CN107828247B - One kind is suitable for anhydrous woolen dyed disperse dyes of supercritical carbon dioxide and preparation method thereof and colouring method with azo thiazole structure - Google Patents
One kind is suitable for anhydrous woolen dyed disperse dyes of supercritical carbon dioxide and preparation method thereof and colouring method with azo thiazole structure Download PDFInfo
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- CN107828247B CN107828247B CN201710985292.2A CN201710985292A CN107828247B CN 107828247 B CN107828247 B CN 107828247B CN 201710985292 A CN201710985292 A CN 201710985292A CN 107828247 B CN107828247 B CN 107828247B
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- disperse dyes
- compound
- carbon dioxide
- dyeing
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 38
- 239000000986 disperse dye Substances 0.000 title claims abstract description 30
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000004040 coloring Methods 0.000 title abstract description 4
- 239000000975 dye Substances 0.000 claims abstract description 45
- 210000002268 wool Anatomy 0.000 claims abstract description 41
- 238000004043 dyeing Methods 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 239000000835 fiber Substances 0.000 claims description 35
- 239000012954 diazonium Substances 0.000 claims description 30
- 150000001989 diazonium salts Chemical class 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 229960002317 succinimide Drugs 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000006193 diazotization reaction Methods 0.000 claims description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 230000009972 noncorrosive effect Effects 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 14
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 235000010288 sodium nitrite Nutrition 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- -1 azo thiazoles Chemical class 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 102000011782 Keratins Human genes 0.000 description 5
- 108010076876 Keratins Proteins 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 229940126062 Compound A Drugs 0.000 description 4
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OMRXVBREYFZQHU-UHFFFAOYSA-N 2,4-dichloro-1,3,5-triazine Chemical compound ClC1=NC=NC(Cl)=N1 OMRXVBREYFZQHU-UHFFFAOYSA-N 0.000 description 3
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 3
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000001054 cortical effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 2
- ZFMRDDYYJJCBKC-UHFFFAOYSA-N 2-amino-1,3-thiazole-5-carboxylic acid Chemical compound NC1=NC=C(C(O)=O)S1 ZFMRDDYYJJCBKC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001494479 Pecora Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 2
- 235000018417 cysteine Nutrition 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- ZIRGWUZHKJDYKT-UHFFFAOYSA-N 1,3-thiazole-2-carbonitrile Chemical compound N#CC1=NC=CS1 ZIRGWUZHKJDYKT-UHFFFAOYSA-N 0.000 description 1
- HIMMCCJEMMCUJS-UHFFFAOYSA-N 4-fluorotriazine Chemical compound FC1=CC=NN=N1 HIMMCCJEMMCUJS-UHFFFAOYSA-N 0.000 description 1
- HCXJFMDOHDNDCC-UHFFFAOYSA-N 5-$l^{1}-oxidanyl-3,4-dihydropyrrol-2-one Chemical group O=C1CCC(=O)[N]1 HCXJFMDOHDNDCC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- XYQYTXDJSYHZAQ-UHFFFAOYSA-N N1=CN=CN=C1.[F] Chemical compound N1=CN=CN=C1.[F] XYQYTXDJSYHZAQ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 125000000539 amino acid group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004044 disperse dyeing Methods 0.000 description 1
- 238000009973 dope dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000010792 warming Methods 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/008—Preparations of disperse dyes or solvent dyes
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
- C09B29/0074—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms
- C09B29/0077—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms containing a five-membered heterocyclic ring with one nitrogen and one sulfur as heteroatoms
- C09B29/0085—Thiazoles or condensed thiazoles
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
-
- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0079—Azoic dyestuff preparations
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
- D06P1/18—Azo dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/94—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in solvents which are in the supercritical state
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
- D06P3/143—Wool using dispersed dyes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Coloring (AREA)
Abstract
The present invention provides one kind and is suitable for the anhydrous woolen dyed disperse dyes of supercritical carbon dioxide, preparation method and colouring method, the dyestuff, the structure with general formula I with azo thiazole structure.It is anhydrous woolen dyed that such dyestuff can be used for supercritical carbon dioxide, this kind of compound is in supercritical carbon dioxide with the dissolubility of certain level, simultaneously using in active group and wool amino or hydroxyl chemically reacted, reaction product is non-corrosive to supercritical CO 2 dyeing device.In general formula I: m, n are respectively integer；X, Y are respectively and independently selected from as-H ,-CN ,-CH3O ,-COOCH3OrR0Selected from R1、R2Or R3；Ar is selected from Ar1；
Description
Technical field
The present invention relates to dyestuff chemistry technical fields, and in particular to one kind have azo thiazole structure be suitable for it is overcritical
Anhydrous woolen dyed disperse dyes of carbon dioxide and preparation method thereof and colouring method.
Background technique
Carbon dioxide (CO2), a kind of main greenhouse gases, because it is as a kind of main source of climate change, therefore
And carbon dioxide becomes the focus of scientific attention.Under potential economic benefit and environmental benefit, more effective way is needed
To stablize and using the carbon dioxide in atmosphere or from industrial discharge, when temperature and pressure is more than certain temperature and pressure
(i.e. 31.10 DEG C, 7.39MPa) afterwards, CO when reaching the temperature and pressure2Become above-critical state, supercritical CO2In addition to toxicity is low,
Outside the advantages that viscosity is lower, he also has high diffusivity and penetrating power, therefore supercritical CO2It is a kind of with important benefit
With the commercial and industrial solvent of value.
Since Schollmeyer in 1988 is introduced into supercritical carbon dioxide as green solvent in dope dyeing,
Supercritical carbon dioxide waterless staining technique is just widely deployed in field of textiles.Compared with traditional water dye, supercritical CO2It is anhydrous
Dyeing can overcome traditional water to contaminate relevant all economic disadvantages with ecology, supercritical CO2Use greatly reduce making for water
With and energy consumption.Currently, with disperse dyes in supercritical CO2In very big progress has been obtained to chemical fibers dyeing, and
Dyestuff is modified using a variety of methods, modified dyestuff can dye natural fabric (such as cotton, hair).It is the most frequently used
Method be based on natural fiber it is traditional water dye dyeing mechanism, by disperse dyes group introduce active group (chlorine is equal
Triazine, dichloro s-triazine, fluorine s-triazine etc.) design synthesizing new reactive disperse dyes.Such as professor seminar, imperial PCI-SLR Technology sets
Meter synthesized three dichloro s-triazine types reactive disperse dyes (Journal of Cleaner Production, 2016,
133:746-756. molecular structure is as follows)；M.V.Fernandez Cid et al. devises fluorotriazine activity point
It dissipates dyestuff (Green Chemistry, 2005,7 (8): 609-616. molecular structure is as follows)；A.Schmidt et al. is also set
Having counted dichloro s-triazine type type reactive disperse dyes, (Dyes and Pigments, 2003,56 (1): 27-35. molecular structure is such as
Shown in lower), they are respectively by these applications in the dyeing of natural fiber.As can be seen that being suitable for from document report
The dyestuff of supercritical carbon dioxide natural fiber dyeing has achieved some successes, but these dyestuffs still have some lack
Point.For example, being carried out according to reaction principle using between the active group of disperse dyes and the hydroxyl of natural fiber and amino
SNAr reaction.However, the by-product of these reactions is mainly HCl, HF, both products have high corrosion to dyeing installation
Property.
The molecular structure of several reactive disperse dyes being reported
Wool fiber is important natural protein fibre, such as elastic, warming, anti-since it is with excellent characteristic
Electrostatic and dirt-removing power, highest attention of the wool by customers.As keratin fiber, wool is a kind of hemicrystalline
Hmw protein forms by 18 kinds with upper amino acid, therefore amino acid residue is arranged in the polymer chain of wool, molecule
It is played an important role in terms of the formation of cohesiveness and intramolecular disulfide bond.It is woolen dyed main in traditional water dyeing technique
Using acid dyes, mordant dyes and reactive dye three categories, however, these dyestuffs are in supercritical CO2In extremely not
It is molten, therefore dispersion class dye derivate is studied in supercritical CO2In have great importance to woolen dyed.
Summary of the invention
The limitation of technology based on the above background, the application propose that some new disperse dyes can be in supercritical carbon dioxide
In natural wool fiber is dyed, keep its coloration result good, degree of fixation is up to state standards, while dyestuff and fiber
Product after acting on fixation equips no corrosivity to dyeing.
In the first aspect of the present invention, the present invention is directed to the existing reactive disperse dyes for natural fiber not
Foot, provides a type disperse dye, has having structure general formula I:
In general formula I:
M, n is respectively integer；
X, Y are respectively and independently selected from as-H ,-CN ,-CH3O ,-COOCH3Or
R0Selected from R1、R2Or R3；
Ar is selected from Ar1；
Disperse dyes with above structure general formula I can be used for wool and dye in supercritical carbon dioxide, in embodiment
The application of dyestuff is listed, experimental result shows that such compound has good dissolubility in supercritical carbon dioxide, this
This kind of compound while also active group of invention, can be improved the binding ability of dyestuff and wool fiber, to improve dye
The degree of fixation of color.
Another aspect is designed to provide dye composite, the conjugation comprising above-mentioned disperse dyes or the disperse dyes
Object.
Another further aspect is designed to provide above-mentioned dyestuff or dye composite answering in supercritical CO 2 dyeing
With.
Preferably, for the dyeing of natural fiber.
It is highly preferred that the natural fiber is wool fiber.
The present invention also provides a kind of methods for preparing above-mentioned dyestuff, the described method comprises the following steps:
(1) compound II or compound III and diazotization agent carry out diazo-reaction, obtain diazonium salt II or diazonium salt respectively
III；
(2) diazonium salt II or diazonium salt III and compound iv carries out coupling reaction, obtains product IV respectively or intermediate produces
Object V；
(3) using midbody product V as raw material, under conditions of activated carboxylic catalysts, be added succinimide or
Maleimide reacts 1~24 hour, and pillar layer separation obtains product VI or product VII respectively；
Activated carboxylic catalysts of the present invention are preferably but not limited to dicyclohexylcarbodiimide and 4- dimethylamino
At least one of pyridine.
Preferably, in the step (2) and (3), the solvent used in the reaction is water, methylene chloride, chloroform, second
At least one of alcohol, methanol, acetonitrile, ethyl acetate, toluene, dimethylbenzene, o-dichlorobenzene or concentrated sulfuric acid.
The present invention also provides a kind of methods that supercritical carbon dioxide is woolen dyed, including by above-mentioned disperse dyes or dyestuff
Composition is used for woolen dyed step.
Disperse dyes of the present invention have following characteristics:
The molecular structure of compounds is simple, and molecular weight is small, and dissolubility is good in supercritical carbon dioxide；
Contain the thiazole structure insensitive to light in the molecular structure of compounds, therefore compound has excellent light steady
It is qualitative, applied to after textile dyeing have low photobleaching；
Containing the active group that can be reacted with amino in wool or hydroxyl in the molecular structure of compounds, sheep is improved
Various color fastness after wool textile dyeing；
No longer there is product after the compound molecule is reacted with amino in wool or hydroxyl traditional activated dispersion to contaminate
The corrosive gas molecule that material generates after reacting with hydroxyl in wool or amino, i.e., the product after being reacted with the compound
It is more environmental-friendly；
The noval chemical compound product side effect is small, and raw material is easy to get, and structure is simple, easily prepared, and easy industrialization passes through 2 steps
It can be obtained to the reaction of 3 steps.
These features of the invention and advantage and other feature and advantage will be shown after reference following specific embodiments
And it is clear to.
In consideration of it, azo thiazoles reactive disperse dyes of the present invention can be applied to the anhydrous sheep of supercritical carbon dioxide
In wool dyeing.
The deficiency and active dispersal of poor color fastness when being dyed present invention improves over existing disperse dyes for wool fiber
The shortcomings that corrosion dyeing apparatus by-product is generated after dyeing designs and synthesizes out and is suitable for overcritical dioxy carbon wool original
The dyestuff of position dyeing, introduces the active group that can be reacted with groups such as the amino of wool fiber, sulfydryls, these active groups
Group includes isothiocyanates group, succinimide group and maleimide base group, and active group and amino, mercapto
Base will not be generated after having reacted corrosion device gas and by-product (by-product be urea, succinimide or maleimide,
These three types of substances energy non-corrosive to dyeing apparatus), and the effect between dyestuff and wool fiber can also be increased.Such point
Scattered dyestuff small, good light stability with molecular polarity.In addition, supercritical carbon dioxide can be depressurized to after the completion of woolen dyed
Room temperature, carbon dioxide can be utilized by storage again.
The surface of wool is very different with typical synthetic fibers and other natural fibers.On the one hand, wool itself
It is made of being divided as blastema, the structure type of cell composition is broadly divided into two kinds, including scale layer and cortical layer.Squama
Contain about 12% cysteine in lamella, it has very strong hydrophobicity, prevents the attack of chemical reagent and enzyme.Scale layer
Surface alignment at one layer of monoester layer structure, non-polar group arrange outward make wool surfaces layer have hydrophobicity.Meanwhile
Cortical layer containing about 35% cysteine also contributes the hydrophobicity effect of wool, therefore the hydrophobicity of cortical layer improves
Affinity between wool and carbon dioxide, to make wool in supercritical CO2It is possibly realized with disperse dyeing.
Under supercritical carbon dioxide high-temperature and high-pressure conditions, the S -- S in wool fiber keratin is broken, after fracture
Sulfydryl is exposed, exposed sulfydryl can form weak S -- S, thus increase with the S effect in azo thiazoles dyestuff
Effect between dyestuff and wool fiber, meanwhile, the azo structure in dyestuff can be in the hydrophobic cavity of wool keratin
It rotates freely, which increases the effects of keratin in dyestuff and wool fiber.Therefore, containing the azo dyes of thiazole structure
Wool can be dyed in supercritical carbon dioxide.Active group isothiocyanate group and succinimido can be with
Exposed NH in keratin2It is reacted, it is shown that the reaction mechanism is as follows:
Active group dimaleoyl imino can be in supercritical CO2Weak acid environment under and the sulfydryl that exposes of keratin
It is reacted, it is shown that the reaction mechanism is as follows:
According to the above reaction mechanism, achieve the effect that improve fixation efficiency.
Specific embodiment
Disperse dyes of the present invention, the structure with following general formula I:
Unless otherwise stated, term used herein has following meanings.
R0Selected from R1、R2Or R3；
R1、R2And R3Respectively isothiocyanate group, succinamide ester group and maleimide ester group.
Ar is selected from Ar1；Ar1For thiazole.
X, Y are respectively and independently selected from-H ,-CN ,-CH3O ,-COOCH3Or
The m is integer, and preferably m is the integer of 1-18；
The n is integer, and preferably n is the integer of 1-18.
Another aspect of the present invention provides the preparation method of the disperse dyes, it may be assumed that it is a variety of first to prepare thiazolamine respectively
The diazonium salt (compound II or compound III) of aniline category matter, then by compound II or compound III respectively with chemical combination
Coupling reaction obtains product to object iv under alkaline condition, and specific synthetic schemes is as described below:
(1) by compound ii or compound iii vitriolization and phosphoric acid solution, ice salt bath control mixeding liquid temperature be-
5~5 DEG C.Sodium nitrite is weighed, it is soluble in water, sodium nitrite in aqueous solution is slowly added dropwise to above compound ii or compound
In the mixed liquor of iii and acid, it is -5~0 DEG C that temperature is kept during being added dropwise, and is kept stirring, and is reacted 0.1~48 hour or so,
The nearly colourless solution of light red is obtained, reaction system is examined with starch-kalium iodide test paper, test paper becomes blue, indicate that reaction is completed,
Obtain diazonium salt II or diazonium salt III.
Reaction temperature is -5~5 DEG C, and the reaction time is 1~48 hour；
Compound ii or compound iii and sulfuric acid press 1:5~1:30 molar ratio, sulfuric acid and phosphoric acid and press 1:1~1:1.5 moles
Than feeding intake,
The concentration of aqueous sulfuric acid is 3~18.4mol/L；
The concentration of phosphate aqueous solution is 15mol/L~20mol/L,
The concentration of the sodium nitrite in aqueous solution is 0.1mol/L~2mol/L.
In one preferred embodiment, reaction temperature is -5~4 DEG C, and the reaction time is 3~40 hours；
In a preferred embodiment, reaction temperature is -5~2 DEG C, and the reaction time is 2~30 hours；
In most preferred embodiments, reaction temperature is -5~0 DEG C, and the reaction time is 1~24 hour.
(2) it is soluble in water to weigh aniline category matter (compound iv), it is soluble in water to weigh sodium hydroxide, controls under ice salt bath
Then the aqueous solution of the two is uniformly mixed by reaction temperature processed, keeping temperature of reaction system is -15~20 DEG C, then to reaction
Diazonium salt made from step (1) (II or III) solution is slowly added dropwise in system, by IV and diazonium salt II or III moles of diazonium salt
The reaction was continued after being added dropwise to complete for 1:1~20, under low temperature 1~24 hour, and filtering removes insoluble atrament, then uses
The pH that hydrochloric acid adjusts reaction system is 1~14, filters precipitate, is washed to neutrality, separates to obtain solid (product IV or intermediate
Product V).
With molar ratio computing, compound IV: sodium hydroxide=1:5~1:15；
The concentration of the aqueous solution of the compound IV is 0.1mol/L, and the concentration of the sodium hydroxide solution is 2mol/L.
Compound IV and the molar ratio of diazonium salt II or diazonium salt III are 1:1~20.
Reaction temperature is -10~10 DEG C, and the reaction time is 4~20 hours, compound iv and diazonium salt (II or III)
Molar ratio is 1:1~20, and pH is 2~10；
In one preferred embodiment, reaction temperature is -10~5 DEG C, and the reaction time is 3~15 hours, compound
The molar ratio of iv and diazonium salt (II or III) are 1:3~15, and pH is 3~9；
In a preferred embodiment, reaction temperature is -10~0 DEG C, and the reaction time is 2~10 hours, chemical combination
The molar ratio of object iv and diazonium salt (II or III) are 1:3~10, and pH is 4~8；
In most preferred embodiments, reaction temperature be -5~0 DEG C, the reaction time be 1~5 hour, compound iv with
The molar ratio of diazonium salt (II or III) is 1:3~5, and pH is 5~7.
(3) using compound V as raw material dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP) according to
It is catalyzed reaction under the conditions of molar ratio rate 1:1~30, is added succinimide or maleimide, reaction temperature is 10~
Under the conditions of 200 DEG C, react 1~48 hour, pillar layer separation obtains Formula IV and VII.
Reaction temperature be 50~180 DEG C, the reaction time be 4~48 hours, reaction dissolvent be selected from methylene chloride, chloroform,
Or mixtures thereof ethyl alcohol, methanol, acetonitrile, ethyl acetate, toluene, dimethylbenzene, o-dichlorobenzene, compound V and succinimide
Or the molar ratio of maleimide is 1:1~30；
In preferred embodiment, reaction temperature is 60~160 DEG C, and the reaction time is 3~36 hours, reaction dissolvent choosing
From or mixtures thereof methylene chloride, ethyl alcohol, methanol, acetonitrile, ethyl acetate, toluene, dimethylbenzene, o-dichlorobenzene, compound V with
The molar ratio of succinimide or maleimide is 1:1~20；
In further preferred embodiment, reaction temperature is 70~140 DEG C, and the reaction time is 2~24 hours, reaction
Solvent is selected from or mixtures thereof methylene chloride, methanol, acetonitrile, ethyl acetate, compound V and succinimide or maleimide
The molar ratio of amine is 1:2~10；
In most preferred embodiment, reaction temperature is 80~90 DEG C, and the reaction time is 1~12 hour, reaction dissolvent choosing
From methylene chloride, compound V is 1:3~5 with the molar ratio of succinimide or maleimide.
In the description of the above-mentioned preparation method to disperse dyes of the present invention, the definition of each substituent group and preferably, and this
In invention in the description of compound definition and preferably it is identical.
To the present invention using the disperse dye compound of above method synthesis, confirmed using nmr spectrum or mass spectrum
Its structure, and it is aided with carbon spectrum, mass spectrometric measurement to assist confirming its structure.
The embodiment of the present invention carries out the detection of fastness to soaping and color fastness to light to the wool fiber after dyeing, wherein
Fastness to soaping is according to GB/T 3921-2008 " textile color stability test fastness to soaping " standard, light shine color jail
Degree is according to GB/T 14576-2009 " textile color stability tests fast light, the compound color fastness of sweat " standard.
Embodiment 1 prepares azo thiazoles dye composition A1
It prepares 5- isothiocyanates-thiazolamine: the triphosgene of 0.4eq is dissolved in dimethyl carbonate solvent, it is cooling
It, then will be in addition dissolved with the thiazolamine of 0.4eq, 2eq triethylamine and 0.1eq catalytic amount DMAP (4- dimethylamino to 0 DEG C
Pyridine) dimethyl carbonate be added drop-wise in the triphosgene solution of above-mentioned cooling.It drips off and reacts what half an hour production needed at 0 DEG C
5- isothiocyanates-thiazolamine.The product is unpurified directly to carry out next step reaction.
(1) synthesis of diazonium salt 1
5- isocyanates -2- the cyano thiazole (1.5722g, 0.01mol) of preparation is dissolved in 50mL sulfuric acid (3~18.4mol
/ L) and 80mL phosphoric acid (85%) mixed solution in, be added in the 500mL three neck round bottom flask with blender, ice salt bath control
Mixeding liquid temperature processed is -5~0 DEG C.Sodium nitrite (3.449g, 0.05mol) is weighed, is dissolved in 100mL water, by sodium nitrite
Aqueous solution is slowly added dropwise into aniline category matter and sulfuric acid and phosphoric acid mixed liquor, and it is -5~0 DEG C that temperature is kept during being added dropwise,
It is kept stirring, reacts 5.5 hours or so, obtain the nearly colourless solution of light red, reaction system is examined with starch-kalium iodide test paper,
Test paper becomes blue, indicates that reaction is completed, obtains diazonium salt 1.Diazonium salt 1 is without purifying, directly progress next step reaction.
(2) compound A1Synthesis
By N, N- diethylaniline (1.49g, 0.01mol) is dissolved in 100mL water, weighs sodium hydroxide (4g, 0.1mol)
It is dissolved in 50mL water, reaction temperature -5~0 DEG C is controlled under ice salt bath, is then uniformly mixed the aqueous solution of the two, keep reaction
System temperature is -5~0 DEG C, and diazonium salt 1 made from step (1) is then slowly added dropwise into reaction system.It is low after being added dropwise to complete
Temperature is lower, and the reaction was continued 3 hours, and filtering removes insoluble atrament, is then 5~7 with the pH that hydrochloric acid adjusts reaction system, mistake
Precipitate is filtered, is washed to neutrality, pillar layer separation obtains solid A1。1H NMR(400MHz,CHCl3-d)δ8.54(s,1H),7.92–
7.85 (m, 2H), 6.94-6.88 (m, 2H), 3.29 (q, J=8.0Hz, 4H), 1.10 (t, J=8.0Hz, 6H)13C NMR
(100MHz,CHCl3-d)δ175.78,172.79, 150.03,144.53,142.18,141.11,125.64,110.48,
44.99,12.44.(ESI+Tof)m/z Found 318.08 M+1,calculated 317.08for C14H15N5S2。
Embodiment 2 prepares azo thiazoles dye composition A2
(1) synthesis of diazonium salt 2
5- carboxyl-thiazolamine (1.4415g, 0.01mol are purchased from lark prestige chemical reagents corporation) is dissolved in 50mL
In sulfuric acid (3~18.4mol/L) and 80mL phosphoric acid (15mol/L) mixed solution, it is added to tri- mouthfuls of 500mL with blender
In round-bottomed flask, it is -5~0 DEG C that ice salt bath, which controls mixeding liquid temperature,.Sodium nitrite (2.4871g, 0.01mol) is weighed, is dissolved in
In 100mL water, sodium nitrite in aqueous solution is slowly added dropwise into 5- carboxyl-thiazolamine and sulfuric acid and phosphoric acid mixed liquor, is dripped
It is -5~0 DEG C that temperature is kept during adding, and is kept stirring, and reacts 5.0 hours or so, light red solution is obtained, with starch-iodine
Change potassium test paper and examine reaction system, test paper becomes blue, indicates that reaction is completed, obtains diazonium salt 2.Diazonium salt 2 is without purifying, directly
Carry out next step reaction.
(2) synthesis of midbody product 2 '
By N, N- diethylaniline (1.49g, 0.01mol) is dissolved in 100mL water, weighs sodium hydroxide (4g, 0.1 mol)
It is dissolved in 50mL water, reaction temperature -5~0 DEG C is controlled under ice salt bath, is then uniformly mixed the aqueous solution of the two, keep reaction
System temperature is -5~0 DEG C, and diazonium salt 2 made from step (1) is then slowly added dropwise into reaction system.It is low after being added dropwise to complete
Temperature is lower, and the reaction was continued 3 hours, and filtering removes insoluble atrament, is then 5~7 with the pH that hydrochloric acid adjusts reaction system, mistake
Precipitate is filtered, is washed to neutrality, pillar layer separation obtains midbody product 2 '.
(3) compound A2Synthesis
With above-mentioned midbody product 2 ' (0.304g, 0.001mol) be raw material, DCC (dicyclohexylcarbodiimide,
0.206g, 0.001mol) and DMAP (4-dimethylaminopyridine, 0.123g, 0.001mol) under the conditions of, be added N- bromo amber
Acid imide (3.6000g, 0.02mol) reacts 3 hours, and pillar layer separation obtains formula A2。1H NMR(500MHz, Chloroform-
D) δ 8.71 (s, 1H), 7.96-7.70 (m, 2H), 6.93-6.63 (m, 2H), 3.29 (q, J=8.0Hz, 4H), 2.80 (s,
4H), 1.10 (t, J=8.0Hz, 6H)13C NMR(100MHz,Chloroform-d)δ175.82, 169.11,157.65,
150.52,150.03,142.18,127.58,125.64,110.48,44.99,25.68,12.44. (ESI+Tof)m/z
Found 402.44M+1,calculated 401.44for C19H19N5O4S。
Embodiment 3 prepares azo thiazoles dye composition A3
(1) synthesis of diazonium salt 2
Synthetic method is same as Example 2.
(2) synthesis of midbody product 2 '
By N, N- diethylaniline (1.49g, 0.01mol) is dissolved in 100mL water, weighs sodium hydroxide (4g, 0.1mol)
It is dissolved in 50mL water, reaction temperature -5~0 DEG C is controlled under ice salt bath, is then uniformly mixed the aqueous solution of the two, keep reaction
System temperature is -5~0 DEG C, and diazonium salt 2 made from step (1) is then slowly added dropwise into reaction system.It is low after being added dropwise to complete
Temperature is lower, and the reaction was continued 3 hours, and filtering removes insoluble atrament, is then 5~7 with the pH that hydrochloric acid adjusts reaction system, mistake
Precipitate is filtered, is washed to neutrality, pillar layer separation obtains midbody product 2 '.
(3) product A3Synthesis
With above-mentioned midbody product 2 ' for raw material, in DCC (dicyclohexylcarbodiimide, 2.06g, 0.01mol) and DMAP
It under the conditions of (4-dimethylaminopyridine, 1.23g, 0.01mol), is added maleimide (3.6000g, 0.02mol), reaction 3 is small
When, pillar layer separation obtains formula A3。1H NMR(400MHz,CHCl3-d)δ7.85–7.78(m,1H), 7.07(s,1H),6.78–
6.72 (m, 1H), 3.29 (q, J=8.0Hz, 2H), 1.10 (t, J=8.0Hz, 3H)13C NMR(100MHz,CHCl3-d)δ
175.82,167.44,157.65,150.52,150.03,142.18,132.05, 127.58,125.64,110.48,44.99,
12.44.(ESI+Tof)m/z Found 400.10M+1,calculated 399.10 for C19H17N5O4S。
Embodiment 4
Using supercritical carbon dioxide non-aqueous dyeing device disclosed in Chinese invention patent ZL200510136782.2 and
The compound A that embodiment 1 synthesizes1Carry out the dyeing of wool fiber.Compound A has been determined1Dyestuff is overcritical for wool fiber
CO2The optimum process condition of dyeing are as follows: fluid flow rate 30g/min, 100 mesh of dye particle size dye pressure 25MPa, dyeing temperature
120 DEG C, dyeing time 120min.Experimental result shows that the fastness to soaping and light shine color fastness of dyeing wool fiber divide
It not can achieve 4-5 grades and 5 grades.
Embodiment 5
Using the compound A of equipment same as Example 4 and experiment synthesis2Carry out having determined of dyeing of wool fiber
Close object A2Dyestuff is used for wool fiber supercritical CO2The optimum process condition of dyeing are as follows: fluid flow rate 25g/min, dye particle size
100 mesh, dye pressure 25MPa, 120 DEG C of dyeing temperature, dyeing time 120min.And the resistance to color jail of soaping of dyeing wool fiber
Degree and light shine color fastness can achieve 4-5 grades and 5 grades respectively.
Embodiment 6
Using the compound A of equipment same as Example 4 and experiment synthesis3Carry out the dyeing of wool fiber.It has determined
Compound A3Dyestuff is used for wool fiber supercritical CO2The optimum process condition of dyeing are as follows: fluid flow rate 25g/min, dyestuff grain
It spends 80 mesh, dyes pressure 25MPa, 120 DEG C of dyeing temperature, dyeing time 150min.And the resistance to color jail of soaping of dyeing wool fiber
Degree and light shine color fastness can achieve 4-5 grades respectively.
The above description is merely a specific embodiment, but protection scope of the present invention be not limited to it is above
Embodiment, anyone skilled in the art within the technical scope disclosed by the invention, can be without creative works
The change or replacement expected, should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with
Subject to protection scope defined by claims.
Claims (8)
1. a type disperse dye, the structure with general formula I:
In general formula I:
M, n is respectively integer；M is the integer of 1-18；N is the integer of 1-18；
X, Y are respectively and independently selected from as-H ,-CN ,-CH3O ,-COOCH3Or
R0Selected from R1、R2Or R3；
Ar is selected from Ar1；
。
2. dye composite, the conjugate comprising disperse dyes described in claim 1 or the disperse dyes.
3. application of the dye composite described in dyestuff or claim 2 described in claim 1 in supercritical CO 2 dyeing.
4. application according to claim 3, which is characterized in that the dyeing for natural fiber.
5. application according to claim 4, which is characterized in that the natural fiber is wool fiber.
6. the preparation method of disperse dyes described in claim 1, includes the following steps:
(1) compound II or compound III and diazotization agent carry out diazo-reaction, obtain diazonium salt II or diazonium salt III respectively；
(2) diazonium salt II or diazonium salt III and compound iv carries out coupling reaction, obtains product IV or midbody product V respectively；
(3) using midbody product V as raw material, under conditions of activated carboxylic catalysts, succinimide or Malaysia is added
Acid imide reacts 1~24 hour, and pillar layer separation obtains product VI or product VII respectively；
。
7. preparation method according to claim 6, which is characterized in that in the step (2) and (3), used in the reaction
The solvent arrived is water, methylene chloride, chloroform, ethyl alcohol, methanol, acetonitrile, ethyl acetate, toluene, dimethylbenzene, o-dichlorobenzene or dense
At least one of sulfuric acid.
8. a kind of method that supercritical carbon dioxide is woolen dyed, including disperse dyes described in claim 1 or right are wanted
Dye composite described in asking 2 is used for woolen dyed step.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982508A (en) * | 2010-08-24 | 2011-03-02 | 浙江理工大学 | Carboxylic ester type disperse dye capable of being washed by alkali and preparation method thereof |
| CN103031756A (en) * | 2012-12-20 | 2013-04-10 | 中国科学院福建物质结构研究所 | Method for dyeing pure cotton fiber |
| CN106497139A (en) * | 2016-08-31 | 2017-03-15 | 沈阳化工研究院有限公司 | A kind of supercritical CO2With vinyl-sulfone reactive disperse dyes and its preparation method and application |
| CN106928745A (en) * | 2017-01-26 | 2017-07-07 | 浙江龙盛化工研究有限公司 | The bright blue dye composition of one kind dispersion, dye composite and its application |
-
2017
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982508A (en) * | 2010-08-24 | 2011-03-02 | 浙江理工大学 | Carboxylic ester type disperse dye capable of being washed by alkali and preparation method thereof |
| CN103031756A (en) * | 2012-12-20 | 2013-04-10 | 中国科学院福建物质结构研究所 | Method for dyeing pure cotton fiber |
| CN106497139A (en) * | 2016-08-31 | 2017-03-15 | 沈阳化工研究院有限公司 | A kind of supercritical CO2With vinyl-sulfone reactive disperse dyes and its preparation method and application |
| CN106928745A (en) * | 2017-01-26 | 2017-07-07 | 浙江龙盛化工研究有限公司 | The bright blue dye composition of one kind dispersion, dye composite and its application |
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