.05g, 0.04mol), 60 DEG C anti-
After answering 2 hours, it is azo structure contained active cationic dye 100g to obtain product P-1, yield 93.7%.Under room temperature condition, P-1
For khaki thick liquid, structural formula is shown in figure (2).
By products therefrom P-1 with nuclear magnetic resonance (1H-NMR) method is characterized,1H-NMR(D2O) result：δ=8.0
(s, 1H)；δ=7.09~7.91 (d, 7H)；δ=2.05 (s, 3H)；δ=2.36 (s, 9H)；δ=2.16~2.46 (t, 67H).
Embodiment 2
(1) by disperse yellow 4, (53.5g, 0.2mol, filter cake dry powder, purity 99.5%, the double peaches in Qingdao are refined Co., Ltd's life
Production) fully stirred in the mixed solvent of 300ml acetonitriles and 200ml water with trifluoro s-triazine (27g, 0.2mol, Chinese medicines group production)
Mix, it is 5-6 to connect pH value of reaction system with 10% sodium carbonate liquor, and after -5 DEG C are reacted 6 hours, it is standby to isolate product.1H-
NMR (DMSO) result：δ=7.9~8.05 (d, 4H)；δ=7.73 (d, 1H)；δ=7.62 (s, 2H)；δ=7.43 (s, 2H)；δ
=5.16 (s, 1H).
(2) by diethylamine (14.6g, 0.2mol) and methoxy poly (ethylene glycol) (1000) glycidol ether (220g,
0.2mol, Jiangsu Zhongshang Chemical Co., Ltd.'s production) abundant compound, 100 DEG C of fully reactions 8 hours, collect product；
(3) product (113g, 0.08mol) for reacting the product (38g, 0.1mol) of (1) step reaction with (2) step etc.
The amount mixing of material, it is 4-6 to adjust pH value of reaction system with sodium carbonate, after 65 DEG C are reacted 6 hours, is isolated with acetone extract
Product, with anhydrous sodium sulfate drying to anhydrous, add dimethyl suflfate (6.32g, 0.05mol), after 60 DEG C of reactions 2 hours,
Obtain the azo structure contained active cationic dye 152g of product P-2, yield 96.3%.Under room temperature condition, product is golden yellow sticky
Liquid, structural formula are shown in figure (3).
By products therefrom P-1 with nuclear magnetic resonance (1H-NMR) method is characterized,1H-NMR(D2O) result：δ=7.85
~8.07 (d, 4H)；δ=7.73 (d, 1H)；δ=7.62 (s, 2H)；δ=7.44 (s, 2H)；δ=5.26 (s, 1H)；δ=3.72
(q, 1H)；δ=3.66 (t, 2H)；δ=3.54 (t, 88H)；δ=3.35 (t, 6H)；δ=3.26 (s, 6H)；δ=3.23 (s, 3H)
δ=3.06 (s, 2H)；
Embodiment 3
(1) by disperse yellow 60 (169g, 0.5mol, the production of Zhejiang mountain valley dyestuff company, filter cake dry powder, purity 99.5%) with
Trichloro-triazine (92.5g, 0.5mol, Chinese medicines group production) is molten in the mixing of 1000ml dioxane and 500ml deionized waters
It is sufficiently stirred under agent, it is 5-6 to connect pH value of reaction system with 10% sodium carbonate liquor, after 5 DEG C are reacted 8 hours, isolates product
It is standby.1H-NMR (DMSO) result：δ=8.05 (d, 2H)；δ=7.43 (d, 2H)；δ=7.32 (s, 5H)；δ=3.83 (s,
3H)；δ=3.26 (s, 3H).
(2) by dibenzylamine (118.4g, 0.6mol) and methoxy poly (ethylene glycol) (2000) glycidol ether (1050g,
0.5mol, Jiangsu Zhongshang Chemical Co., Ltd.'s production) abundant compound, 120 DEG C of fully reactions 7 hours, vacuum rotary steam, separation is more
Remaining dibenzylamine, collect product；
(3) by the product of product (240g, 0.48mol) and (2) step reaction of (1) step reaction (1100g,
The amount mixing of material such as 0.48mol), it is 4-6 to adjust pH value of reaction system with sodium carbonate, after 65 DEG C of reactions 6 hours, uses acetonitrile
Extract and separate goes out product, with anhydrous sodium sulfate drying to being added in high-temperature high-pressure reaction kettle after anhydrous.Add chloromethanes gas
Body (25.3g, 0.5mol), in autoclave 80 DEG C reaction 4 hours after, obtain the azo structure contained cation activities of product P-3
Dyestuff 1270g, product are waxy yellow lotion, yield 93.2%.Under room temperature condition, P-3 is yellow waxy material, and structural formula is shown in
Scheme (4).
Embodiment 4
(1) by disperse yellow 76 (50.3g, 0.1mol, laboratory self-control, purity 99.5%) with trichloro-triazine (18.5g,
0.1mol) it is sufficiently stirred in 200mlDMF, it is 5-6 to connect pH value of reaction system with 10% sodium carbonate liquor, is reacted 5 hours at 5 DEG C
Afterwards, it is standby to isolate product.1H-NMR (DMSO) result：δ=8.00 (d, 2H)；δ=7.50 (d, 1H)；δ=7.41 (d, 2H)；
δ=7.35 (s, 2H)；δ=7.32 (s, 2H)；δ=3.88 (s, 3H)；δ=3.76 (s, 3H).
(2) by diphenylamines (25.4g, 0.15mol) and methoxy poly (ethylene glycol) (1500) glycidol ether (165g,
0.1mol) abundant compound, 120 DEG C are fully reacted 5 hours, vacuum rotary steam, separate unnecessary diphenylamines, collect product；
(3) by the product of product (50g, 0.075mol) and (2) step reaction of (1) step reaction (136.5g,
The amount mixing of material such as 0.075mol), it is 5 with potassium carbonate regulation pH value of reaction system, after 75 DEG C of reactions 8 hours, uses tetrahydrochysene
Furans extract and separate goes out product, with anhydrous sodium sulfate drying to anhydrous, adds iodomethane (10.65g, 0.075mol), 40 DEG C
After back flow reaction 2 hours, the azo structure contained active cationic dye 182.4g of product P-4, yield 92.5% are obtained.Room temperature condition
Under, P-4 is yellow waxy material, and structural formula is shown in figure (5).
Embodiment 5
(1) by disperse yellow 83 (130g, 0.4mol, laboratory self-control, purity 99.6%) with trichlorine rate triazine (74g,
0.4mol) it is sufficiently stirred in 500ml dioxane and 500ml deionized water in the mixed solvents, it is reversed with 10% sodium carbonate liquor
It is 5.5 to answer system pH, and after 10 DEG C are reacted 8 hours, it is standby to isolate product.1H-NMR (DMSO) result：δ=9.21 (s,
1H)；δ=8.21 (d, 1H)；δ=7.72 (d, 1H)；δ=7.50 (d, 2H)；δ=6.37 (s, 2H)；δ=6.21 (s, 2H)；δ=
4.48 (s, 1H)；δ=3.76 (s, 2H)；δ=3.46 (d, 2H)；δ=3.36~3.24 (t, 3H).
(2) by methylphenylamine (53.58g, 0.5mol) and methoxy poly (ethylene glycol) (1500) glycidol ether (660g,
0.4mol) abundant compound, 90 DEG C are fully reacted 6 hours, vacuum rotary steam, separate unnecessary methylphenylamine, collect product；
(3) product (350g, 0.2mol) for reacting the product (100g, 0.2mol) of (1) step reaction with (2) step etc.
The amount mixing of material, it is 4.5 with sodium carbonate regulation pH value of reaction system, it is washed with dioxane after 75 DEG C are reacted 5 hours
Filter is spin-dried for collecting product, with anhydrous sodium sulfate drying to anhydrous, adds dimethyl carbonate (18.14g, 0.2mol), 90 DEG C anti-
After answering 2 hours, the azo structure contained active cationic dye 440g of product P-5, yield 94% are obtained.Under room temperature condition, P-5 is yellowish-brown
Color waxy substance, structural formula are shown in figure (6).
Embodiment 6
(1) by disperse yellow 241 (33.7g, 0.1mol, the production of Jiangsu Ya Bang companies, wheat cake superfine powder, purity 99.5%) with
Three Cyanuric trifluorides (13.5g, 0.1mol) are sufficiently stirred in 100ml acetone and 50ml deionized water mixed solvents, with 10% sodium carbonate
It is 5.5 that solution, which connects pH value of reaction system, and after 0 DEG C is reacted 4 hours, it is standby to isolate product；
(2) by methylphenylamine (16g, 0.15mol) and methoxy poly (ethylene glycol) (750) glycidol ether (80g,
0.1mol) abundant compound, 950 DEG C are fully reacted 7 hours, vacuum rotary steam, separate unnecessary methylphenylamine, collect product；
(3) by the product of product (24.1g, 0.05mol) and (2) step reaction of (1) step reaction (45.3g,
The amount mixing of material such as 0.05mol), it is 4.5 with sodium carbonate regulation pH value of reaction system, after 65 DEG C of reactions 4 hours, uses dioxy
Six washing-rounds are washed, and extraction decompression is spin-dried for isolating product, with anhydrous sodium sulfate drying to anhydrous, add benzyl chloride (6.33g,
0.05mol), 60 DEG C reaction 2 hours after, obtain the azo structure contained active cationic dye 70g of product P-6, yield 92.43%.Production
Thing P-6 structural formulas are shown in figure (7).
Embodiment 7
(1) by disperse orange 3 (48.5g, 0.2mol, the double peaches in Qingdao are refined Co., Ltd, purity 99%) and trichloro-triazine
(37g, 0.2mol) is sufficiently stirred in 500ml acetone, and it is 5-6 to connect pH value of reaction system with 10% sodium carbonate liquor, in 5 DEG C of reactions
After 8 hours, it is standby to isolate product；
(2) by N, N, N '-trimethyl ethylenediamine (20.45g, 0.2mol) and methoxy poly (ethylene glycol) (1500) glycidol
Ether (320g, 0.2mol) abundant compound, 120 DEG C are fully reacted 5 hours, vacuum rotary steam, separate unnecessary N, N, N '-trimethyl
Ethylenediamine, collect product；
(3) by (1) step react product 63.2g, 0.15mol) with (2) step reaction product (255g, 0.15mol)
Amount Deng material mixes, and is 5.5 with sodium carbonate regulation pH value of reaction system, after 60 DEG C are reacted 6 hours, with acetonitrile extraction, rotation
Product is steamed, with anhydrous sodium sulfate drying to anhydrous, adds dimethyl suflfate (18.94g, 0.15mol), 750 DEG C are reacted 3 hours
Afterwards, the azo structure contained active cationic dye 320.3g of product P-7, yield 95% are obtained.P-7 structural formulas are shown in figure (8).
Embodiment 8
(1) by disperse orange 5 (3.75g, 0.01mol, the lucky magnificent Chemical Manufacture in Zhejiang, purity 99%) and trichloro-triazine
(1.85g, 0.01mol) is sufficiently stirred in 30ml acetone, and it is 5-6 to connect pH value of reaction system with 10% sodium carbonate liquor, anti-at 5 DEG C
After answering 4 hours, it is standby to isolate product；
(2) by N, N, N '-trimethyl ethylenediamine (1.53g, 0.015mol) and methoxy poly (ethylene glycol) (750) glycidol
Ether (8g, 0.01mol) abundant compound, 110 DEG C are fully reacted 5 hours, vacuum rotary steam, separate unnecessary N, N, N '-trimethyl
Ethylenediamine, collect product；
(3) by the product of product (4.4g, 0.008mol) and (2) step reaction of (1) step reaction (7.216g,
The amount mixing of material such as 0.008mol), it is 6.5 with sodium carbonate regulation pH value of reaction system, after 65 DEG C of reactions 4 hours, with third
Ketone extract and separate goes out product, with anhydrous calcium chloride drying to anhydrous, adds dimethyl suflfate (1g, 0.008mol), 60 DEG C anti-
After answering 2 hours, the azo structure contained active cationic dye 10g of product P-8, yield 79.3% are obtained.P-8 structural formulas are shown in figure (9).
Embodiment 9
(1) by disperse orange 3 (73g, 0.3mol, intercalation native chemical industry, filter cake dry powder, purity 99%) and trichloro-triazine
(55.5g, 0.3mol) is sufficiently stirred, with 10% sodium carbonate liquor in 500ml acetonitriles and 300ml deionized water mixed solutions
It is 5.5 to connect pH value of reaction system, and after 5 DEG C are reacted 8 hours, it is standby to isolate product；
(2) N, N, N '-trimethyl -1,3- propane diamine (35g, 0.3mol) are shunk sweet with methoxy poly (ethylene glycol) (1000)
The abundant compound of oily ether (340g, 0.3mol), 120 DEG C are fully reacted 5 hours, collect product；
(3) by the product of product (118.2g, 0.28mol) and (2) step reaction of (1) step reaction (350g,
The amount mixing of material such as 0.28mol), it is 6 with sodium carbonate regulation pH value of reaction system, after 65 DEG C of reactions 7 hours, is extracted with acetonitrile
Separation and washed product are taken, with anhydrous sodium sulfate drying to anhydrous, adds dithyl sulfate (43.2g, 0.28mol), 60 DEG C
After reaction 2 hours, the azo structure contained active cationic dye 500g of product P-9, yield 97.7% are obtained.Under room temperature condition, P-9 is
Orange red body of paste, structural formula are shown in figure (10).
Embodiment 10
(1) by Red-1 200 (95g, 0.3mol, intercalation native Chemical Group, purity 99.5%) and trichloro-triazine (55.5g,
0.3mol) it is sufficiently stirred in 100ml acetone, it is 5-6 to connect pH value of reaction system with 10% sodium carbonate liquor, is reacted 8 hours at 5 DEG C
Afterwards, it is standby to isolate product；
(2) N, N, N '-trimethyl -1,3- propane diamine (35g, 0.3mol) are shunk sweet with methoxy poly (ethylene glycol) (1000)
The abundant compound of oily ether (340g, 0.3mol), 120 DEG C are fully reacted 5 hours, collect product；
(3) by the product of product (129.2g, 0.28mol) and (2) step reaction of (1) step reaction (350g,
The amount mixing of material such as 0.28mol), it is 4-6 to adjust pH value of reaction system with sodium carbonate, after 65 DEG C of reactions 6 hours, uses acetone
Extract and separate goes out product, with anhydrous sodium sulfate drying to anhydrous, adds dithyl sulfate (43.2g, 0.28mol), 60 DEG C anti-
After answering 2 hours, the azo structure contained active cationic dye 510g of product P-10, yield 97.6% are obtained.Under room temperature condition, P-10 is
Large red thick liquid, structural formula are shown in figure (11).
Embodiment 11
(1) by dimethylamine (16.05g, 0.15mol) and methoxy poly (ethylene glycol) (750) glycidol ether (80g,
0.1mol) abundant compound, 90 DEG C are fully reacted 5 hours, vacuum rotary steam, separate unnecessary dimethylamine, collect product；
(2) (1) step product (90.7g, 0.1mol) and trichloro-triazine (18.5g, 0.1mol) are mixed, with 5% hydrogen
It is 5-6 that sodium hydroxide solution, which connects pH value of reaction system, and after being kept for 5 DEG C react 3 hours, product without isolation, adds Red-1 200 7
(35g, 0.1mol, Hangzhou Bai Hui chemical industry, purity 99%), is warming up to 45 DEG C, and it is 5-6 to continue to react pH, is reacted 6 hours,
Product is separated with acetonitrile extraction, and decompression is spin-dried for.
(3) (2) step product is dried, adds dimethyl suflfate (6.3g, 0.05mol), 60 DEG C are reacted 3 hours, must be produced
The azo structure contained active cationic dye 98.6g of thing P-11, yield 95%.Under room temperature condition, P-11 is aubergine thick liquid,
Structural formula is shown in figure (12).
Embodiment 12
(1) by N, N, N '-trimethyl ethylenediamine (20.4g, 0.2mol) and methoxy poly (ethylene glycol) (1000) glycidol
Ether (165g, 0.15mol) abundant compound, 90 DEG C are fully reacted 5 hours, vacuum rotary steam, separate unnecessary N, N, N '-trimethyl
Ethylenediamine, collect product；
(2) (1) step product (180.3g, 0.15mol) and trifluoro s-triazine (20.25g, 0.15mol) are mixed, used
It is 5.5 that 5% sodium hydroxide solution, which connects pH value of reaction system, and after being kept for -5 DEG C react 3 hours, product without isolation, adds scattered
Red 118 (80g, 0.15mol, the good sphering work in Hangzhou, purity 98%), are warming up to 30 DEG C, and it is 5-6 to continue to react pH, reaction 6
Hour, product is separated with acetonitrile extraction, and decompression is spin-dried for.
(3) (2) step product is dried, adds dimethyl suflfate (18.9g, 0.15mol), 60 DEG C are reacted 3 hours, must be produced
The azo structure contained active cationic dye 280g of thing P-12, yield 93.5%.P-12 structural formulas are shown in figure (13).
Embodiment 13
(1) N, N, N '-trimethyl -1,3- propane diamine (35g, 0.3mol) are shunk sweet with methoxy poly (ethylene glycol) (2000)
The abundant compound of oily ether (630g, 0.3mol), 120 DEG C are fully reacted 5 hours, collect product P13a, and product P13a structural formulas are shown in
Scheme (14-1)；
(2) (1) step product P13a (221g, 0.1mol) and trichloro-triazine (18.5g, 0.1mol) are mixed, with 5%
It is 5-6 that sodium hydroxide solution, which connects pH value of reaction system, and after being kept for 5 DEG C react 3 hours, product without isolation, adds disperse red 221
(35g, 0.1mol, Hangzhou Bai Hui chemical industry, purity 99%), is warming up to 45 DEG C, and it is 5-6 to continue to react pH, is reacted 6 hours,
Product is separated with acetonitrile extraction, and decompression is spin-dried for, and obtains product P13b, and product P13b structural formulas are shown in figure (14-2).
(3) (2) step product is dried, adds dimethyl suflfate (12.6g, 0.1mol), 60 DEG C are reacted 3 hours, must be produced
The azo structure contained active cationic dye 270g of thing P-13, yield 95.7%.P-13 structural formulas are shown in figure (14).
Embodiment 14
(1) N, N, N '-trimethyl -1,3- propane diamine (35g, 0.3mol) and methoxy poly (ethylene glycol) (2000) glycidol
Ether (630g, 0.3mol) abundant compound, 120 DEG C are fully reacted 5 hours, collect product P13a；
(2) (1) step product P13a (221g, 0.1mol) and trichloro-triazine (18.5g, 0.1mol) are mixed, with 5%
It is 5-6 that sodium hydroxide solution, which connects pH value of reaction system, and after being kept for 5 DEG C react 3 hours, product without isolation, adds disperse red 58
(38g, 0.1mol, Zhejiang Shanyu Dyestuff Chemical Co., Ltd., purity 99.5%), is warming up to 45 DEG C, continues to reaction pH and is
5-6, react 6 hours, product is separated with acetonitrile extraction, and decompression is spin-dried for, and obtains product P14b, and product P14b structural formulas are shown in figure (15-
1)。
(3) (2) step product is dried, adds dimethyl suflfate (12.6g, 0.1mol), 60 DEG C are reacted 3 hours, must be produced
The azo structure contained active cationic dye 280g of thing P-14, yield 96.55%.P-14 structural formulas are shown in figure (15)
Embodiment 15
(1) N, N, N '-trimethyl ethylenediamine (15.3g, 0.15mol) and methoxy poly (ethylene glycol) (1500) glycidol ether
(160g, 0.1mol) abundant compound, 110 DEG C are fully reacted 5 hours, and vacuum rotary steam collects unnecessary N, N, N '-front three respectively
Base ethylenediamine and product P15a, product P15a structural formulas are shown in figure (16-1).
(2) (1) step product P15a (170g, 0.1mol) and trifluoro s-triazine (13.5g, 0.1mol) are mixed, with 5%
It is 5-6 that sodium hydroxide solution, which connects pH value of reaction system, and after being kept for 0 DEG C react 3 hours, product without isolation, adds DISPERSE Red 13 7
(43.5g, 0.1mol, Zhejiang Shanyu Dyestuff Chemical Co., Ltd., purity 99.5%), is warming up to 45 DEG C, continues to react pH
For 5-6, react 6 hours, product is separated with acetonitrile extraction, and decompression is spin-dried for, and obtains product P15b, and product P15b structural formulas are shown in figure (16-
2)。
(3) (2) step product is dried, adds cylite (34.2g, 0.2mol), 60 DEG C are reacted 3 hours, obtain product P-
15 azo structure contained active cationic dye 240g, yield 96.8%.Under room temperature condition, P-15 is red pasty masses, structure
Formula is shown in figure (16).
Embodiment 16
(1) by N- methylbenzylamines (18.17g, 0.15mol) and methoxy poly (ethylene glycol) (1500) glycidol ether (160g,
0.1mol) abundant compound, 90 DEG C are fully reacted 5 hours, vacuum rotary steam, separate unnecessary N- methylbenzylamines, collect product；
(2) (1) step product (172.1g, 0.1mol) and trifluoro s-triazine (13.5g, 0.1mol) are mixed, with 5% hydrogen
It is 5-6 that sodium hydroxide solution, which connects pH value of reaction system, and after being kept for -5 DEG C react 3 hours, product without isolation, adds disperse violet 7
(50g, 0.1mol, Zhejiang mountain valley Chemical Co., Ltd., purity 99.5%), is warming up to 35 DEG C, and it is 5-6 to continue to react pH,
Reaction 6 hours, product is separated with acetonitrile extraction, and decompression is spin-dried for.
(3) (2) step product is dried, adds cylite (17.1g, 0.1mol), 75 DEG C are reacted 3 hours, are obtained product and are contained
Azo structure active cationic dye P-16245g, yield 97.2%.Under room temperature condition, P-16 is atropurpureus pasty masses, knot
Structure formula is shown in figure (17).
Embodiment 17
Using N, N, N '-trimethyl ethylenediamine and methoxy poly (ethylene glycol) (1500) trifluoro s-triazine, dimethyl suflfate and
Disperse blue 96, operating method are shown in embodiment 16, can obtain azo structure contained active cationic dye P-16, yield 94%.Room temperature bar
Under part, P-17 is blue pasty masses, and P-17 structural formulas are shown in figure (18).
Embodiment 18
Using N, N, N '-trimethyl ethylenediamine and methoxy poly (ethylene glycol) (1500) trifluoro s-triazine, dimethyl suflfate and
Disperse blue 102, operating method are shown in embodiment 16, can obtain azo structure contained active cationic dye P-18, yield 97%.Room temperature bar
Under part, P-18 is blue pasty masses, structural formula below figure (19).
Embodiment 19
Using N, N, N '-trimethyl ethylenediamine and methoxy poly (ethylene glycol) (2000) trichloro-triazine, dithyl sulfate and
Disperse brown 1, operating method are shown in embodiment 16, can obtain azo structure contained active cationic dye P-19, yield 94%.Room temperature condition
Under, P-19 is sepia waxy substance, and body structural formula is shown in figure (20).
Embodiment 20
Using N, N, N '-trimethyl ethylenediamine and methoxy poly (ethylene glycol) (1500) trichloro-triazine, chloromethanes and scattered
Black 4, operating method is shown in embodiment 16 and embodiment 3, can obtain azo structure contained active cationic dye P-20, yield 94%.Room
Under the conditions of temperature, P-20 is black body of paste, and structural formula is shown in figure (21).
Claims (10)
1. a kind of azo structure contained active cationic dye, it is characterised in that there is structure shown in below figure (D)
Wherein：N is 2 to 50 natural number；X is F or Cl atoms；
D is azo structure dyestuff chromogen；
Q is the group containing quaternary ammonium salt structure, such as following formula (a), (b), (c), shown group：
And R1, R2, R3, R4, R5For methyl, ethyl, phenyl, benzyl.
2. azo structure contained active cationic dye according to claim 1, it is characterised in that prepare raw material used
Including hydroxyl or amino azo dispersion dyes, three halo s-triazine, secondary amine compound, mono methoxy polyethylene glycol glycidol
Ether, quaternizing agent.
3. azo structure contained active cationic dye according to claims 1 to 2, it is characterised in that containing amino or hydroxyl
Azo dispersion dyes, wherein, the azo dispersion dyes containing amino or hydroxyl are：Disperse yellow 3, disperse yellow 4, disperse yellow 5, disperse yellow
7th, disperse yellow 10, disperse yellow 23, disperse yellow 50, disperse yellow 56, disperse yellow 60, disperse yellow 70, disperse yellow 76, disperse yellow 79, point
Dissipate Huang 83, disperse yellow 97, disperse yellow 102, disperse yellow 103, disperse yellow 114, disperse yellow 119, disperse yellow 123, disperse yellow 126,
Disperse yellow 134, disperse yellow 165, disperse yellow 199, DISPERSE Yellow 211, disperse yellow 221, disperse yellow 231, disperse yellow 241；Disperse orange
5th, disperse orange 10, disperse orange 13, disperse orange 17, disperse orange 20, disperse orange 21, disperse orange 29, disperse orange 38, disperse orange 42, point
Dissipate orange 66, disperse orange 74, disperse orange 121, disperse orange 138, Red-1 200, disperse red 2, disperse red 220, disperse red 221, scattered
Red 5, disperse red 6, disperse red 8, Red-1 200 2, DISPERSE Red 13, Red-1 200 6, Red-1 200 7, Red-1 200 9, disperse red 30, point
Dissipate red 32, disperse red 43, Disperse Blue 56, disperse red 58, disperse red 64, disperse red 88, disperse red 97, disperse red 98, disperse red
107th, Red-1 200 09, dispersion red 11 8, Red-1 200 26, Red-1 200 28, Red-1 200 29, DISPERSE Red 13 7, Red-1 200 41, point
Dissipate red 151, Red-1 200 56, Red-1 200 57, disperse red 200, disperse red 334, disperse violet 7, disperse violet 12, disperse violet 13, point
Dissipate purple 24, disperse violet 43；Disperse blue 15, disperse blue 38, disperse blue 82, disperse blue 85, disperse blue 90, disperse blue 94, disperse blue
96th, disperse blue 102, disperse blue 122, disperse blue 128, disperse blue 146, disperse blue 264, disperse blue 344；Disperse brown 1: 1, disperse
Palm fibre 4, disperse brown 5, scattered black 4.
4. azo structure contained active cationic dye according to claims 1 to 2, it is characterised in that three halo s-triazine,
Wherein, three halo s-triazine are trichloro-triazine and trifluoro s-triazine.
5. azo structure contained active cationic dye according to claims 1 to 2, it is characterised in that secondary amine compound, its
In, secondary amine compound is dimethylamine, diethylamine, diphenylamines, dibenzylamine, N- methylbenzylamines, methylphenylamine, N, N, N '-front three
Base ethylenediamine, N, N, N '-trimethyl -1,3- propane diamine.
6. azo structure contained active cationic dye according to claims 1 to 2, it is characterised in that the poly- second two of mono methoxy
Alcohol glycidol ether, wherein, mono methoxy polyethylene glycol glycidol ether be methoxy poly (ethylene glycol) (400) glycidol ether,
Methoxy poly (ethylene glycol) (750) glycidol ether, methoxy poly (ethylene glycol) (1000) glycidol ether, methoxy poly (ethylene glycol)
(1500) glycidol ether, methoxy poly (ethylene glycol) (2000) glycidol ether and methoxy poly (ethylene glycol) (2500) glycidol
Ether.
7. azo structure contained active cationic dye according to claims 1 to 2, it is characterised in that quaternizing agent, its
In, quaternizing agent be dimethyl suflfate, dithyl sulfate, dimethyl carbonate, iodomethane, chloromethanes, bromomethane, chloroethanes,
Iodoethane, benzyl chloride, cylite.
A kind of 8. preparation method of azo structure contained active cationic dye as described in claim 1~7, it is characterised in that
Comprise the following steps：
Step 1. by the azo dispersion dyes containing amino or hydroxyl and three halo s-triazine acetone, 1,2- dioxane, acetonitrile,
The in the mixed solvent of tetrahydrofuran, dimethylformamide equal solvent or itself and water is sufficiently stirred, and is adjusted and connect with sodium carbonate or potassium carbonate
PH value of reaction system is 4-6, after -5 DEG C~15 DEG C are reacted 4~9 hours, isolates product.
By secondary amine compound and the abundant compound of methoxy poly (ethylene glycol) glycidol ether, 60~140 DEG C are fully reacted step 2.
3-6 hours, isolate product.
Step 3. mixes the amount of the materials such as product that the product that the 1st step is reacted reacts with the 2nd step, with sodium carbonate, potassium carbonate, hydrogen
Sodium oxide molybdena or potassium hydroxide regulation pH value of reaction system are 4-6, after 30-65 DEG C is reacted 4~9 hours, isolate product, then
The quaternizing agent of certain amount of substance is added, after 60-110 DEG C of reaction 2-8 hour, obtains the azo structure contained cation activity dye of product
Material.
9. the preparation method of azo structure contained active cationic dye according to claim 8, it is characterised in that：
In the step 1, the ratio between amount of substance of three halo s-triazine and azo dispersion dyes chromogen is 1: 1~4: 1；
In the step 1, solvent used is that acetone, 1,2- dioxane, acetonitrile, tetrahydrofuran, dimethylformamide etc. are molten
Agent or its mixed solvent with water；
In the step 1, reaction temperature is -5 DEG C -15 DEG C, and the reaction time is 4-9 hours；
In the step 2, the ratio of secondary amine compound and the amount of the material of methoxy poly (ethylene glycol) glycidyl ether compound is 1: 1
~5: 1；
In the step 2, reaction temperature is 60~140 DEG C, hour in reaction time 3-8；
In the step 3, the amount of the material such as product of product and step 2 reaction that step 1 is reacted；
In the step 3, it is 4-6 that need to adjust pH value of reaction system with sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide；
In the step 3,30-65 DEG C of reaction temperature, the reaction time is after 2~9 hours.
10. the preparation method of azo structure contained active cationic dye according to claim 8, it is characterised in that：Step 1
The described azo dispersion dyes containing amino or hydroxyl be disperse yellow 3, disperse yellow 4, disperse yellow 5, disperse yellow 7, disperse yellow 10, point
Dissipate Huang 23, disperse yellow 50, disperse yellow 56, disperse yellow 60, disperse yellow 70, disperse yellow 76, disperse yellow 79, disperse yellow 83, disperse yellow
97th, disperse yellow 102, disperse yellow 103, disperse yellow 114, disperse yellow 119, disperse yellow 123, disperse yellow 126, disperse yellow 134, scattered
Huang 165, disperse yellow 199, DISPERSE Yellow 211, disperse yellow 221, disperse yellow 231, disperse yellow 241；Disperse orange 5, disperse orange 10, disperse
Orange 13, disperse orange 17, disperse orange 20, disperse orange 21, disperse orange 29, disperse orange 38, disperse orange 42, disperse orange 66, disperse orange 74,
It is disperse orange 121, disperse orange 138, Red-1 200, disperse red 2, disperse red 220, disperse red 221, disperse red 5, disperse red 6, scattered
Red 8, Red-1 200 2, DISPERSE Red 13, Red-1 200 6, Red-1 200 7, Red-1 200 9, disperse red 30, disperse red 32, disperse red 43,
Disperse Blue 56, disperse red 58, disperse red 64, disperse red 88, disperse red 97, disperse red 98, Red-1 200 07, Red-1 200 09, point
Dissipate red 118, Red-1 200 26, Red-1 200 28, Red-1 200 29, DISPERSE Red 13 7, Red-1 200 41, Red-1 200 51, disperse red
156th, Red-1 200 57, disperse red 200, disperse red 334, disperse violet 7, disperse violet 12, disperse violet 13, disperse violet 24, disperse violet
43；Disperse blue 15, disperse blue 38, disperse blue 82, disperse blue 85, disperse blue 90, disperse blue 94, disperse blue 96, disperse blue 102,
Disperse blue 122, disperse blue 128, disperse blue 146, disperse blue 264, disperse blue 344；Disperse brown 1：1st, disperse brown 4, disperse brown 5,
Scattered black 4, three described halo s-triazine are trichloro-triazine and trifluoro s-triazine, and the secondary amine compound described in step 2 is two
Methylamine, diethylamine, diphenylamines, dibenzylamine, N- methylbenzylamines, methylphenylamine, N, N, N '-trimethyl ethylenediamine, N, N, N '-three
Methyl isophthalic acid, 3- propane diamine, described mono methoxy polyethylene glycol glycidol ether are methoxy poly (ethylene glycol) (400) glycidol
Ether, methoxy poly (ethylene glycol) (750) glycidol ether, methoxy poly (ethylene glycol) (1000) glycidol ether, the poly- second two of methoxyl group
Alcohol (1500) glycidol ether, methoxy poly (ethylene glycol) (2000) glycidol ether and methoxy poly (ethylene glycol) (2500) shrink sweet
Oily ether, the quaternizing agent described in step 3 is dimethyl suflfate, dithyl sulfate, dimethyl carbonate, iodomethane, chloromethanes, bromine
Methane, chloroethanes, iodoethane, benzyl chloride, cylite.
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| CN201710593412.4A CN107353671A (en) | 2017-07-17 | 2017-07-17 | A kind of azo structure contained active cationic dye and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109825110A (en) * | 2019-03-29 | 2019-05-31 | 盐城工业职业技术学院 | A kind of weaving active cationic dye and preparation method thereof and tint applications |
| CN109852101A (en) * | 2018-12-30 | 2019-06-07 | 沈阳化工研究院有限公司 | A kind of yellow azo pigments composition and preparation method and application |
| CN109880397A (en) * | 2019-03-26 | 2019-06-14 | 盐城工业职业技术学院 | A kind of dye composition and its preparation method and application |
| CN110387141A (en) * | 2019-07-10 | 2019-10-29 | 东华大学 | A kind of dye matrix is azo cationic reactive dye and its preparation and the application of benzothiazoles |
| CN110776439A (en) * | 2019-11-06 | 2020-02-11 | 蓬莱嘉信染料化工股份有限公司 | Azo compound, preparation method and application thereof, dye composition, dye, preparation method and application thereof |
| CN116640460A (en) * | 2023-06-15 | 2023-08-25 | 中原工学院 | Preparation method and application of reactive disperse dye |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109852101A (en) * | 2018-12-30 | 2019-06-07 | 沈阳化工研究院有限公司 | A kind of yellow azo pigments composition and preparation method and application |
| CN109852101B (en) * | 2018-12-30 | 2020-06-30 | 沈阳化工研究院有限公司 | Yellow azo pigment composition, preparation method and application thereof |
| CN109880397A (en) * | 2019-03-26 | 2019-06-14 | 盐城工业职业技术学院 | A kind of dye composition and its preparation method and application |
| CN109825110A (en) * | 2019-03-29 | 2019-05-31 | 盐城工业职业技术学院 | A kind of weaving active cationic dye and preparation method thereof and tint applications |
| CN110387141A (en) * | 2019-07-10 | 2019-10-29 | 东华大学 | A kind of dye matrix is azo cationic reactive dye and its preparation and the application of benzothiazoles |
| CN110776439A (en) * | 2019-11-06 | 2020-02-11 | 蓬莱嘉信染料化工股份有限公司 | Azo compound, preparation method and application thereof, dye composition, dye, preparation method and application thereof |
| CN110776439B (en) * | 2019-11-06 | 2022-11-01 | 蓬莱嘉信染料化工股份有限公司 | Azo compound, preparation method and application thereof, dye composition, dye, preparation method and application thereof |
| CN116640460A (en) * | 2023-06-15 | 2023-08-25 | 中原工学院 | Preparation method and application of reactive disperse dye |
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