CN114752229B - Reactive grey dye - Google Patents
Reactive grey dye Download PDFInfo
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- CN114752229B CN114752229B CN202210376030.7A CN202210376030A CN114752229B CN 114752229 B CN114752229 B CN 114752229B CN 202210376030 A CN202210376030 A CN 202210376030A CN 114752229 B CN114752229 B CN 114752229B
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- 238000004043 dyeing Methods 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000009833 condensation Methods 0.000 claims description 18
- 230000005494 condensation Effects 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000005457 ice water Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004537 pulping Methods 0.000 claims description 12
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- NWWAJXCJQQOLIU-UHFFFAOYSA-M sodium;2,3-diaminobenzenesulfonate Chemical compound [Na+].NC1=CC=CC(S([O-])(=O)=O)=C1N NWWAJXCJQQOLIU-UHFFFAOYSA-M 0.000 claims description 6
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- XSXHWVKGUXMUQE-UHFFFAOYSA-N osmium dioxide Inorganic materials O=[Os]=O XSXHWVKGUXMUQE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 239000012048 reactive intermediate Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 27
- 239000004744 fabric Substances 0.000 abstract description 21
- 239000000835 fiber Substances 0.000 abstract description 11
- 239000000985 reactive dye Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 32
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 description 16
- 229920000742 Cotton Polymers 0.000 description 14
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 description 10
- 238000007792 addition Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0072—Preparations with anionic dyes or reactive dyes
- C09B67/0073—Preparations of acid or reactive dyes in liquid form
-
- 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
- C09B62/515—Metal complex azo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or 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
- D06P1/384—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 not 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
- D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not 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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/06—After-treatment with organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coloring (AREA)
Abstract
The invention relates to a reactive gray dye, which belongs to the technical field of reactive dyes and comprises the following raw materials in parts by weight: 0.04-0.06 part of dyeing component, 7 parts of color fixing component, 100 parts of water and 5 parts of anhydrous sodium sulfate; the reactive gray dye contains a dyeing component of beta-sulfate ethyl sulfone active groups, and the required fixation temperature is generally 60 ℃, so that the reactive gray dye is convenient to process; the dyeing component structure contained in the prepared dyeing agent contains more hydrophilic groups, so that the dyeing agent has high solubility and symmetrical structure, and the reaction opportunity with fibers is improved; the color fixing component improves the stability of the dyeing component, improves the dyeing effect of the dye and improves the color fixing rate. The bonding stability of dyeing components on the fiber is improved, so that the dyed fabric has good sun-drying and wet-processing fastness.
Description
Technical Field
The invention belongs to the technical field of reactive dyes, and particularly relates to a reactive gray dye.
Background
Natural or synthetic polyamide fibers, wool, etc. may be dyed by complexing with reactive dyes and metal complex dyes. The need for improved quality and one-time success rate of dyeing on related fabrics with reactive dyes is highly desirable. Thus, there is a need for new reactive dye mixtures with improved properties, in particular the dyes should have a high reproducibility on dyeing, a high exhaustion rate, good leveling and a high fixation, and ease of cleaning of unfixed dyes. The known gray varieties do not meet these requirements in terms of overall performance.
Patent documents of patent numbers US482852, CN108559306 and CN105585874 disclose the preparation of reactive grey, in which the exhaustion rate and fixation rate of the dye are low and the residual amount of the dye in the sewage is large, so that the reactive grey is not suitable for dyeing fabrics, but is only suitable for printing fabrics. A black color disclosed in patent document US3484432 is suitable for dyeing, but is not commercially available due to the difficulty in producing intermediates.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention provides a reactive gray dye.
The aim of the invention can be achieved by the following technical scheme:
The reactive gray dye comprises the following raw materials in parts by weight: 0.04-0.06 part of dyeing component, 7 parts of color fixing component, 100 parts of water and 5 parts of anhydrous sodium sulfate;
The structural general formula of the dyeing component is as follows:
Further, D has the structural formula of
R 1 is H or SO 3 Na;
R 2 is-SO 2CH2CH2OSO2 OH;
X is halogen Cl;
n is 2;
Me is the element Cr or Co.
Further, the structure of the staining component is as follows:
Step S1, preparing a dyeing component:
Step S11, primary condensation: pulping 9.7g of cyanuric chloride and 100mL of ice water mixture for 30min, dissolving 55-58g of reaction intermediate with deionized water, adding sodium bicarbonate to adjust the pH value to 5-6, reacting for 6h, and maintaining the temperature in the range of 0-5 ℃ to obtain a condensate;
Step S12, secondary condensation: adding 21g of sodium diaminobenzene sulfonate aqueous solution into the first condensate, adjusting the pH value to 6-7 by sodium carbonate, and reacting for 8 hours at the temperature of 20-25 ℃ to obtain a second condensate;
Step S13, carrying out para-ester condensation: mixing 28.1-36g of para-ester and 150mL of ice-water mixture, and then adding 6g of sodium bicarbonate to stir and dissolve to obtain para-ester solution; pulping 9.7g of cyanuric chloride and 100mL of ice water mixture for 30min, then dropwise adding para-ester solution, controlling the pH value to be 2-3, adjusting the pH value to be 5-6 by sodium carbonate after the addition is finished, and reacting for 8h to obtain para-ester monocondensate;
And S14, mixing the di-shrinkage and the para-ester mono-shrinkage, heating to 35-40 ℃, adjusting the pH value to 5-6 by using sodium carbonate, reacting for 10 hours, and drying after the reaction is finished to obtain the dyeing component. In the prior art, the reactive dye containing the triazine active groups with two active chlorine atoms has the color fixing temperature of about 20-40 ℃ and the reactive dye containing the triazine active groups with one active chlorine atom has the color fixing temperature of about 90-95 ℃ and the reactive gray dye contains the dyeing component of the beta-sulfate ethyl sulfone active groups, and the color fixing temperature is generally 60 ℃.
The molecular structure of the reactive dye is composed of a dye matrix, a reactive group and a bridging group. In the dyeing process, the dye and the hydroxyl groups on the surface of the fiber are subjected to affinity substitution to form covalent bond combination, meanwhile, part of dyeing components are hydrolyzed to lose the bonding capability with the hydroxyl groups, after hydrolysis, the subsequent dyeing processing procedure is not enough, and in addition, the covalent bonds formed by the dyeing components and the fiber are unstable when meeting acid and alkali, so that in the storage process, acid gas and water are met, bond breakage can occur, and particularly under the damp-heat condition, the bond breakage is easier, and the dye has poor wet fastness.
Step S2, preparing a color fixing component:
S21, mixing 2, 4-dihydroxybenzophenone and epichlorohydrin, heating to 88 ℃, then adding sodium hydroxide aqueous solution to keep the temperature unchanged, continuing to react for 2 hours, washing the obtained reaction liquid with deionized water after the reaction is finished, drying the reaction liquid with anhydrous sodium sulfate, and removing a solvent by rotary evaporation to obtain an ultraviolet resistant component;
Step S22, mixing the ultraviolet-resistant component with water at the temperature of 50 ℃, then dropwise adding the mixture into a diethylenetriamine aqueous solution, then heating to 55 ℃, carrying out heat preservation reaction for 2 hours to obtain a mixed solution, dropwise adding the obtained mixed solution into epichlorohydrin, keeping the temperature at 55 ℃, continuing stirring and reacting for 2 hours, cooling to 35 ℃, regulating the pH value to about 8 by using sodium hydroxide, keeping the temperature unchanged, and reacting for 5 hours to obtain the color-fixing component.
Further, in step S21, the mass fraction of the aqueous sodium hydroxide solution is 50%; the dosage mass ratio of the 2, 4-dihydroxybenzophenone, the epichlorohydrin and the sodium hydroxide aqueous solution is 2.2:4.7:10; the dosage mass ratio of the ultraviolet resistant component, the diethylenetriamine and the epichlorohydrin in the step S22 is 2.7:2:5. according to the invention, the stability of the dyeing component is improved through the prepared fixation component, the dyeing effect of the dye is improved, one end of the epoxy group in the fixation component reacts with the hydroxyl group on the fiber, the other end of the epoxy group in the fixation component reacts with the sulfonic acid group in the dyeing component, and the fixation component can strengthen the covalent bond-formed dyeing component, so that the bond breaking phenomenon in the use and storage processes of the fabric is prevented; for the hydrolyzed dyeing component, the color fixing component can react with the hydrolyzed dyeing component to reestablish the connection, thereby improving the color fixing rate. The fixation component can also generate crosslinking reaction to form netlike macromolecules, and a protective layer is formed on the surface of the fiber, so that the bonding stability of the dyeing component on the fiber is improved.
Further, the para-ester in step S13 may be replaced with a sulfonated para-ester.
Further, the structure of the reaction intermediate in step S11 is
One of the following; prepared by the method of example 1 in patent US 3484432.
The invention has the beneficial effects that:
Aiming at the defects of the reactive dye in the prior art, the stability of the dyeing component is improved through the prepared fixation component, the dyeing effect of the dye is improved, and the fixation rate is improved. The bonding stability of the dyeing component on the fiber is improved. The reactive gray dye contains a dyeing component of beta-sulfate ethyl sulfone active groups, and the required fixation temperature is generally 60 ℃, so that the reactive gray dye is convenient to process.
The dyeing component structure contained in the prepared dyeing agent contains more hydrophilic groups, so that the dyeing agent has high solubility and symmetrical structure, the reaction opportunity with fibers is improved, and the self-made color fixing agent is added, so that the dyed fabric has good sunlight and wet-proof fastness.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing a color fixing component:
S21, mixing 2, 4-dihydroxybenzophenone and epichlorohydrin, heating to 88 ℃, then adding sodium hydroxide aqueous solution to keep the temperature unchanged, continuing to react for 2 hours, washing the obtained reaction liquid with deionized water after the reaction is finished, drying the reaction liquid with anhydrous sodium sulfate, and removing a solvent by rotary evaporation to obtain an ultraviolet resistant component; the mass fraction of the sodium hydroxide aqueous solution is 50%; the dosage mass ratio of the 2, 4-dihydroxybenzophenone, the epichlorohydrin and the sodium hydroxide aqueous solution is 2.2:4.7:10;
Step S22, mixing the ultraviolet-resistant component with water at the temperature of 50 ℃, then dropwise adding the mixture into a diethylenetriamine aqueous solution, then heating to 55 ℃, carrying out heat preservation reaction for 2 hours to obtain a mixed solution, dropwise adding the obtained mixed solution into epichlorohydrin, keeping the temperature at 55 ℃, continuing stirring and reacting for 2 hours, cooling to 35 ℃, regulating the pH value to about 8 by using sodium hydroxide, keeping the temperature unchanged, and reacting for 5 hours to obtain the color-fixing component. The dosage mass ratio of the ultraviolet resistant component, the diethylenetriamine and the epichlorohydrin is 2.7:2:5.
Example 2
Preparing a dyeing component:
step S11, primary condensation: pulping 9.7g of cyanuric chloride and 100mL of ice water mixture for 30min, dissolving 55g of reaction intermediate with deionized water, adding sodium bicarbonate to adjust the pH value to 5, reacting for 6h, and maintaining the temperature in the range of 0-5 ℃ to obtain a condensate;
step S12, secondary condensation: adding 21g of sodium diaminobenzene sulfonate aqueous solution into the first condensate, adjusting the pH value to 6 by sodium carbonate, and reacting for 8 hours at the temperature of 20 ℃ to obtain a second condensate;
step S13, carrying out para-ester condensation: mixing 28.1g of para-ester with 150mL of ice-water mixture, and then adding 6g of sodium bicarbonate to stir and dissolve to obtain para-ester solution; pulping 9.7g of cyanuric chloride and 100mL of ice water mixture for 30min, then dropwise adding para-ester solution, controlling the pH value to be 2-3, adjusting the pH value to be 5 by sodium carbonate after the addition is finished, and reacting for 8h to obtain para-ester monocondensate;
and S14, mixing the di-condensate and the para-ester mono-condensate, heating to 35 ℃, adjusting the pH value to 5 by using sodium carbonate, reacting for 10 hours, and drying after the reaction is finished to obtain the dyeing component (I).
Wherein the structure of the reaction intermediate in the step S11 is
Example 3
Preparing a dyeing component:
step S11, primary condensation: pulping 9.7g of cyanuric chloride and 100mL of ice water mixture for 30min, dissolving 55g of reaction intermediate with deionized water, adding sodium bicarbonate to adjust the pH value to 5, reacting for 6h, and maintaining the temperature in the range of 0-5 ℃ to obtain a condensate;
step S12, secondary condensation: adding 21g of sodium diaminobenzene sulfonate aqueous solution into the first condensate, adjusting the pH value to 6 by sodium carbonate, and reacting for 8 hours at the temperature of 20 ℃ to obtain a second condensate;
step S13, carrying out para-ester condensation: 36g of sulfonated para-ester and 150mL of ice-water mixture are mixed, and then 6g of sodium bicarbonate is added to be stirred and dissolved, so as to obtain para-ester solution; pulping 9.7g of cyanuric chloride and 100mL of ice water mixture for 30min, then dropwise adding para-ester solution, controlling the pH value to be 2-3, adjusting the pH value to be 5 by sodium carbonate after the addition is finished, and reacting for 8h to obtain para-ester monocondensate;
And S14, mixing the di-condensate and the para-ester mono-condensate, heating to 35 ℃, adjusting the pH value to 5 by using sodium carbonate, reacting for 10 hours, and drying after the reaction is finished to obtain the dyeing component (II).
Wherein the structure of the reaction intermediate in the step S11 is
Example 4
Preparing a dyeing component:
Step S11, primary condensation: pulping 9.7g of cyanuric chloride and 100mL of ice water mixture for 30min, dissolving 58g of reaction intermediate with deionized water, adding sodium bicarbonate to adjust the pH value to 6, reacting for 6h, and maintaining the temperature in the range of 0-5 ℃ to obtain a condensate;
Step S12, secondary condensation: adding 21g of sodium diaminobenzene sulfonate aqueous solution into the first condensate, adjusting the pH value to 7 by sodium carbonate, and reacting for 8 hours at the temperature of 25 ℃ to obtain a second condensate;
Step S13, carrying out para-ester condensation: mixing 28.1g of para-ester with 150mL of ice-water mixture, and then adding 6g of sodium bicarbonate to stir and dissolve to obtain para-ester solution; pulping 9.7g of cyanuric chloride and 100mL of ice water mixture for 30min, then dropwise adding para-ester solution, controlling the pH value to be 2-3, adjusting the pH value to be 6 by sodium carbonate after the addition is finished, and reacting for 8h to obtain para-ester monocondensate;
And S14, mixing the di-condensate and the para-ester mono-condensate, heating to 40 ℃, adjusting the pH value to 6 by using sodium carbonate, reacting for 10 hours, and drying after the reaction is finished to obtain the dyeing component (III).
Wherein the structure of the reaction intermediate in the step S11 is
Example 5
Preparing a dyeing component:
Step S11, primary condensation: pulping 9.7g of cyanuric chloride and 100mL of ice water mixture for 30min, dissolving 58g of reaction intermediate with deionized water, adding sodium bicarbonate to adjust the pH value to 6, reacting for 6h, and maintaining the temperature in the range of 0-5 ℃ to obtain a condensate;
Step S12, secondary condensation: adding 21g of sodium diaminobenzene sulfonate aqueous solution into the first condensate, adjusting the pH value to 7 by sodium carbonate, and reacting for 8 hours at the temperature of 25 ℃ to obtain a second condensate;
Step S13, carrying out para-ester condensation: 36g of sulfonated para-ester and 150mL of ice-water mixture are mixed, and then 6g of sodium bicarbonate is added to be stirred and dissolved, so as to obtain para-ester solution; pulping 9.7g of cyanuric chloride and 100mL of ice water mixture for 30min, then dropwise adding para-ester solution, controlling the pH value to be 2-3, adjusting the pH value to be 6 by sodium carbonate after the addition is finished, and reacting for 8h to obtain para-ester monocondensate;
And S14, mixing the di-condensate and the para-ester mono-condensate, heating to 40 ℃, adjusting the pH value to 6 by using sodium carbonate, reacting for 10 hours, and drying after the reaction is finished to obtain the dyeing component (IV).
Wherein the structure of the reaction intermediate in the step S11 is
Example 6
By weight, 0.04 part of the dyeing component prepared in example 2, 100 parts of water and 5 parts of anhydrous sodium sulfate are uniformly stirred, then cotton cloth is added into the mixture, heating is carried out at 1 ℃/min, heat is preserved for 30min at 60 ℃, then 7 parts of the color fixing agent prepared in example 1 is added, and color fixing is carried out for 45min, thus obtaining gray black cotton cloth.
Example 7
By weight, 0.05 part of the dyeing component prepared in example 3, 100 parts of water and 5 parts of anhydrous sodium sulfate are uniformly stirred, then cotton cloth is added into the mixture, heating is carried out at 1 ℃/min, heat is preserved for 30min at 60 ℃, then 7 parts of the color fixing agent prepared in example 1 is added, and color fixing is carried out for 45min, thus obtaining gray black cotton cloth.
Example 8
By weight, 0.05 part of the dyeing component prepared in example 4, 100 parts of water and 5 parts of anhydrous sodium sulfate are uniformly stirred, then cotton cloth is added into the mixture, heating is carried out at 1 ℃/min, heat is preserved for 30min at 60 ℃, then 7 parts of the color fixing agent prepared in example 1 is added, and color fixing is carried out for 45min, thus obtaining gray black cotton cloth.
Example 9
By weight, 0.06 part of the dyeing component prepared in example 5, 100 parts of water and 5 parts of anhydrous sodium sulfate are uniformly stirred, then cotton cloth is added into the mixture, heating is carried out at 1 ℃/min, heat is preserved for 30min at 60 ℃, then 7 parts of the color fixing agent prepared in example 1 is added, and color fixing is carried out for 45min, thus obtaining gray black cotton cloth.
Comparative example 1
By weight, 0.06 part of the dyeing component prepared in example 5, 100 parts of water and 5 parts of anhydrous sodium sulfate are uniformly stirred, then cotton cloth is added into the mixture, heating is carried out at 1 ℃/min, heat preservation is carried out at 60 ℃ for 30min, then 7 parts of sodium carbonate is added, and fixation is carried out for 45min, thus obtaining gray black cotton cloth.
Comparative example 2
By weight, 0.06 part of the dyeing component prepared in example 5, 100 parts of water and 5 parts of anhydrous sodium sulfate were stirred uniformly, then cotton cloth was added thereto, heating was performed at 1 ℃/min, and heat was preserved at 60 ℃ for 30min, to obtain gray black cotton cloth.
The gray black cotton cloth prepared in examples 6-9 and comparative examples 1-2 was tested; gray black cotton cloth is tested according to GB/T2391, ISO205C04, ISO105B02, ISO105E04 and ISO105-X12 detection standards; testing the properties of the dye;
The test results are shown in table 1 below:
TABLE 1
As can be seen from the above Table 1, the dyeing composition structure of the dyeing agent prepared by the invention contains more hydrophilic groups, so that the dyeing agent has high solubility and symmetrical structure, the reaction opportunity with the fiber is improved, and the self-made color fixing agent is added, so that the dyed fabric has good light fastness and wet fastness.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (5)
1. The reactive gray dye is characterized by comprising the following raw materials in parts by weight: 0.04-0.06 part of dyeing component, 7 parts of color fixing component, 100 parts of water and 5 parts of anhydrous sodium sulfate;
The structural general formula of the dyeing component is as follows:
the structural formula of D in the general formula is R 1 is H or SO 3Na;R2 is-SO 2CH2CH2OSO2 OH; x is halogen Cl; n is 2; me is the element Cr or Co.
2. A reactive grey dye according to claim 1, wherein the dyeing component is prepared by:
Step S11, primary condensation: pulping the mixture of cyanuric chloride and ice water for 30min, dissolving the reaction intermediate with deionized water, adding the solution, adjusting the pH value to 5-6, reacting for 6h, and maintaining the temperature in the range of 0-5 ℃ to obtain a condensate;
Step S12, secondary condensation: adding sodium diaminobenzenesulfonate aqueous solution into the first condensate, adjusting pH value to 6-7, and reacting at 20-25deg.C for 8 hr to obtain second condensate;
step S13, carrying out para-ester condensation: mixing para-ester and ice-water mixture, adding sodium bicarbonate, stirring and dissolving to obtain para-ester solution; pulping a cyanuric chloride and ice water mixture for 30min, then dropwise adding a para-ester solution, controlling the pH value to be 2-3, adjusting the pH value to be 5-6 after the adding is finished, and reacting for 8h to obtain a para-ester-condensed product;
and step S14, mixing the di-shrinkage and the para-ester mono-shrinkage, heating to 35-40 ℃, adjusting the pH value to 5-6, reacting for 10 hours, and drying after the reaction is finished to obtain the dyeing component.
3. A reactive grey dye according to claim 2, wherein the para-ester in step S13 is replaced by a sulphonated para-ester.
4. A reactive grey dye according to claim 2, wherein the reactive intermediate in step S11 has the structure
One of them.
5. A reactive grey dye according to claim 1, characterized in that the fixing component is prepared by the steps of:
Mixing 2, 4-dihydroxybenzophenone and epichlorohydrin, heating to 88 ℃, then adding sodium hydroxide aqueous solution to keep the temperature unchanged, and continuing to react for 2 hours to obtain an ultraviolet resistant component;
Mixing the ultraviolet-resistant component with water at 50 ℃, then dropwise adding the mixture into a diethylenetriamine aqueous solution, then heating to 55 ℃, carrying out heat preservation reaction for 2 hours to obtain a mixed solution, dropwise adding the obtained mixed solution into epichlorohydrin, keeping the temperature at 55 ℃, continuing stirring and reacting for 2 hours, cooling to 35 ℃, regulating the pH value to about 8, keeping the temperature unchanged, and reacting for 5 hours to obtain the color-fixing component.
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| CN105585874A (en) * | 2015-12-28 | 2016-05-18 | 浙江劲光实业股份有限公司 | Gray reactive dye and preparation method thereof |
| CN108559306A (en) * | 2018-05-18 | 2018-09-21 | 无锡润新染料有限公司 | A kind of grey dyestuff cleanly production technique of the activity for the stamp can be used for people cotton |
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| CN105585874A (en) * | 2015-12-28 | 2016-05-18 | 浙江劲光实业股份有限公司 | Gray reactive dye and preparation method thereof |
| CN108559306A (en) * | 2018-05-18 | 2018-09-21 | 无锡润新染料有限公司 | A kind of grey dyestuff cleanly production technique of the activity for the stamp can be used for people cotton |
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