CN109679366B - Anthraquinone carboxylate disperse dye and preparation method thereof - Google Patents
Anthraquinone carboxylate disperse dye and preparation method thereof Download PDFInfo
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- CN109679366B CN109679366B CN201811610069.0A CN201811610069A CN109679366B CN 109679366 B CN109679366 B CN 109679366B CN 201811610069 A CN201811610069 A CN 201811610069A CN 109679366 B CN109679366 B CN 109679366B
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- disperse dye
- anthraquinone
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- carboxylate
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- 239000000986 disperse dye Substances 0.000 title claims abstract description 48
- POPBYCBXVLHSKO-UHFFFAOYSA-N 9,10-dioxoanthracene-1-carboxylic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(=O)O POPBYCBXVLHSKO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000975 dye Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 26
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 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 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 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
- -1 benzoic acid compound Chemical class 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- 229960004050 aminobenzoic acid Drugs 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
- 239000007864 aqueous solution 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 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
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 12
- 150000001733 carboxylic acid esters Chemical group 0.000 abstract description 7
- 239000000835 fiber Substances 0.000 abstract description 6
- 229920000728 polyester Polymers 0.000 abstract description 6
- 150000007942 carboxylates Chemical group 0.000 abstract description 5
- 238000000859 sublimation Methods 0.000 abstract description 3
- 230000008022 sublimation Effects 0.000 abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 abstract description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 abstract description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract description 2
- 238000004043 dyeing Methods 0.000 description 19
- 239000004744 fabric Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 6
- 239000000980 acid dye Substances 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 239000007788 liquid 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
- 238000004140 cleaning Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 238000007639 printing 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
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000005165 hydroxybenzoic acids Chemical class 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 231100000175 potential carcinogenicity Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- 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 an anthraquinone carboxylate disperse dye, the molecular structure of which contains carboxylate groups, and the structural general formula is as follows:
Description
Technical Field
The invention relates to an anthraquinone carboxylate disperse dye and a preparation method thereof.
Background
The yield of disperse dyes in China is the first world, but at present, dye manufacturing enterprises generally have the problems of old varieties, backward technology and the like, so that the profit rate of the disperse dyes in China is low, and meanwhile, the environmental protection pressure is continuously increased, so that the development of the whole textile industry faces a dilemma. The development of novel high-fastness dye and the improvement of the existing dye production technology and the increase of the technical content of the dye are the necessary routes for the development of the dye industry. The development of low-pollution dyes reduces the use of harmful chemicals in the processes of dye manufacture, application and post-treatment, fundamentally solves the industrial problems of high toxicity of printing and dyeing wastewater, high COD and BOD distortion, difficult treatment and the like, and is the important factor in the future development of the dye manufacture and printing and dyeing industry.
Three wastes (waste water, waste residue and waste gas) are inevitably generated in the production and use processes of the traditional dye manufacturing enterprises. After dyeing, the disperse dyes used in the current market must be reduced and cleaned to remove loose color on the surface of the fabric, so as to improve various color fastness of the fabric. Because a large amount of sodium hydrosulfite and strong alkaline solution with higher concentration are used in the reduction cleaning process, high-concentration unreacted sodium hydrosulfite, sodium hydroxide and arylamine compounds with potential carcinogenicity or mutagenicity exist in the treated reduction solution, and the wastewater discharged into rivers can cause serious pollution to water bodies. In addition, the safety powder has potential safety hazards in the storage and use processes, and the safety powder is easy to spontaneously combust after absorbing moisture and has potential fire hazards; a large amount of irritant gas can escape during the use process, which aggravates environmental pollution and harms health.
The invention 'heterocyclic ring alkali washable carboxylic acid ethyl ester type disperse dye and a preparation method thereof' with the application number of 201510523507X selects the existing commercial disperse dye containing cyano as a raw material, converts the cyano into a carboxylic ester group by adopting a unit reaction of an alcoholysis method, and then prepares the carboxylic ester type disperse dye.
C.I. disperse orange 25 containing cyano is used as a raw material, absolute ethyl alcohol is used as a solvent and a reactant, concentrated sulfuric acid is used as a catalyst, and the carboxylic ester type azo disperse dye D1 is prepared by utilizing the alcoholysis reaction of the cyano.
After the C.I. disperse orange 25 and the D1 are respectively sanded and dyed on terylene, the obtained dyed fabric adopts the national standard' light fastness and sunlight of textile color fastness test (GB/T8426 plus 1998) to measure the light fastness, the light fastness of the C.I. disperse orange 25 dyed cloth sample is grade 6, and the light fastness of the D1 dyed cloth sample is grade 4-5. It is thus seen that the substitution of the cyano group by an ester group deteriorates the light fastness properties of the dye.
Disclosure of Invention
The invention aims to solve the technical problem of providing an anthraquinone carboxylate disperse dye and a preparation method thereof, wherein the disperse dye has the characteristics of high dye uptake and good color fastness when being applied to polyester dyeing, and has the characteristics of easy alkali washing, no sodium hydrosulfite and the like during post-treatment.
In order to solve the technical problems, the invention provides an anthraquinone carboxylate disperse dye, the molecular structure of which contains carboxylate groups, and the structural general formula of which is as follows:
in the formula: r is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl and the like; x is NH or O.
As a further improvement of the anthraquinone carboxylic ester disperse dye, the disperse dye has a structural formula as follows:
the invention also provides a preparation method of the anthraquinone carboxylate disperse dye, which comprises the following steps:
1) mixing 1, 4-dichloroanthraquinone, benzoic acid compounds, magnesium oxide, copper oxide, potassium hydroxide and an alcohol-water solution, and placing the mixture in a kettle to react at the temperature of 150 +/-20 ℃ for 20 +/-2 hours; to obtain a carboxylic acid intermediate;
1, 4-dichloroanthraquinone: a benzoic acid compound in a molar ratio of 1:5 to 6 (preferably 1: 5.6);
1.6 plus or minus 0.2g of magnesium oxide, 0.4 plus or minus 0.05g of copper oxide and 8.0 plus or minus 1g of potassium hydroxide are used for every 0.025mol of 1, 4-dichloroanthraquinone;
the benzoic acid compound is an aminobenzoic acid compound or a hydroxybenzoic acid compound;
2) adding anhydrous alcohol substances and sulfuric acid (concentrated sulfuric acid) into the carboxylic acid intermediate obtained in the step 1), and carrying out reflux reaction for 1.5-2.5 hours (detecting the reaction end point by thin-layer chromatography); then distilling until anhydrous alcohol substances are distilled out (all distilled out); then the following steps are carried out in sequence: cooling to room temperature, adjusting pH to neutral, standing at room temperature for 1 + -0.2 h, filtering, and oven drying the filter cake (80 deg.C to constant weight) to obtain anthraquinone carboxylate dye;
4. + -. 0.2g of sulfuric acid (concentrated sulfuric acid) are used per 0.01mol of carboxylic acid intermediate.
As an improvement of the preparation method of the anthraquinone carboxylic ester disperse dye of the invention:
the aminobenzoic acid compound is anthranilic acid, m-aminobenzoic acid and p-aminobenzoic acid;
the hydroxybenzoic acid compounds are ortho-hydroxybenzoic acid, meta-hydroxybenzoic acid and para-hydroxybenzoic acid.
As a further improvement of the preparation method of the anthraquinone carboxylic ester disperse dye of the invention:
the alcohol aqueous solution in the step 1) is isobutanol: water is a mixed solution with a volume ratio of 1: 13-17 (preferably 1: 15);
60-70 ml of alcohol-water solution is added to every 0.025mol of 1, 4-dichloroanthraquinone.
As a further improvement of the preparation method of the anthraquinone carboxylic ester disperse dye of the invention:
in the step 1), diluting reaction liquid obtained after the reaction of every 0.025mol of 1, 4-dichloroanthraquinone with 500 plus or minus 50ml of water, and then acidifying with 10 plus or minus 1ml of sulfuric acid (concentrated sulfuric acid); standing and cooling to room temperature, filtering, washing a filter cake with water, and drying to constant weight to obtain a carboxylic acid intermediate.
As a further improvement of the preparation method of the anthraquinone carboxylic ester disperse dye of the present invention, in the step 2):
the anhydrous alcohol substance is ethanol and tert-butanol;
40-60 mL of anhydrous alcohol substances are added in each 0.01mol of carboxylic acid intermediate.
As a further improvement of the preparation method of the anthraquinone carboxylic ester disperse dye, in the step 2): the pH was adjusted with saturated sodium carbonate solution.
In the present invention, concentrated sulfuric acid means sulfuric acid having a concentration of 98%.
The reaction formula of the invention is as follows:
the preparation method of the anthraquinone carboxylic ester disperse dye provided by the invention selects the prepared carboxylic group-containing anthraquinone intermediate (namely, the carboxylic acid intermediate prepared in the step 1) as a raw material, and adopts an esterification method to prepare the carboxylic ester disperse dye. The reaction raw materials selected in the dye preparation process are easy to obtain and low in toxicity, the synthetic route is short, the reaction conversion rate is high, the generation of harmful substances and three wastes can be effectively reduced, and green production is realized.
The carboxylic acid dye is synthesized by a one-step method of directly esterifying the carboxylic acid dye with alcohol, and the carboxylic acid dye is converted into the carboxylic ester by only one-step reaction, so that the reaction conditions are milder.
The anthraquinone carboxylate disperse dye developed by the invention has good dyeing performance, high dye uptake and good color fastness when being applied to polyester dyeing, and when the PET fiber is treated after dyeing, only dilute alkaline solution is needed to treat the fiber, so that the dye ester group is hydrolyzed to generate carboxylic acid dye containing water-soluble groups and low-toxicity alcohol substances, and the generated carboxylic acid dye can be recycled by acidification and other methods. The method not only eliminates the use of sodium hydrosulfite, but also effectively reduces the treatment difficulty of the wastewater.
The anthraquinone carboxylate disperse dye is used for dyeing PET hydrophobic polyester fibers, and the dyeing process comprises the following steps: adding 0.5-2 g of carboxylate dye, 0.5-2 g of dispersant NNO, 10-40 g of zirconium beads (with the diameter of 1-2 mm) and 20-60 mL of water into a sand mill, sanding for 4-8 hours, filtering through fine nylon filter cloth after sanding, collecting dye dispersion liquid, and fixing the volume in a 250mL volumetric flask to obtain dye color paste; transferring the disperse dye color paste according to the chromaticity requirement of 0.5-2%, and mixing the disperse dye color paste according to the bath ratio of 1: 30-50 of water is added, the mixture is transferred to a dyeing cup, the mixture is added with PET fabric to be dyed and placed into a high-temperature high-pressure dyeing instrument, the temperature is rapidly increased to 90 ℃ at the temperature increase speed of 2 ℃/min, then the temperature is slowly increased to 130 ℃ at the speed of 1 ℃/min, the temperature is maintained for 1 hour and then is reduced to room temperature, a dyed cloth sample is taken out, the dyed cloth sample is washed, dye solutions before and after dyeing are respectively absorbed, the absorbance is measured at the maximum absorption wavelength (lambda max) by an ultraviolet-visible spectrophotometer, and the dye uptake of the dye is solved by utilizing the Lambert-beer.
The anthraquinone carboxylate disperse dye has the advantages that carboxylic ester groups with strong polarity are introduced into the dye structure, the affinity and the sublimation fastness resistance of the dye on polyester fibers can be improved, and the anthraquinone carboxylate disperse dye has excellent alkali washability, so that the anthraquinone carboxylate disperse dye has a wide application prospect.
In conclusion, the dye developed by the invention has the advantages of easily obtained reaction raw materials, low toxicity, short synthetic route and high reaction conversion rate in the production process, can effectively reduce the generation of harmful substances and three wastes, and realizes green production. When the dye is applied to polyester dyeing, the dye-uptake is high, the color fastness is good, alkali washing is easy during post-treatment, the hydrolysate is low in toxicity, and the hydrolyzed dye is easy to recycle and can be recycled. Therefore, the industrial problems of COD, BOD distortion and the like of the wastewater in the manufacturing and printing and dyeing processes of the disperse dye can be effectively solved by the advantages of easy washing, low toxicity, low pollution and the like.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1, a method for preparing an anthraquinone carboxylate disperse dye, sequentially performing the following steps:
1) 1, 4-dichloroanthraquinone (0.025mol) was used as a raw material, and this was mixed with p-aminobenzoic acid (18.5g, 0.14mol), magnesium oxide (1.6g), copper oxide (0.4g), potassium hydroxide (8.0g), water (60ml), and isobutanol (4ml), and then placed in a reactor to react at 150 ℃ for 20 hours. After the reaction, the reaction solution was diluted with 500ml of water and acidified with 10ml of concentrated sulfuric acid (98%). Standing and cooling to room temperature, filtering, washing the filter cake with water (until the pH of the washing liquid is neutral), and drying the washed filter cake at 80 ℃ to constant weight; to give carboxylic acid intermediate a 1.
2) Adding 4.8g (0.01mol) of carboxylic acid intermediate A1, 50mL of ethanol (absolute ethanol) and 4g of concentrated sulfuric acid into a three-neck flask, refluxing for about 2h (detecting the reaction end point by thin-layer chromatography), distilling, ending the reaction after all the ethanol is evaporated, transferring the reaction solution into the beaker, cooling to room temperature, dropwise adding saturated sodium carbonate to adjust the pH to be neutral, standing for 1h at room temperature, and finally performing suction filtration; and drying the filter cake (80 ℃) to constant weight to obtain the anthraquinone carboxylate dye B1.
1H NMR(400MHz,DMSO-d6)：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)。
Examples 2,
1) Example 1, step 1) was modified as follows: replacing p-aminobenzoic acid with p-hydroxybenzoic acid under the same conditions to obtain carboxylic acid intermediate A2 with structural formula
2) The same molar amount of the carboxylic acid intermediate A2 as that of the carboxylic acid intermediate A1 is used instead of the carboxylic acid intermediate A1, and the procedure is the same as that of the step 2) of the example 1, so that the anthraquinone carboxylic acid ester dye B2 is obtained.
1H NMR(400MHz,DMSO-d6)：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)。
Examples 3,
1) Same as example 1, step 1);
2) and the ethanol is replaced by the tert-butyl alcohol with the same volume and dosage, and the rest is equal to the step 2) of the example 1, so that the anthraquinone carboxylate dye B3 is obtained.
1H NMR(400MHz,DMSO-d6)：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)。
Examples 4,
1) Same as example 2, step 1);
2) the same volume of tert-butanol was used instead of ethanol, and the remainder was the same as in step 2) of example 2, whereby anthraquinone-type carboxylate dye B4 was obtained.
1H NMR(400MHz,DMSO-d6)：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)。
The following experiment shows the application of the anthraquinone carboxylate disperse dye in dyeing PET fiber.
Experiment 1,
Adding 10.5g of the dye B10, 0.5g of a dispersing agent NNO, 10g of zirconium beads (with the diameter of 1mm) and 20mL of water synthesized in the embodiment 1 into a sand mill, sanding for 8 hours, filtering through fine nylon filter cloth after sanding, collecting dye dispersion liquid, and fixing the volume in a volumetric flask with the volume of 250mL to obtain dye color paste; transferring disperse dye color paste according to the chromaticity requirement of 2 percent, and mixing the disperse dye color paste according to the bath ratio of 1:50, adding water, transferring the mixture into a dyeing cup, adding a PET fabric to be dyed, putting the PET fabric into a high-temperature high-pressure dyeing instrument, quickly heating to 90 ℃ at the heating rate of 2 ℃/min, slowly heating to 130 ℃ at the temperature of 1 ℃/min, keeping the temperature for 1 hour, cooling to room temperature, taking out a dyed cloth sample, respectively sucking 1mL of dye solution before and after dyeing into a 10mL volumetric flask, adding acetone to the scale, measuring the absorbance at the maximum absorption wavelength (lambda max) by using an ultraviolet-visible spectrophotometer, and solving the dye uptake of the dye to be 95.4% by using the Lambert-beer law.
The dyed cloth sample is subjected to reduction cleaning by adopting a post-treatment method of national standard 'measuring method of dyeing color and intensity of disperse dyes' (GB/T2394-1980) (reduction cleaning process is 2g/L sodium hydrosulfite, 1g/L NaOH, bath ratio is 1:50, 70 ℃ and 15min), and the dyed cloth sample has water color fastness of 4 grade, dry rubbing fastness of 4 grade, wet rubbing fastness of 4-5 grade and sublimation color fastness of 4-5 grade.
In addition, the surface of the PET fabric is subjected to loose color removal by an alkali washing method, which comprises the following specific steps: treating the dyed sample in 0.1g/L NaOH aqueous solution at 70 ℃ for 15min, and rinsing the sample with hot water and cold water for multiple times; after the alkali washing treatment, the water fastness and the dry rubbing fastness of the sample are respectively 4-5 grades, 4-5 grades and 4-5 grades. The color fastnesses are equal to or slightly higher than those of the samples obtained after reduction washing.
The dyes obtained in examples 2 to 4 were examined as in experiment 1 above, and the results are shown in table 1:
TABLE 1
The results in Table 1 show that the alkali washing method can obtain color fastness results superior to or equal to the national standard reductive alkali washing method for the anthraquinone-type carboxylate disperse dye of the present invention, and the alkali washing method uses alkali with concentration (0.1g/L NaOH aqueous solution) much lower than that of reductive alkali washing (1g/L NaOH aqueous solution), and dispenses with the use of sodium hydrosulfite, which is very advantageous for the post-treatment of the washing residual liquid.
Comparative experiment 1, C.I. solvent Green 3 (CAS: 128-80-3), structural formula:
the c.i. solvent green 3 and 1, 4-dichloroanthraquinone as the raw material were measured by the method described in the above experiment 1, and the results are shown in the following table 2. The corresponding test for light fastness was carried out, and the results are shown in Table 2 below.
TABLE 2
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (6)
1. The anthraquinone carboxylate disperse dye is characterized in that the structural formula of the disperse dye is any one of the following:
2. the process for producing the anthraquinone carboxylic ester disperse dye according to claim 1, which comprises the steps of:
1) mixing 1, 4-dichloroanthraquinone, benzoic acid compounds, magnesium oxide, copper oxide, potassium hydroxide and an alcohol-water solution, and placing the mixture in a kettle to react at the temperature of 150 +/-20 ℃ for 20 +/-2 hours; to obtain a carboxylic acid intermediate;
1, 4-dichloroanthraquinone: benzoic acid compounds in a molar ratio of 1: 5-6;
every 0.025mol of 1, 4-dichloroanthraquinone is mixed with 1.6 plus or minus 0.2g of magnesium oxide, 0.4 plus or minus 0.05g of copper oxide and 8.0 plus or minus 1g of potassium hydroxide;
the benzoic acid compound is p-aminobenzoic acid or p-hydroxybenzoic acid;
2) adding anhydrous alcohol substances and sulfuric acid into the carboxylic acid intermediate obtained in the step 1), and performing reflux reaction for 1.5-2.5 hours; then distilling until the anhydrous alcohol substance is distilled out; then the following steps are carried out in sequence: cooling to room temperature, adjusting pH to neutral, standing at room temperature for 1 + -0.2 h, filtering, and oven drying the filter cake to obtain anthraquinone carboxylate dye;
4 plus or minus 0.2g of sulfuric acid is used for every 0.01mol of the carboxylic acid intermediate;
the anhydrous alcohol is ethanol or tert-butanol.
3. The method for producing the anthraquinone carboxylic ester disperse dye according to claim 2, wherein:
the alcohol aqueous solution in the step 1) is isobutanol: water is a mixed solution with the volume ratio of 1: 13-17;
60-70 ml of alcohol-water solution is added to every 0.025mol of 1, 4-dichloroanthraquinone.
4. The process for producing the anthraquinone carboxylic ester disperse dye according to claim 3, wherein:
in the step 1), diluting reaction liquid obtained after the reaction of every 0.025mol of 1, 4-dichloroanthraquinone with 500 plus or minus 50ml of water, and then acidifying with 10 plus or minus 1ml of sulfuric acid; standing and cooling to room temperature, filtering, washing a filter cake with water, and drying to constant weight to obtain a carboxylic acid intermediate.
5. The method for preparing the anthraquinone carboxylic ester disperse dye according to claim 2, wherein in the step 2):
40-60 mL of anhydrous alcohol substances are added in each 0.01mol of carboxylic acid intermediate.
6. The method for preparing the anthraquinone carboxylic ester disperse dye according to claim 5, wherein in the step 2): the pH was adjusted with saturated sodium carbonate solution.
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