CN109679366A - Anthraquinone type carboxylate disperse dyes and preparation method thereof - Google Patents
Anthraquinone type carboxylate disperse dyes and preparation method thereof Download PDFInfo
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- CN109679366A CN109679366A CN201811610069.0A CN201811610069A CN109679366A CN 109679366 A CN109679366 A CN 109679366A CN 201811610069 A CN201811610069 A CN 201811610069A CN 109679366 A CN109679366 A CN 109679366A
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- Prior art keywords
- disperse dyes
- anthraquinone type
- carboxylate
- preparation
- type carboxylate
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Links
- 150000007942 carboxylates Chemical class 0.000 title claims abstract description 44
- 239000000986 disperse dye Substances 0.000 title claims abstract description 41
- 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 title claims abstract description 37
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000975 dye Substances 0.000 claims abstract description 46
- -1 normal-butyl Chemical group 0.000 claims abstract description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims abstract description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims abstract description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 7
- CAHGWVAXFJXDNI-UHFFFAOYSA-N 1,4-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(Cl)=CC=C2Cl CAHGWVAXFJXDNI-UHFFFAOYSA-N 0.000 claims description 6
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 4
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 150000005165 hydroxybenzoic acids Chemical class 0.000 claims description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 claims description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 12
- 238000004140 cleaning Methods 0.000 abstract description 12
- 239000000835 fiber Substances 0.000 abstract description 6
- 229920000728 polyester Polymers 0.000 abstract description 3
- 238000000859 sublimation Methods 0.000 abstract description 3
- 230000008022 sublimation Effects 0.000 abstract description 3
- 238000004043 dyeing Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000004744 fabric Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical class [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 229960004756 ethanol Drugs 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 229920004933 Terylene® Polymers 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- ZSPPPAFDNHYXNW-UHFFFAOYSA-N 3-[n-ethyl-4-[(4-nitrophenyl)diazenyl]anilino]propanenitrile Chemical compound C1=CC(N(CCC#N)CC)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1 ZSPPPAFDNHYXNW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- TVRGPOFMYCMNRB-UHFFFAOYSA-N quinizarine green ss Chemical compound C1=CC(C)=CC=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1 TVRGPOFMYCMNRB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 231100001231 less toxic Toxicity 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004044 disperse dyeing Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 231100000175 potential carcinogenicity Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009941 weaving 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
- C09B1/32—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/02—Hydroxy-anthraquinones; Ethers or esters thereof
- C09B1/06—Preparation from starting materials already containing the anthracene nucleus
- C09B1/14—Dyes containing ether groups
-
- 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
- D06P1/20—Anthraquinone 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
- 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
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
The invention discloses a kind of anthraquinone type carboxylate disperse dyes, contain carboxylate group, general structure in molecular structure are as follows:
Description
Technical field
The present invention relates to a kind of anthraquinone type carboxylate disperse dyes and preparation method thereof.
Background technique
Yield the first in the world of China's disperse dyes, but the generally existing kind of dyestuff manufacturing enterprise is outmoded at present, technology
The problems such as falling behind, causes the profit margin of domestic disperse dyes relatively low, and the continuous increase of environmental protection pressure simultaneously, so that entire weaving
The development of industry is faced adverse conditions.It develops novel high fastness dyestuff and promotes existing DYE PRODUCTION technology, the technology for increasing dyestuff contains
Amount will be the only way of dye industry development.Develop low dirty type dye, reduces dyestuff manufacture, application, has in last handling process
The use of evil chemicals, fundamentally solve that dyeing waste water toxicity is big and COD, BOD it is abnormal it is high, the industries such as to be difficult to handle difficult
Topic is the most important thing of dyestuff manufacture and dyeing future development.
Conventional dyes manufacturing enterprise inevitably generates the three wastes (waste water, waste residue, exhaust gas) in production, use process.
Disperse dyes used in currently on the market are after dyeing, it is necessary to fabric surface loose colour are removed by reduction cleaning, to improve fabric
Every color fastness.Due to using a large amount of sodium hydrosulfites and the higher strong base solution of concentration during reduction cleaning, treated also
There is the unreacted sodium hydrosulfite of high concentration, sodium hydroxide and arylamine chemical combination with potential carcinogenicity or mutagenicity in stoste
Object, these waste water, which are discharged into rivers, to be caused seriously to pollute to water body.In addition, sodium hydrosulfite is also deposited in storage and use process
Spontaneous combustion is easy after security risk, the sodium hydrosulfite moisture absorption, there are fire hazards；A large amount of irritations can be also escaped in use
Gas aggravates environmental pollution, harm health.
Application No. is the invention of 201510523507X " heterocycles can alkali cleaning carboxylic acid, ethyl ester type disperse dyes and preparation method thereof "
The commodity disperse dyes for choosing existing cyano-containing are raw material, convert carboxylate for cyano using alcoholysis method this unit process
Base, although this method is one-step method, converts carboxylate for the cyano in dyestuff so that carboxylic acid ester type disperse dyes be made
Not only reaction condition is more harsh, but also will cause the decline (generally resulting in 1-2 grades of decline) of sunlight fastness, deteriorates dyestuff
Certain application performances.
Using the C.I. disperse orange 25 containing cyano as raw material, dehydrated alcohol is solvent and reactant, and the concentrated sulfuric acid is catalyst,
Carboxylic acid ester type azo dispersion dyes D1 is made using cyano alcoholysis reaction.
C.I. disperse orange 25 and D1 respectively through sand milling and to dyeing terylene after, the dyed fabric of acquisition uses national standard
" textile color stability tests color fastness to light daylight " (GB/T 8426-1998) measures color fastness to light, C.I. disperse orange 25 dye
The color fastness to light of painting cloth sample is 6 grades, and the color fastness to light that D1 dyes cloth specimen is 4-5 grades.It can be seen that cyano is replaced by ester group
Deteriorate the color fastness to light performance of dyestuff.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of anthraquinone type carboxylate disperse dyes and preparation method thereof, this points
Dissipating dyestuff has dye-uptake height, good color fastness when being applied to dyeing terylene, has easy alkali cleaning in post-processing, exempts from sodium hydrosulfite etc.
Feature.
In order to solve the above technical problem, the present invention provides a kind of anthraquinone type carboxylate disperse dyes, in molecular structure
Containing carboxylate group, general structure is as follows:
In formula: R is ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, n-hexyl etc.；X is NH or O.
As the further improvement of anthraquinone type carboxylate disperse dyes of the invention, the structural formula of the disperse dyes is following
It is any:
The present invention goes back while providing the preparation method of above-mentioned anthraquinone type carboxylate disperse dyes, includes the following steps:
1), 1,4- dichloroanthraquinone, benzoic acid derivative, magnesia, copper oxide, potassium hydroxide, alcohol solution are mixed
Afterwards, it is placed in kettle and is reacted 20 ± 2 hours in 150 ± 20 DEG C；Obtain carboxylic acid intermediate；
1,4- dichloroanthraquinone: benzoic acid derivative=1:5~6 molar ratio (preferably 1:5.6)；
Every 0.025mol 1,4- dichloroanthraquinone 1.6 ± 0.2g of adapted magnesia, 0.4 ± 0.05g copper oxide, 8.0 ± 1g hydrogen
Potassium oxide；
The benzoic acid derivative is aminobenzoic acids compound or hydroxybenzoic acids；
2) anhydrous alcohols material, sulfuric acid (concentrated sulfuric acid), back flow reaction, are added in the resulting carboxylic acid intermediate of step 1)
1.5~2.5 hours (thin-layered chromatography detection reaction end)；Then it distills, (is all steamed until anhydrous alcohols material is distilled out of
Out)；Then it successively follows the steps below: being first cooled to room temperature, then adjust pH for neutrality, then stand 1 ± 0.2h at room temperature, most
After filter, gained filter cake dry (80 DEG C drying to constant weight), obtain anthraquinone type carboxylate dyestuff；
The sulfuric acid (concentrated sulfuric acid) of 4 ± 0.2g of carboxylic acid intermediate adapted of every 0.01mol.
The improvement of preparation method as anthraquinone type carboxylate disperse dyes of the invention:
Aminobenzoic acids compound is ortho-aminobenzoic acid, gavaculine, p-aminobenzoic acid；
Hydroxybenzoic acids are septichen, m-hydroxybenzoic acid, P-hydroxybenzoic acid.
The further improvement of preparation method as anthraquinone type carboxylate disperse dyes of the invention:
The alcohol solution of the step 1) is isobutanol: the mixed liquor of water=1:13~17 (preferably 1:15) volume ratio；
The alcohol solution of 60~70ml of every 0.025mol 1,4- dichloroanthraquinone adapted.
The further improvement of preparation method as anthraquinone type carboxylate disperse dyes of the invention:
In step 1), resulting reaction solution first uses 500 ± 50ml water to every 0.025mol Isosorbide-5-Nitrae-dichloroanthraquinone after reaction
Dilution, then be acidified with 10 ± 1ml sulfuric acid (concentrated sulfuric acid)；After standing is cooled to room temperature, filter cake is washed with water in filtering, dry to perseverance
Weight, obtains carboxylic acid intermediate.
The further improvement of preparation method as anthraquinone type carboxylate disperse dyes of the invention, in the step 2):
Anhydrous alcohols material is ethyl alcohol, the tert-butyl alcohol；
The anhydrous alcohols material of 40~60mL of carboxylic acid intermediate adapted of every 0.01mol.
The further improvement of preparation method as anthraquinone type carboxylate disperse dyes of the invention, in step 2): utilizing
Saturated sodium carbonate solution adjusts pH.
In the present invention, the concentrated sulfuric acid refers to that concentration is 98% sulfuric acid.
Reaction equation of the invention is as follows:
The preparation method of anthraquinone type carboxylate disperse dyes of the invention chooses the intermediate of anthraquinone containing carboxylic acid group of preparation
(that is, step 1) prepares resulting carboxylic acid intermediate) is raw material, and carboxylic acid ester type disperse dyes are made using esterification process.Dyestuff preparation
Selected reaction raw materials are easy to get, are less toxic in the process, and synthetic route is short, reaction conversion ratio is high, can effectively reduce nocuousness
Green production is realized in the generation of substance and the three wastes.
That is, the present invention be first prepare carboxylic acid dyestuff using simple substituted anthraquinone as raw material, then by with alcohol direct esterification
One-step synthesis method carboxylate dyestuff is that carboxylate only needs single step reaction from carboxylic acid dye conversion, and reaction condition is milder.
The anthraquinone type carboxylate disperse dyes that the present invention develops have good dyeability, are applied to dyeing terylene Shi Shangran
Rate is high, good color fastness only need to handle fiber through diluter alkaline solution, send out dyestuff ester group when PET fiber is dyed and post-processed
Unboiled water solution generates the alcohols material of the carboxylic acid dyestuff containing water soluble group and low toxicity, and the carboxylic acid dyestuff generated can pass through
The methods of acidification recycling.The method not only eliminates the use of sodium hydrosulfite, and the processing for effectively reducing waste water is difficult
Degree.
Anthraquinone type carboxylate disperse dyes are used for the dyeing of PET hydrophobic polyester fiber, dyeing are as follows: take the present invention
0.5~2g of carboxylate dyestuff, 0.5~2g of dispersing agent NNO, zirconium pearl (1~2mm of diameter) 10~40g, 20~60mL of water be added
It is sanded 4~8 hours in sand mill, after sand milling, through the filtering of thin nylon filtering cloth, collects dye dispersion liquid and constant volume in 250mL
Volumetric flask obtains dye paste；Disperse dyes mill base is pipetted by 0.5~2% chromaticity requirements, after water is added by bath raio 1:30~50
It is transferred in dyeing cup, the PET fabric to be dyed is added and is put into high-temperature pressure dyeing instrument, the heating rate by 2 DEG C/min is fast
Speed is warming up to 90 DEG C, then is to slowly warm up to 130 DEG C with 1 DEG C/min, and room temperature is down in heat preservation after 1 hour, taken out dyeing cloth specimen, washed
It washs, draws dyeing front and back dye liquor respectively, measure extinction at maximum absorption wavelength (λ max) with ultraviolet-visible spectrophotometer
Degree solves the dye-uptake of dyestuff using Lambert-Beer's law.
Anthraquinone type carboxylate disperse dyes of the invention introduce the strong carboxylate group of polarity in dye structure, can
Improve affinity and fastness to sublimation of the dyestuff on polyester fiber, and with it is excellent can alkali cleaning performance, to have wide
Wealthy application prospect.
In conclusion the dyestuff developed of the present invention, in production process selected reaction raw materials be easy to get, low toxicity, and
Synthetic route is short, reaction conversion ratio is high, can effectively reduce the generation of harmful substance and the three wastes, realizes green production.It is applied to
Dye-uptake is high when dyeing terylene, good color fastness, in post-processing easy alkali cleaning, hydrolysate low toxicity, hydrolised dye easily recycle and
It can recycle.Therefore, many advantages such as easy to wash, less toxic, low dirt can effectively solve the problem that disperse dyes manufacture and print and dye
The abnormal high industry problems of waste water COD, BOD in journey.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This:
Embodiment 1, a kind of preparation method of anthraquinone type carboxylate disperse dyes, successively follow the steps below:
1), with Isosorbide-5-Nitrae-dichloroanthraquinone (0.025mol) for raw material, by it with p-aminobenzoic acid (18.5g, 0.14mol),
Magnesia (1.6g), copper oxide (0.4g), potassium hydroxide (8.0g), water (60ml), isobutanol (4ml) mixing be placed in kettle in
150 DEG C are reacted 20 hours.After reaction, reaction solution is diluted with 500ml water, then is acidified with the 10ml concentrated sulfuric acid (98%).It stands
After being cooled to room temperature, filters and be washed with water filter cake (until the pH of cleaning solution is neutrality), the filter cake after washing is in 80 DEG C of dryings
To constant weight；Obtain carboxylic acid intermediate A1.
2) it is dense that 4.8g (0.01mol) carboxylic acid intermediate A1,50mL ethyl alcohol (dehydrated alcohol), 4g, are added in three-necked flask
Sulfuric acid flows back about 2h (thin-layered chromatography detection reaction end), is then distilled, knot is then reacted after ethyl alcohol all steams
Beam, and reaction solution move in beaker after temperature be cooled to room temperature with saturated sodium carbonate dropwise addition so that pH is adjusted to neutrality after at room temperature
1h is stood, is finally filtered；By filter cake drying (80 DEG C) to constant weight, anthraquinone type carboxylate dyestuff B1 is obtained.
1H NMR (400MHz, DMSO-d6): δ 10.2 (s, 2H), 7.80 (d, 2H), 7.72 (d, 4H), 7.55 (t, 2H),
6.57(d,4H),6.50(d,2H),4.29(q,4H),1.30(t,6H)；ESI MS (m/z, %): 535.17 ([M+H]+,
100)。
Embodiment 2,
1) following change, is made to 1 step 1) of embodiment: replacing p-aminobenzoic acid, other conditions with P-hydroxybenzoic acid
It is constant, carboxylic acid intermediate A2 is obtained, structural formula is
2) carboxylic acid intermediate A1, is substituted with the carboxylic acid intermediate A2 of identical mole dosage, remaining with 1 step 2) of embodiment,
Obtain anthraquinone type carboxylate dyestuff B2.
1H NMR (400MHz, DMSO-d6): δ 7.93 (d, 4H), 7.80 (d, 2H), 7.55 (t, 2H), 7.17 (d, 2H),
7.03(d,4H),4.30(q,4H),1.32(t,6H)；ESI MS (m/z, %): 537.15 ([M+H]+,100)。
Embodiment 3,
1), with 1 step 1) of embodiment；
2) ethyl alcohol, is substituted with the tert-butyl alcohol of same volume dosage, remaining is equal to 1 step 2) of embodiment, obtains anthraquinone type carboxylic
Acid esters dyestuff B3.
1H NMR (400MHz, DMSO-d6): δ 10.3 (s, 2H), 7.81 (d, 2H), 7.74 (d, 4H), 7.57 (t, 2H),
6.57(d,4H),6.50(d,2H),1.40(s,18H)；ESI MS (m/z, %): 591.20 ([M+H]+,100)。
Embodiment 4,
1), with 2 step 1) of embodiment；
2) ethyl alcohol, is substituted with the tert-butyl alcohol of same volume dosage, remaining obtains anthraquinone type carboxylate with 2 step 2) of embodiment
Dyestuff B4.
1H NMR (400MHz, DMSO-d6): δ 7.95 (d, 4H), 7.82 (d, 2H), 7.57 (t, 2H), 7.17 (d, 2H),
7.03(d,4H),1.40(s,18H)；ESI MS (m/z, %): 593.25 ([M+H]+,100)。
Illustrate the application of anthraquinone type carboxylate disperse dyes of the invention in PET fiber dyeing below by experiment.
Experiment 1,
Dyestuff B1 0.5g, dispersing agent NNO 0.5g, zirconium pearl (diameter 1mm) 10g, the water 20mL synthesized in Example 1 adds
Enter in sand mill and be sanded 8 hours, after sand milling, holds through the filtering of thin nylon filtering cloth, collection dye dispersion liquid and constant volume in 250mL
Measuring bottle obtains dye paste；Disperse dyes mill base is pipetted by 2% chromaticity requirements, is transferred to dyeing after water is added by bath raio 1:50
In cup, the PET fabric to be dyed is added and is put into high-temperature pressure dyeing instrument, is rapidly heated by the heating rate of 2 DEG C/min to 90
DEG C, then 130 DEG C are to slowly warm up to 1 DEG C/min, room temperature is down in heat preservation after 1 hour, dyeing cloth specimen is taken out, before drawing dyeing respectively
Acetone is added to scale, with ultraviolet-visible spectrophotometer in maximum absorption wavelength in 10mL volumetric flask in each 1mL of dye liquor afterwards
Absorbance is measured at (λ max), is 95.4% using the dye-uptake that Lambert-Beer's law solves dyestuff.
Above-mentioned dyeing cloth specimen is used into national standard " measuring method of disperse dyeing coloured light and intensity " (GB/T
2394-1980) after post-processing approach reduction cleaning (reduction cleaning technique are as follows: 2g/L sodium hydrosulfite, 1g/L NaOH, bath raio 1:50,
70 DEG C, 15min), color fastness to water is 4 grades, and resistance to dry fastness is 4 grades, and wet rubbing fastness is 4-5 grades, the color of resistance to distillation
4-5 grades of fastness.
In addition, removing the loose colour of PET fabric surface using alkali wash, the specific method is as follows: the sample contaminated is in 0.1g/L
After handling 15min at 70 DEG C in NaOH aqueous solution, then repeatedly rinse through hot water and cold water；After alkali wash processing, above-mentioned sample
Color fastness to water is 4-5 grades, and resistance to dry fastness is 4-5 grades, and wet rubbing fastness is 4-5 grades, 4-5 grades of color fastness to sublimation.
Every color fastness is equal to or slightly higher than every color fastness of the sample obtained after reduction cleaning.
By the resulting dyestuff of 2~embodiment of embodiment 4 as above-mentioned experiment 1 detects, acquired results are as described in Table 1:
Table 1
It can illustrate that alkali wash can obtain excellent for anthraquinone type carboxylate disperse dyes of the invention according to the result of table 1
In or equal to national standard reduction alkali wash color fastness as a result, and alkali concentration used in alkali wash (0.1g/L NaOH aqueous solution) is remote low
In reduction alkali cleaning (1g/L NaOH aqueous solution), and the use of sodium hydrosulfite is eliminated, had very much to the post-processing of washing raffinate
Benefit.
Comparative experiments 1, C.I. solvent green 3 (CAS:128-80-3), structural formula are as follows:
By C.I. solvent green 3, as Isosorbide-5-Nitrae-dichloroanthraquinone of raw material, detected according to above-mentioned 1 the method for experiment, institute
Result is obtained to be described in table 2 below.And the detection of corresponding color fastness to light has been carried out, as a result it is described in table 2 below.
Table 2
The above list is only a few specific embodiments of the present invention for finally, it should also be noted that.Obviously, this hair
Bright to be not limited to above embodiments, acceptable there are many deformations.Those skilled in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (8)
1. anthraquinone type carboxylate disperse dyes, it is characterised in that: contain carboxylate group, general structure in molecular structure are as follows:
In formula: R is ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, n-hexyl；X is NH or O.
2. anthraquinone type carboxylate disperse dyes according to claim 1, it is characterised in that the structural formula of the disperse dyes is
It is any below:
3. the preparation method of anthraquinone type carboxylate disperse dyes as claimed in claim 1 or 2, it is characterised in that including walking as follows
It is rapid:
1) it after, mixing Isosorbide-5-Nitrae-dichloroanthraquinone, benzoic acid derivative, magnesia, copper oxide, potassium hydroxide, alcohol solution, sets
It is reacted 20 ± 2 hours in kettle in 150 ± 20 DEG C；Obtain carboxylic acid intermediate；
1,4- dichloroanthraquinone: benzoic acid derivative=1:5~6 molar ratio；
Every 0.025mol1,4- dichloroanthraquinone 1.6 ± 0.2g of adapted magnesia, 0.4 ± 0.05g copper oxide, 8.0 ± 1g hydroxide
Potassium；
The benzoic acid derivative is aminobenzoic acids compound or hydroxybenzoic acids；
2), it is added anhydrous alcohols material, sulfuric acid in the resulting carboxylic acid intermediate of step 1), back flow reaction 1.5~2.5 hours；
Then it distills, until anhydrous alcohols material is distilled out of；Then it successively follows the steps below: being first cooled to room temperature, then adjust during pH is
Property, 1 ± 0.2h is then stood at room temperature, is finally filtered, and the drying of gained filter cake obtains anthraquinone type carboxylate dyestuff；
The sulfuric acid of 4 ± 0.2g of carboxylic acid intermediate adapted of every 0.01mol.
4. the preparation method of anthraquinone type carboxylate disperse dyes according to claim 3, it is characterised in that:
Aminobenzoic acids compound is ortho-aminobenzoic acid, gavaculine, p-aminobenzoic acid；
Hydroxybenzoic acids are septichen, m-hydroxybenzoic acid, P-hydroxybenzoic acid.
5. the preparation method of anthraquinone type carboxylate disperse dyes according to claim 4, it is characterised in that:
The alcohol solution of the step 1) is isobutanol: water=1:13~17 volume ratios mixed liquor；
The alcohol solution of 60~70ml of every 0.025mol 1,4- dichloroanthraquinone adapted.
6. the preparation method of anthraquinone type carboxylate disperse dyes according to claim 4 or 5, it is characterised in that:
In step 1), every 0.025mol1, resulting reaction solution first uses 500 ± 50ml water to dilute to 4- dichloroanthraquinone after reaction,
It is acidified again with 10 ± 1ml sulfuric acid；After standing is cooled to room temperature, filter cake is washed with water in filtering, dry to constant weight, is obtained among carboxylic acid
Body.
7. the preparation method of anthraquinone type carboxylate disperse dyes according to claim 3, it is characterised in that the step 2)
In:
Anhydrous alcohols material is ethyl alcohol, the tert-butyl alcohol；
The anhydrous alcohols material of 40~60mL of carboxylic acid intermediate adapted of every 0.01mol.
8. the preparation method of anthraquinone type carboxylate disperse dyes according to claim 7, it is characterised in that the step 2)
In: pH is adjusted using saturated sodium carbonate solution.
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| US4585574A (en) * | 1980-12-12 | 1986-04-29 | Bayer Aktiengesellschaft | Anthraquinone dyestuffs, processes for their preparation, their use, and liquid-crystalline materials containing anthraquinone dyestuffs |
| JPH0413654A (en) * | 1990-04-27 | 1992-01-17 | Sumitomo Chem Co Ltd | Anthraquinone-based compound and near infrared ray absorbing filter using the same |
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| CN102639647A (en) * | 2009-11-24 | 2012-08-15 | 美利肯公司 | Polymeric violet anthraquinone colorant compositions and methods for producing the same |
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| US4585574A (en) * | 1980-12-12 | 1986-04-29 | Bayer Aktiengesellschaft | Anthraquinone dyestuffs, processes for their preparation, their use, and liquid-crystalline materials containing anthraquinone dyestuffs |
| JPH0413654A (en) * | 1990-04-27 | 1992-01-17 | Sumitomo Chem Co Ltd | Anthraquinone-based compound and near infrared ray absorbing filter using the same |
| JPH05330254A (en) * | 1992-05-29 | 1993-12-14 | Mitsui Toatsu Chem Inc | Cyan dye for thermal sublimation transfer recording |
| US20060178400A1 (en) * | 2004-11-05 | 2006-08-10 | Beutel Bruce A | Novel acetyl-CoA carboxylase (ACC) inhibitors and their use in diabetes, obesity and metabolic syndrome |
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