CN110938039A - Purple reactive dye based on trisazo multichromosome and preparation and application thereof - Google Patents
Purple reactive dye based on trisazo multichromosome and preparation and application thereof Download PDFInfo
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- 239000000985 reactive dye Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000005859 coupling reaction Methods 0.000 claims abstract description 34
- 239000000975 dye Substances 0.000 claims abstract description 31
- 238000010168 coupling process Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920000742 Cotton Polymers 0.000 claims abstract description 14
- 230000008878 coupling Effects 0.000 claims abstract description 14
- 238000004043 dyeing Methods 0.000 claims abstract description 13
- 239000012954 diazonium Substances 0.000 claims abstract description 11
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 28
- 238000006482 condensation reaction Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 19
- -1 aromatic primary amine Chemical class 0.000 claims description 18
- 235000010288 sodium nitrite Nutrition 0.000 claims description 16
- 238000006193 diazotization reaction Methods 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 7
- 238000005185 salting out Methods 0.000 claims description 6
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 claims 8
- 239000004744 fabric Substances 0.000 abstract description 12
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000010186 staining Methods 0.000 abstract description 2
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000001047 purple dye Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- HFIYIRIMGZMCPC-YOLJWEMLSA-J remazole black-GR Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(\N=N\C=3C=CC(=CC=3)S(=O)(=O)CCOS([O-])(=O)=O)C(O)=C2C(N)=C1\N=N\C1=CC=C(S(=O)(=O)CCOS([O-])(=O)=O)C=C1 HFIYIRIMGZMCPC-YOLJWEMLSA-J 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- LZKGFGLOQNSMBS-UHFFFAOYSA-N 4,5,6-trichlorotriazine Chemical compound ClC1=NN=NC(Cl)=C1Cl LZKGFGLOQNSMBS-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- SQYUJKVKVFILNB-UHFFFAOYSA-N methyl 2-amino-4-[(2,5-dichlorophenyl)carbamoyl]benzoate Chemical compound C1=C(N)C(C(=O)OC)=CC=C1C(=O)NC1=CC(Cl)=CC=C1Cl SQYUJKVKVFILNB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000988 sulfur dye Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/50—Two nitrogen atoms with a halogen atom attached to the third ring carbon atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/507—Azo dyes
- C09B62/513—Disazo or polyazo 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
- D06P1/38—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 reactive dyes
- D06P1/382—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 reactive dyes reactive group directly attached to heterocyclic group
-
- 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
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
- D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
Abstract
The invention relates to a purple reactive dye based on a trisazo multichromosome, and a preparation method and an application thereof. The reactive dye has a structural formula shown as (I). The preparation comprises the following steps: preparing a first condensate, preparing a coupling liquid, preparing a second condensate diazonium salt, preparing an acid coupling product and preparing a purple reactive dye. The purple reactive dye prepared by the method is novel in structure and color light, high in color development strength, free of staining when used for printing and dyeing cotton fabrics, good in lifting force performance and color fastness, capable of realizing color matching performance in molecules by introducing red and blue color bodies in the molecules simultaneously, and capable of avoiding the problem of poor compatibility when compounding single-color dyes.
Description
Technical Field
The invention belongs to the field of reactive dyes and preparation and application thereof, and particularly relates to a purple reactive dye based on trisazo multichromophore and preparation and application thereof.
Background
The reactive dye has the advantages of bright color, excellent wet-processing color fastness, low synthesis cost, wide color spectrum, wide application range and the like. Especially, in recent years, due to the advantage that the reactive dye does not contain carcinogenic aromatic amine in the structure, the reactive dye slowly replaces direct dye, vat dye, ice dye and sulfur dye in the market, and the application of the reactive dye on cellulose fiber is continuously expanded. With the increase of the color light demand of people on new color light, the fiber is printed by adopting the dye mixed by single color light or different color light, and the printed fabric with complete color spectrum can be obtained. Purple is used as a medium color, most of the purple is obtained by compounding red dye and blue dye, and due to different molecular structures of the compounded dye, the dye has different dye uptake and printing depth on cotton fabrics, so that unstable color light, poor reproducibility and low one-time success rate are easy to occur in the printing and dyeing process, the pollution is serious, and the requirements of energy conservation, emission reduction and clean production cannot be met. Therefore, a class of reactive dyes containing red and blue color bodies in a molecule are developed, intramolecular color matching is realized, the dye with a purple single structure is obtained, and the problems of poor compatibility and poor color light reproducibility of the two dyes are solved. The traditional purple dye obtained by matching active black 5 has the problems of unstable color light, poor reproducibility and low one-time success rate.
Disclosure of Invention
The invention aims to solve the technical problem of providing a purple reactive dye based on a trisazo multichromosome and preparation and application thereof, so as to solve the problems of insufficient color development strength, lifting power performance and color fastness of the purple reactive dye and poor compatibility of a compound purple reactive dye during color matching between two dye molecules in the prior art.
The invention provides a purple reactive dye based on a trisazo multichromosome, and the structural formula of the dye is as follows:
in the formula, R1And R2The method comprises the following steps:
The structural formula of the dye is as follows:
The invention also provides a preparation method of the purple reactive dye based on the trisazo multichromosome, which comprises the following steps:
(1) dripping an H acid aqueous solution into the uniformly pulped cyanuric chloride suspension, and carrying out condensation reaction to obtain a condensed liquid, wherein the molar ratio of cyanuric chloride to H acid is 1.02: 1-1: 1;
(2) adding a hydrochloric acid solution into an aromatic primary amine aqueous solution containing sulfonic groups, dropwise adding a sodium nitrite solution while stirring, performing diazotization reaction, adding the obtained diazonium salt into the first condensate obtained in the step (1), and adjusting the pH value to 6.0-6.5 to perform coupling reaction to obtain a coupling solution (red), wherein the molar ratio of the aromatic primary amine containing sulfonic groups to the H acid in the step (1) is 0.97: 1-0.99: 1, and the molar ratio of the aromatic primary amine containing sulfonic groups to hydrochloric acid to sodium nitrite is 0.97:0.97: 1-1: 1.1;
(3) adding 2, 4-diaminobenzene sulfonic acid into the coupling solution in the step (2), performing condensation reaction, adding hydrochloric acid solution into the obtained second condensate, dropwise adding sodium nitrite solution while stirring, and performing diazotization reaction to obtain second condensate diazonium salt, wherein the molar ratio of the 2, 4-diaminobenzene sulfonic acid to the H acid in the step (1) is 0.95: 1-0.98: 1, and the molar ratio of the second condensate, hydrochloric acid and sodium nitrite is 0.95:1.5: 1.1-1: 2: 1.2;
(4) adding a hydrochloric acid solution into an aromatic primary amine aqueous solution containing sulfonic groups, dropwise adding a sodium nitrite solution while stirring, performing diazotization reaction to obtain diazonium salt, adding H acid, and performing coupling reaction to obtain an acid coupling product, wherein the molar ratio of the aromatic primary amine containing the sulfonic groups to the H acid in the step (1) is 0.8: 1-0.9: 1, the molar ratio of the aromatic primary amine containing the sulfonic groups to hydrochloric acid to sodium nitrite is 0.8:0.8: 1-1: 1.1, and the molar ratio of the H acid to the aromatic primary amine containing the sulfonic groups is 0.8: 1-1: 1;
(5) and (3) adding the diazosalt of the second condensate obtained in the step (3) into the acid coupling product obtained in the step (4), adjusting the pH value to 6.0-6.5 for coupling reaction, salting out the obtained coupling solution, filtering and drying to obtain the purple reactive dye.
And (2) adjusting the pH value of the H acid aqueous solution in the step (1) to 5.8-6.0 by using 10% by mass of sodium hydroxide.
The mass fraction of the H acid aqueous solution in the step (1) is 20-25%; the mass fraction of the cyanuric chloride suspension is 15-25%.
The pulping of the cyanuric chloride suspension in the step (1) is carried out for 0.5-0.8 h at the temperature of 0-2 ℃.
In the step (1), the condensation reaction temperature is 0-5 ℃, the condensation reaction time is 3-5 h, and the condensation reaction pH value is 4-4.5.
The coupling reaction for adjusting the pH value to 6.0-6.5 in the step (2) comprises the following steps: adding 15 percent of Na by mass2CO3Adjusting the pH value of the solution to 6.0-6.5, reacting for 5-10min at 0-5 ℃, and then continuing to react for 4-6 h at 8-15 ℃.
The structural formula of the aromatic primary amine containing sulfonic acid group in the steps (2) and (4) comprises:
The mass fraction of the aromatic primary amine aqueous solution containing sulfonic acid groups in the steps (2) and (4) is 15-25%.
The hydrochloric acid solution and the sodium nitrite solution in the steps (2), (3) and (4) are aqueous solutions, and the mass fractions of the aqueous solutions are 36.5% and 25.0-35%, respectively.
In the steps (2), (3) and (4), the diazotization reaction temperature is 0-5 ℃, and the diazotization reaction time is 1-3 h.
In the step (3), the condensation reaction temperature is 28-32 ℃, the condensation reaction time is 2-4 h, and the condensation reaction pH value is 3.5-4.5.
In the step (4), the coupling reaction temperature is 8-15 ℃, the coupling reaction time is 5-7 h, and the pH value of the coupling reaction is not required to be adjusted.
The coupling reaction for adjusting the pH value to 6.0-6.5 in the step (5) comprises the following steps: adding 15 percent of Na by mass2CO3Adjusting the pH value of the solution to 6.0-6.5, reacting for 25-35 min at 0-5 ℃, and then continuing to react for 8-10 h at 20-25 ℃.
The salting-out in the step (5) is as follows: weighing KCl according to 10% of the total liquid amount after the reaction is finished, and salting out; the filtration is suction filtration; the drying temperature is 60-65 ℃.
The purple reactive dye in the step (5) can also contain part of other dye components and part of impurities, because a small part of impurity dye and electrolyte powder (sodium chloride and the like) are inevitably carried in the condensation, diazotization and coupling processes of the reactive dye.
The invention provides an application of a purple reactive dye based on a trisazo multichromosome in dyeing or printing cotton, hemp, regenerated fibers, protein fibers or textiles thereof.
The cotton comprises rayon cotton.
According to the invention, a red H acid azo structure is introduced into a blue azo structure through condensation, diazotization and coupling reaction, and a series of purple reactive dyes with intramolecular synergetic chromophoric effect based on trisazo multichromophore are synthesized through intramolecular color matching of the dyes.
Advantageous effects
(1) The purple reactive dye prepared by the invention has novel structure and color light, high color development intensity, no staining when being used for printing and dyeing cotton fabrics, and good lifting force performance and color fastness.
(2) The purple reactive dye prepared by the invention realizes the intramolecular color matching performance by simultaneously introducing the red and blue color bodies into molecules, and avoids the problem of poor compatibility when compounding monochromatic dyes.
Drawings
FIG. 1 is an IR spectrum of a violet reactive dye prepared in example 1.
FIG. 2 is an IR spectrum of a violet reactive dye prepared in example 2.
FIG. 3 is an IR spectrum of a violet reactive dye prepared in example 3.
FIG. 4 is a UV-VIS absorption spectrum of the violet reactive dye of example 4.
FIG. 5 is a graph showing the lifting force of the purple reactive dye on the printing of cotton fabric in example 5.
FIG. 6 is a process curve of dyeing cotton fabric with the violet reactive dye of example 6.
FIG. 7 is a curve of the lifting force of the purple reactive dye on the dyeing of cotton fabric in example 6.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
H acid and trichlorotriazine are from Zhejiang Wanfeng chemical company, and other chemicals are from Shanghai national medicine group, Inc.
Example 1
The synthesis process of the purple reactive dye with the structure as follows:
(1) preparation of a condensate: 18.8g (0.102mol) of cyanuric chloride is prepared into a suspension with the mass fraction of 20 percent, and the suspension is pulped in an ice-water bath for 0.6h at the temperature of 0-2 ℃. Accurately weighing 34.1g (0.100mol) of H acid to prepare 20% aqueous solution by mass, adjusting the pH value to 6.0 by using 10% NaOH by mass, dropwise adding the aqueous solution into evenly pulped cyanuric chloride at the temperature of 0-5 ℃, keeping the temperature at 3-5 ℃ after dropwise adding, and using 15% Na by mass2CO3Adjusting the pH value to 4.5, reacting for 4h, and detecting the end point of the first condensation reaction by thin-layer chromatography (a developing agent is n-butanol, ethanol and ammonia water are 6:2: 3).
(2) Preparation of o-aminobenzenesulfonic acid diazonium salt: accurately weighing 17.3g (0.098mol) of o-aminobenzenesulfonic acid, preparing into a 20% aqueous solution, stirring for 0.5h, uniformly mixing, cooling to 0-5 ℃, adding 9.8g (0.098mol) of concentrated hydrochloric acid with the mass fraction of 37.5%, stirring for 10min, slowly dripping 6.969g (0.101mol) of sodium nitrite to prepare a 30% aqueous solution, reacting for 2h at the temperature of 2-5 ℃ after dripping, and eliminating excessive nitrous acid by using sulfamic acid after reacting.
(3) Coupling reaction: pouring the diazonium salt in the step (2) into the condensate in the step (1), and using Na with the mass fraction of 15 percent2CO3Adjusting the pH value of the solution to 6.0, reacting at 0-5 ℃ for 10min, then continuing to react at 8-15 ℃ for 5h, and detecting the end point of the first condensation reaction by thin layer chromatography (a developing agent is n-butanol: ethanol: ammonia water: 4:2: 3).
(4) Preparation of the second condensate: accurately weighing 18.4g (0.098mol) of 2, 4-diaminobenzene sulfonic acid, adding into the coupling liquid in the step (3), and adding Na with the mass fraction of 15%2CO3Adjusting the pH value of the solution to 4.0, controlling the reaction temperature to be 28-30 ℃, controlling the reaction time to be about 3 hours, and detecting the end point of the first condensation reaction by thin-layer chromatography (a developing agent is n-butanol, ethanol and ammonia water are 4:2: 3).
(5) ① preparation of diazo salt, namely accurately weighing 23.9g (0.085mol) of 4-ethyl sulfate sulfuryl aniline to prepare 20% aqueous solution, stirring for 0.5h until the mixture is uniformly mixed, cooling to 0-5 ℃, adding 9.8g (0.085mol) of concentrated hydrochloric acid with the mass fraction of 37.5%, stirring for 10min, slowly dripping 6.969g (0.090mol) of sodium nitrite to prepare 30% aqueous solution, reacting for 2h at 2-5 ℃ after dripping is finished, and eliminating excessive nitrous acid by sulfamic acid after the reaction is finished ② coupling reaction, namely accurately weighing 29.0g H acid (0.085mol), adding the acid into the diazo salt in ①, reacting for 10min at 0-5 ℃ without adjusting the pH value, then continuing to react for 5h at 8-15 ℃, and detecting the end point of the condensation reaction by thin layer (the reagent is ethanol: 4:2:3 ammonia water).
(6) Preparation of the dimeric diazonium salt: and (3) cooling the secondary condensate obtained in the step (4) to 0-5 ℃, adding 11.5g (0.166mol) of concentrated hydrochloric acid with the mass fraction of 37.5%, stirring for 10min, slowly dripping 6.969g (0.090mol) of sodium nitrite to prepare an aqueous solution with the mass fraction of 30%, reacting for 2h at the temperature of 2-5 ℃ after dripping, and eliminating excessive nitrous acid by using sulfamic acid after reacting.
(7) Coupling reaction: adding the dimeric substance diazonium salt in the step (6) into the acid coupling product in the step (5) for reaction, and using Na with the mass fraction of 15 percent2CO3Adjusting the pH value of the solution to 6.0, reacting at 0-5 ℃ for 30min, continuing to react at 20-25 ℃ for about 8h, and detecting the reaction end point by thin-layer chromatography (a developing agent is n-butanol: ethanol: ammonia water: 3:2: 4).
(8) Salting out: KCl is weighed according to 10% of the total liquid amount after the reaction is finished, salting out is carried out, suction filtration is carried out, drying is carried out at the temperature of 65 ℃, and the purple reactive dye is obtained, wherein the yield is 78.5% (calculated by H acid feeding amount). The infrared spectrum of the dye after repeated recrystallization purification from a mixture of ethanol and water (2:1) is shown in FIG. 1, and the data is as follows: 3417.6, 1546.7, 1480.0, 1401.6, 1328.7, 1183.7, 1086.7, 1050.3, 886.2cm-1。
Example 2
The reactive dye of this example was synthesized in the same manner as in example 1 except that 17.3g (0.098mol) of orthanilic acid obtained in example 1 was replaced by 26.9g (0.098mol) of aniline-2, 5-disulfonic acid, and the rest was the same as in example 1, to obtain a violet reactive dye having the following structure, and the yield was 75.1% (based on the charged amount of H acid). The dye obtained is mixed with water (2:1) by ethanolAfter multiple recrystallization purifications of the compound, the infrared spectrum is shown in fig. 2, and the data are as follows: 3442.2, 1550.2, 1476.0, 1382.3, 1326.9, 1183.7, 1301.5, 1182.9, 1126.8, 1033.3, 1007.7, 902.0, 802.1cm-1。
Example 3
The reactive dye of this example was synthesized in the same manner as in example 1 except that 17.3g (0.098mol) of orthanilic acid obtained in example 1 was replaced by 27.5g (0.098mol) of 4-sulfatosulfonylaniline, and the rest was the same as in example 1, to obtain the violet reactive dye having the following structure, wherein the yield was 76.9% (calculated by H acid charge). The infrared spectrum of the dye obtained after repeated recrystallization purification from a mixture of ethanol and water (2:1) is shown in FIG. 3, and the data are as follows: 3423.5, 1544.5, 1475.7, 1419.7, 1382.1, 1326.1, 1175.8, 1075.8, 1032.6, 957.5, 901.7, 795.2cm-1。
Example 4
The violet reactive dyes of examples 1, 2 and 3 were prepared as aqueous solutions having a concentration of 0.02g/L, and the visible absorption spectrum curves of the dyes were measured, and as shown in FIG. 4, the spectra showed a beautiful purple color by superimposing the absorption bands of the three chromophores. The molar extinction coefficient is shown in Table 1, and the dye is a purple dye with high color development intensity.
TABLE 1
Example 5
The purple reactive dyes in the embodiments 1, 2 and 3 are respectively used for printing cotton fabrics to obtain purple-tone printed fabrics with excellent color fastness, and the specific steps are as follows:
5 parts of urea, 1 part of anti-dyeing salt, 1.5 parts of baking soda, 5 parts of sodium alginate and 87.5 parts of warm water are mixed into paste in a container and fully stirred to be uniform, so as to prepare the printing paste. The dyes obtained in examples 1, 2 and 3 were each 0.5 part (1%), 1 part (2%), 2 parts (4%), 3 parts (6%), 4 parts (8%) and 5 parts (10%) and uniformly mixed with 49.5 parts, 49 parts, 48 parts, 47 parts, 46 parts and 45 parts of the above printing paste, respectively, to prepare a printing paste, and the cotton cloth was printed with a 200-mesh printing screen, baked at 105 ℃ for 4min and steamed for 8 min. Then washing with a large amount of cold water, soaping, washing with hot water, washing with cold water, and drying. The apparent color depth Integ value of the purple dye is tested, as shown in figure 5, the result shows that the color yield of the purple dye is gradually improved along with the increase of the dye concentration, and the dye has good promotion performance and can print deep and thick colors.
Example 6
The purple reactive dyes in examples 1, 2 and 3 are respectively blended according to the following cotton fabrics: 4g, dye: 1-10% (o.w.f), bath ratio: 1:20, sodium sulfate: 60g/L, sodium carbonate: 20 g/L; the dyeing is carried out by adopting a constant temperature dyeing method at 60 ℃, the dyeing process is shown in figure 6, the lifting force performance is measured, the result is shown in figure 7, the result shows that the color yield of the purple dye is gradually improved along with the increase of the dye concentration, and the dye has good lifting performance and can dye deep color.
Example 7
The various colorfastnesses of the cotton fabric dyed and printed at a dye concentration of 2% (printing: mass fraction, dyeing (o.w.f)) in this example were determined according to the international standards, rubbing fastness ISO 105-X12(2001), washing fastness ISO 105-C03(2010), and the results are shown in tables 2, 3. Tables 2 and 3 show that the purple reactive dye has good friction resistance and washing fastness, and can reach 3-4 grades and above.
TABLE 2 print fastness
TABLE 3 color fastness
Comparative example 1
The reactive black 5 is used as a comparative example, the fastness of the reactive black is shown in the table 4 under the same dyeing and printing conditions, and the results show that the fastness of the dye of the invention is 1-2 grades higher than that of the traditional dye.
TABLE 4 reactive Black 5 fastness
Claims (10)
1. A violet reactive dye based on a trisazo multichromosome, characterized in that the structural formula of the dye is as follows:
in the formula, R1And R2The method comprises the following steps:
2. A preparation method of purple reactive dye based on trisazo multichromophore comprises the following steps:
(1) dripping an H acid aqueous solution into the uniformly pulped cyanuric chloride suspension, and carrying out condensation reaction to obtain a condensed liquid, wherein the molar ratio of cyanuric chloride to H acid is 1.02: 1-1: 1;
(2) adding a hydrochloric acid solution into an aromatic primary amine aqueous solution containing sulfonic groups, dropwise adding a sodium nitrite solution while stirring, performing diazotization reaction, adding the obtained diazonium salt into the first condensate obtained in the step (1), and adjusting the pH value to 6.0-6.5 to perform coupling reaction to obtain a coupling solution, wherein the molar ratio of the aromatic primary amine containing sulfonic groups to the H acid in the step (1) is 0.97: 1-0.99: 1, and the molar ratio of the aromatic primary amine containing sulfonic groups to hydrochloric acid to sodium nitrite is 0.97:0.97: 1-1: 1: 1.1;
(3) adding 2, 4-diaminobenzene sulfonic acid into the coupling solution in the step (2), performing condensation reaction, adding hydrochloric acid solution into the obtained second condensate, dropwise adding sodium nitrite solution while stirring, and performing diazotization reaction to obtain second condensate diazonium salt, wherein the molar ratio of the 2, 4-diaminobenzene sulfonic acid to the H acid in the step (1) is 0.95: 1-0.98: 1, and the molar ratio of the second condensate, hydrochloric acid and sodium nitrite is 0.95:1.5: 1.1-1: 2: 1.2;
(4) adding a hydrochloric acid solution into an aromatic primary amine aqueous solution containing sulfonic groups, dropwise adding a sodium nitrite solution while stirring, performing diazotization reaction to obtain diazonium salt, adding H acid, and performing coupling reaction to obtain an acid coupling product, wherein the molar ratio of the aromatic primary amine containing the sulfonic groups to the H acid in the step (1) is 0.8: 1-0.9: 1, the molar ratio of the aromatic primary amine containing the sulfonic groups to hydrochloric acid to sodium nitrite is 0.8:0.8: 1-1: 1.1, and the molar ratio of the H acid to the aromatic primary amine containing the sulfonic groups is 0.8: 1-1: 1;
(5) and (3) adding the diazosalt of the second condensate obtained in the step (3) into the acid coupling product obtained in the step (4), adjusting the pH value to 6.0-6.5 for coupling reaction, salting out the obtained coupling solution, filtering and drying to obtain the purple reactive dye.
3. The method according to claim 2, wherein the pH value of the aqueous H acid solution in the step (1) is adjusted to 5.8-6.0 by using 10% by mass of sodium hydroxide; pulping the cyanuric chloride suspension for 0.5-0.8 h at the temperature of 0-2 ℃; the condensation reaction temperature is 0-5 ℃, the condensation reaction time is 3-5 h, and the condensation reaction pH value is 4-4.5.
4. The method according to claim 2, wherein the step (2) of adjusting the pH value to 6.0-6.5 comprises the following coupling reaction: adding 15 percent of Na by mass2CO3Adjusting the pH value of the solution to 6.0-6.5, reacting for 5-10min at 0-5 ℃, and then continuing to react for 4-6 h at 8-15 ℃.
5. The method according to claim 2, wherein the formula of the aromatic primary amine containing a sulfonic acid group in the steps (2) and (4) comprises:
wherein X is H, SO3M or OCH3And M ═ H or Na.
6. The method according to claim 2, wherein the diazotization reaction temperature in the steps (2), (3) and (4) is 0-5 ℃, and the diazotization reaction time is 1-3 h.
7. The method according to claim 2, wherein the condensation reaction temperature in the step (3) is 28-32 ℃, the condensation reaction time is 2-4 h, and the condensation reaction pH value is 3.5-4.5.
8. The method according to claim 2, wherein the temperature of the coupling reaction in the step (4) is 8-15 ℃, the time of the coupling reaction is 5-7 h, and the pH value of the coupling reaction is not adjusted.
9. The method according to claim 2, wherein the step (5) of adjusting the pH value to 6.0-6.5 comprises the following coupling reaction: adding 15 percent of Na by mass2CO3Adjusting the pH value of the solution to 6.0-6.5, reacting for 25-35 min at 0-5 ℃, and then continuing to react for 8-10 h at 20-25 ℃.
10. Use of the reactive dye according to claim 1 for dyeing or printing cotton, hemp, regenerated fibre, protein fibre or textiles thereof.
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| CN112940530A (en) * | 2021-01-21 | 2021-06-11 | 上海工程技术大学 | Active dye based on bromoaminoblue multichromosome, and preparation method and application thereof |
| CN113072819A (en) * | 2021-02-26 | 2021-07-06 | 上海工程技术大学 | Disperse dye special for anhydrous dyeing system and preparation and application thereof |
| CN114316626A (en) * | 2021-12-13 | 2022-04-12 | 湖北丽源科技股份有限公司 | Purple reactive dye and preparation method and application thereof |
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| CN1671800A (en) * | 2002-07-24 | 2005-09-21 | 西巴特殊化学品控股有限公司 | Fibre-reactive azo dyes, their preparation and their use |
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| CN112940530A (en) * | 2021-01-21 | 2021-06-11 | 上海工程技术大学 | Active dye based on bromoaminoblue multichromosome, and preparation method and application thereof |
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| CN113072819A (en) * | 2021-02-26 | 2021-07-06 | 上海工程技术大学 | Disperse dye special for anhydrous dyeing system and preparation and application thereof |
| CN114316626A (en) * | 2021-12-13 | 2022-04-12 | 湖北丽源科技股份有限公司 | Purple reactive dye and preparation method and application thereof |
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