CN109021614B - Phthalocyanine azo-based double-chromophore reactive dye with high fixation rate and preparation method and application thereof - Google Patents

Phthalocyanine azo-based double-chromophore reactive dye with high fixation rate and preparation method and application thereof Download PDF

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CN109021614B
CN109021614B CN201811004414.6A CN201811004414A CN109021614B CN 109021614 B CN109021614 B CN 109021614B CN 201811004414 A CN201811004414 A CN 201811004414A CN 109021614 B CN109021614 B CN 109021614B
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侯爱芹
谢孔良
胡柳
高爱芹
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    • 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
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/10—Porphines; Azaporphines
    • 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
    • C09B67/0003—Drying, e.g. sprax drying; Sublimation of the solvent
    • 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

Abstract

The invention relates to a phthalocyanine azo-based double-chromophore reactive dye with high fixation rate and a preparation method and application thereof. The reactive dye is suitable for printing cotton, artificial cotton, hemp, regenerated fiber and textiles thereof, has high color fixing rate, bright color, excellent promotion, good fastness to washing and rubbing and good application prospect.

Description

Phthalocyanine azo-based double-chromophore reactive dye with high fixation rate and preparation method and application thereof
Technical Field
The invention belongs to the field of reactive dyes, and particularly relates to phthalocyanine azo-based double-chromophore reactive dyes with high fixation rate, and a preparation method and application thereof.
Background
Since the advent of reactive dyes, the reactive dyes have become the most important class of cotton reactive dyes, and are bright in color, complete in color spectrum, low in cost and important in development all the time. The reactive dye molecule consists of a water-soluble group, a dye matrix, a connecting group and an active group, and the dye molecule can be hydrolyzed in the application process so as to lose the capability of reacting with fibers, thereby reducing the utilization rate of the dye, causing the problem of ecological environmental protection by discharged dye wastewater and having certain harm to human bodies. Therefore, the development of novel reactive dyes with high fixation rate is of great significance. The copper phthalocyanine reactive dye occupies an important position in the reactive dye, has bright color, high molar extinction coefficient and excellent light fastness, but has low affinity to fiber and low fixation rate, and the fixation rate of the traditional copper phthalocyanine No. 21 reactive turquoise blue is only 40-50 percent, the dye utilization rate is low, the discharge amount of dyeing sewage is large, the depth of wastewater is deep, the dye leveling property is poor, and the clean production of printing and dyeing is not facilitated. The invention of copper phthalocyanine reactive dye with high fixation rate and high utilization rate is urgently needed. The development of phthalocyanine azo mixed color body reactive dyes with high fixation rate is an important research direction and has important significance for printing and dyeing clean production.
Disclosure of Invention
The invention provides phthalocyanine azo-based double-chromophore reactive dyes with high fixation rate, a preparation method and application thereof, and the reactive dyes solve the technical problem of low fixation rate of the existing copper phthalocyanine reactive dyes.
The invention provides phthalocyanine azo-based double-chromophore reactive dyes with high fixation rate, which is characterized in that: the general structural formula is as follows:
Figure GDA0002623225560000011
Figure GDA0002623225560000021
in the formula, x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 2, z is more than 0 and less than or equal to 2, and x + y + z is 3.5-4.
The invention also provides a preparation method of the phthalocyanine azo-based double-chromophore reactive dye with high fixation rate, which comprises the following steps:
(1) adding chlorosulfonic acid into a reaction container at room temperature, adding copper phthalocyanine under stirring at room temperature, performing sulfonation reaction, adding thionyl chloride for chlorination reaction after the reaction is finished, adding a reaction system into ice water, and performing suction filtration to obtain copper phthalocyanine sulfonyl chloride; wherein the molar ratio of the copper phthalocyanine to the chlorosulfonic acid to the thionyl chloride is 1-2: 40-50: 20-25;
(2) preparing the copper phthalocyanine sulfonyl chloride in the step (1) into a solution, pulping, adding a 2, 4-diaminobenzene sodium sulfonate solution and pyridine for reaction, and adding ammonia water for continuous reaction to obtain a turquoise blue base solution; wherein the molar ratio of the copper phthalocyanine sulfonyl chloride to the 2, 4-diaminobenzene sulfonic acid sodium salt to the ammonia water is 1: 1-2: 1-3;
(3) preparing cyanuric chloride into a solution, pulping, adding the turquoise blue base solution obtained in the step (2), and stirring for reaction to obtain a condensate; wherein the molar ratio of the turquoise blue group to the cyanuric chloride is 1: 1.02-2.04;
(4) adding 2, 4-diaminobenzene sulfonic acid sodium into the first condensate solution in the step (3), and stirring for reaction to obtain a second condensate; wherein the molar ratio of the condensate to the 2, 4-diaminobenzene sulfonic acid sodium salt is 1: 1-2;
(5) cooling the secondary condensate solution in the step (4) in an ice water bath, adding concentrated hydrochloric acid, dropwise adding a sodium nitrite solution, and keeping the temperature of-5-0 ℃ for continuous reaction for 1.5-2 hours after the dropwise adding is finished to obtain diazonium salt; wherein the molar ratio of the second condensate to the concentrated hydrochloric acid to the sodium nitrite is 1: 2-3: 1-2;
(6) preparing cyanuric chloride into solution, pulping, adding Rn1Solution reaction to obtain Rn1A condensate is added with Rn after the reaction is finished2Dry powder to obtain Rn1A second condensate; wherein Rn1Cyanuric chloride and Rn2In a molar ratio of 1:1.02: 1;
(7) cooling the secondary condensate in the step (6), adding the secondary condensate into the diazonium salt in the step (5), and performing coupling reaction; wherein the molar ratio of the diazonium salt to the polycondensate in the step (6) is 1: 1-2.
The sulfonation temperature in the step (1) is 130-140 ℃, and the sulfonation time is 3-6 h; the chlorination temperature is 90-105 ℃, and the chlorination time is 1-3 h.
The mass fraction of the copper phthalocyanine sulfonyl chloride solution in the step (2) is 10-20%, the pulping temperature is 0-5 ℃, and the time is 50-70 min; the mass fraction of the 2, 4-diaminobenzene sulfonic acid sodium salt solution is 10-20%.
The reaction conditions after adding the 2, 4-diaminobenzene sodium sulfonate in the step (2) are as follows: the pH value is 6.5-7, and the reaction is carried out for 5-7 h under the condition of 10-20 ℃; the reaction conditions after adding ammonia water are as follows: the pH value is 9-10, the temperature is 30-35 ℃, the reaction is carried out for 4-5 h, and then the reaction is carried out for 2-3 h at the pH value of 9-10 and the temperature of 40-50 ℃.
The mass fraction of the cyanuric chloride solution in the step (3) is 10-20%, the pulping temperature is 0-2 ℃, and the pulping time is 20-40 min; pre-cooling the turquoise blue base solution to below 5 ℃, and reducing the pH value to 6; the reaction temperature is 0-10 ℃, the pH value is adjusted to 3-5, and the reaction time is 7-12 h.
The reaction temperature in the step (4) is 35-40 ℃, the pH value is adjusted to 7-9, and the reaction time is 10-12 h.
The mass fraction of the cyanuric chloride solution in the step (6) is 10-20%, the pulping temperature is 0-2 ℃, and the pulping time is 20-40 min; the first condensation reaction temperature is 0-5 ℃, the reaction pH value is 3-3.5, and the reaction time is 1-2 h; the temperature of the secondary condensation reaction is 30-35 ℃, the pH value of the reaction is 4-4.5, and the reaction time is 5-6 h.
Rn in the step (6)1Is 1-amino-8-naphthol-3, 6-disulfonic acid sodium salt, 2-amino-5-hydroxy-7-naphthalenesulfonic acid or 1-hydroxy-7-amino-3-naphthalenesulfonic acid; rn2Is 4-beta-ethyl sulfuryl sulfate aniline or 3-beta-ethyl sulfuryl sulfate aniline.
The coupling reaction temperature in the step (7) is 10-15 ℃, the pH value is 5.5-6.5, and the reaction time is 6-7 h.
The invention also provides application of the phthalocyanine azo-based double-chromophore reactive dye with high fixation rate, and the phthalocyanine azo-based double-chromophore reactive dye is prepared into a dry powder product after spray drying treatment.
The phthalocyanine azo-based double-color-body reactive dye with high fixation rate can also contain a part of other dye components and a part of impurities, because the dye inevitably contains a small part of impurities and electrolytic powder (sodium chloride and the like) in the conventional synthesis or salting-out process, and the existence of the substances does not influence the technical effect of the invention.
The invention also provides a reactive dye composition printing dye with high color fixing rate for textile products such as cotton, hemp, regenerated fiber and the like.
Advantageous effects
(1) According to the invention, the conjugated azo group is introduced into the copper phthalocyanine molecule, so that the affinity of the copper phthalocyanine dye to cellulose fiber is greatly improved, and a reactive dye with a color fixing rate close to 100% is obtained;
(2) the invention introduces phthalocyanine and azo mixed color system in the molecule, the structure is novel, the molar extinction coefficient is high, and the problems of poor compatibility and color fastness of dye color matching and the like are solved;
(3) the reactive dye with high color fixing rate prepared by the invention is used for printing cotton, hemp and regenerated fiber fabrics, has high dye utilization rate, good lifting power, excellent color fastness and good application prospect.
Drawings
FIG. 1 is a graph of the infrared spectrum of a high fixation reactive dye of example 1;
FIG. 2 is a graph of the infrared spectrum of a high fixation reactive dye of example 2;
FIG. 3 is a graph of the infrared spectrum of a high fixation reactive dye of example 3;
FIG. 4 is a graph of the UV-VIS absorption spectrum of a high fixation reactive dye of example 4;
FIG. 5 is a graph of the printed fixation curves of high fixation reactive dyes on cotton fabric in example 5;
FIG. 6 is a graph of the printing lifting force of the reactive dye with high fixation ratio on the cotton fabric in example 5.
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.
Example 1
Synthesizing the mixed chromogen reactive dye with high fixation rate, wherein the structure is as follows:
Figure GDA0002623225560000041
(1) preparation of copper phthalocyanine sulfonylchloride: under the condition of room temperature, adding 80mL of chlorosulfonic acid into a three-neck flask provided with a reflux condenser tube and a tail gas absorption device, adding 15g of copper phthalocyanine under stirring, heating to 135 ℃ for reaction for 5h, cooling to 60 ℃, adding 22mL of thionyl chloride, heating to 100 ℃ for reaction for 2h, cooling to below 30 ℃, slowly adding the system into ice water under the condition of stirring, carrying out suction filtration, and washing a filter cake with a proper amount of ice water to obtain 58g of copper phthalocyanine sulfonyl chloride filter cake.
(2) Preparation of copper phthalocyanine turquoise blue base: pulping the copper phthalocyanine sulfonyl chloride in the step (1) for 1h under the ice-water bath condition. Accurately weighing 5.04g of 2, 4-diaminobenzene sodium sulfonate (m-bis) to prepare a 15% solution, adjusting the pH value to 6-6.5 by using sodium carbonate, dropwise adding the solution into uniformly pulped copper phthalocyanine sulfonyl chloride, and adding a proper amount of pyridine as a catalyst. Reacting for 7 hours under the conditions that the pH value is 6.5-7 and the temperature is 15-20 ℃, heating to 30-35 ℃, adding 1.03mL of 20% ammonia water, then reacting for 5 hours, heating the pH value to 9-10, heating to 40-45 ℃, reacting for 3 hours, and detecting the reaction end point by using a thin layer chromatography.
(3) Preparation of turquoise blue base condensate: weighing 5.11g of cyanuric chloride to prepare a 20% solution, and pulping in ice water at 0-2 ℃ for 30 min. And (3) cooling the turquoise blue base solution obtained in the step (2) to below 5 ℃, reducing the pH value to 6, dropwise adding into cyanuric chloride, reacting at the temperature of 0-10 ℃, at the pH value of 4-5 for 12h, and detecting the reaction end point by using thin-layer chromatography.
(4) Preparation of the second condensate: and (3) adding 5.04g of 2, 4-diaminobenzene sulfonic acid dry powder into the primary condensed liquid in the step (3), heating to 35-40 ℃, raising the pH to 7-8, reacting for 7 hours, and detecting the reaction end point by using a thin layer chromatography.
(5) Preparation of diazonium salt: and (3) cooling the copper phthalocyanine secondary condensate obtained in the step (4) to below 5 ℃ in an ice water bath, adding 5.20g of concentrated hydrochloric acid solution with the mass fraction of 36.5%, slowly dripping 1.82g of sodium nitrite prepared 30% aqueous solution within 1 hour, and reacting for 1.5 hours at the temperature of-5-0 ℃ after dripping.
(6) 1-amino-8-naphthol-3, 6-sodium disulfonate condensate and dimer condensate preparation: while the reaction is carried out, 5.11g of cyanuric chloride is weighed to prepare a 20% solution, and the solution is pulped in ice water for 30min at the temperature of 0-2 ℃. Preparing 10.26g of 1-amino-8-naphthol-3, 6-disulfonic acid into a 15% solution, adjusting the pH value to be 5.8-6.0, dropwise adding into cyanuric chloride, reacting for 1h at 0-5 ℃ and under the condition that the pH value is 3-3.5, and detecting the reaction end point by utilizing thin-layer chromatography. And after the first condensation reaches the reaction end point, adding 7.62g of 4-beta-ethyl sulfuryl sulfate aniline (para-ester) dry powder into the first condensation, heating to 30-35 ℃, adjusting the pH value to 4-4.5, reacting for 5h, and detecting the reaction end point by using thin layer chromatography.
(7) Coupling reaction: and (3) cooling the secondary condensate in the step (6) to 5 ℃, adding the secondary condensate into the copper phthalocyanine diazonium salt prepared in the step (5), reacting for 7 hours under the conditions of 10-15 ℃ and pH value of 5.5-6.5, and detecting the reaction end point by using thin layer chromatography. And drying the obtained product at the temperature of 65 ℃ to obtain the reactive dye with high fixation rate. Yield 63%, salting out of the dye, DMF-CH2Cl2Recrystallization purification, and its infrared spectrum is shown in FIG. 1.
The dye is 3334.35cm-1The strong broad peak of (A) is a broad peak formed by stretching vibration of N-H and OH; the weak absorption peak at 2989.34 is CH2The stretching vibration absorption peak of (1); 1544.61cm-1The absorption of (a) is C ═ N stretching vibration absorption peak; 1483.73cm-1The absorption of (a) is a characteristic absorption peak of the benzene ring; 1391.10cm-1The absorption of (a) is a C-N telescopic vibration absorption peak on the isoindole ring; 1323.02cm-1The absorption peak of (1) is a broad peak formed by S ═ O stretching vibration and phthalocyanine ring characteristic absorption; 1138.15, 1088.35cm-1And 1037.35cm-1Characteristic absorption peak of phthalocyanine ring; 741.27cm-1Is the stretching vibration peak of C-S and C-Cl; 907.86cm-1Is a Cu-N vibration absorption peak.
Example 2
The synthesis process of the mixed chromogen reactive dye with high fixation rate comprises the following steps:
Figure GDA0002623225560000061
(1) preparation of copper phthalocyanine sulfonylchloride: under the condition of room temperature, adding 80mL of chlorosulfonic acid into a three-neck flask provided with a reflux condenser tube and a tail gas absorption device, adding 15g of copper phthalocyanine under stirring, heating to 135 ℃ for reaction for 5h, cooling to 60 ℃, adding 22mL of thionyl chloride, heating to 100 ℃ for reaction for 2h, cooling to below 30 ℃, slowly adding the system into ice water under the condition of stirring, carrying out suction filtration, and washing a filter cake with a proper amount of ice water to obtain 58g of copper phthalocyanine sulfonyl chloride filter cake.
(2) Preparation of copper phthalocyanine turquoise blue base: pulping the copper phthalocyanine sulfonyl chloride in the step (1) for 1h under the ice-water bath condition. Accurately weighing 5.04g of 2, 4-diaminobenzene sulfonic acid sodium salt (m-bis) to prepare a 15% solution, adjusting the pH value to 6-6.5, dropwise adding the solution into uniformly pulped copper phthalocyanine sulfonyl chloride, and adding a proper amount of pyridine as a catalyst. Reacting for 7 hours under the conditions that the pH value is 6.5-7 and the temperature is 15-20 ℃, heating to 30-35 ℃, adding 1.03mL of ammonia water for reacting for 5 hours, then heating the pH value to 9-10, heating to 40-45 ℃, reacting for 3 hours, and detecting the reaction end point by utilizing thin layer chromatography.
(3) Preparation of turquoise blue base condensate: weighing 5.11g of cyanuric chloride to prepare a 20% solution, and pulping for 1 hour in ice water at the temperature of 0-2 ℃. And (3) cooling the turquoise blue base solution obtained in the step (2) to below 5 ℃, reducing the pH value to 6, dropwise adding into cyanuric chloride, reacting at the temperature of 0-10 ℃, at the pH value of 4-5 for 12h, and detecting the reaction end point by using thin-layer chromatography.
(4) Preparation of the second condensate: and (3) adding 5.04g of 2, 4-diaminobenzene sulfonic acid sodium salt dry powder into the primary condensed liquid obtained in the step (3), heating to 35-40 ℃, raising the pH to 7-8, reacting for 7 hours, and detecting the reaction end point by using a thin layer chromatography.
(5) Preparation of diazonium salt: and (3) cooling the secondary condensate obtained in the step (4) to below 5 ℃ in an ice water bath, adding 5.20g of concentrated hydrochloric acid solution with the mass fraction of 36.5%, slowly dripping 1.82g of 30% aqueous solution prepared from sodium nitrite in 1h, and reacting for 1.5h at the temperature of-5-0 ℃.
(6) Preparation of 2-amino-5-hydroxy-7-naphthalenesulfonic acid condensates and condensates: while the reaction is carried out, 5.11g of cyanuric chloride is weighed to prepare a 20% solution, and the solution is pulped in ice water for 30min at the temperature of 0-2 ℃. Preparing 10.26g of 1-amino-8-naphthol-3, 6-disulfonic acid into a 15% solution, adjusting the pH value to be 5.8-6.0, dropwise adding into cyanuric chloride, reacting for 1h at 0-5 ℃ and under the condition that the pH value is 3-3.5, and detecting the reaction end point by utilizing thin-layer chromatography. The end of the reaction was detected by thin layer chromatography. And after the first condensation reaches the reaction end point, adding 7.62g of 4-beta-ethyl sulfuryl sulfate aniline dry powder into the first condensation, heating to 30-35 ℃, adjusting the pH value to 4-4.5, reacting for 7h, and detecting the reaction end point by using thin layer chromatography.
(7) Coupling reaction: and (3) cooling the secondary condensate in the step (6) to below 5 ℃, adding the secondary condensate into the diazonium salt prepared in the step (5), reacting for 7 hours at the temperature of 10-15 ℃ and under the condition that the pH value is 5.5-6.5, and detecting the reaction end point by utilizing thin-layer chromatography. And drying the obtained product at the temperature of 65 ℃ to obtain the reactive dye with high fixation rate. Yield 55.3%, salting out of dye, DMF-CH2Cl2Recrystallization purification, and its infrared spectrum is shown in FIG. 2.
The dye is 3373.31cm-1The strong broad peak of (A) is a broad peak formed by stretching vibration of N-H and OH; the weak absorption peak at 2996.38 is CH2The stretching vibration absorption peak of (1); 1547.25cm-1The absorption of (a) is C ═ N stretching vibration absorption peak; 1480.54cm-1The absorption of (a) is a characteristic absorption peak of the benzene ring; 1381.71cm-1The absorption of (a) is a C-N telescopic vibration absorption peak on the isoindole ring; 1135.06, 1087.49cm-1And 1047.71cm-1Characteristic absorption peak of phthalocyanine ring; 739.43cm-1Is the stretching vibration peak of C-S and C-Cl; 906.04cm-1Is a Cu-N vibration absorption peak.
Example 3
The synthesis process of the mixed chromogen reactive dye with high fixation rate comprises the following steps:
Figure GDA0002623225560000071
(1) preparation of copper phthalocyanine sulfonylchloride: under the condition of room temperature, adding 80mL of chlorosulfonic acid into a three-neck flask provided with a reflux condenser tube and a tail gas absorption device, adding 15g of copper phthalocyanine under stirring, heating to 135 ℃ for reaction for 5h, cooling to 60 ℃, adding 22mL of thionyl chloride, heating to 100 ℃ for reaction for 2h, cooling to below 30 ℃, slowly adding the system into ice water under the condition of stirring, carrying out suction filtration, and washing a filter cake with a proper amount of ice water to obtain 58g of copper phthalocyanine sulfonyl chloride filter cake.
(2) Preparation of copper phthalocyanine turquoise blue base: pulping the copper phthalocyanine sulfonyl chloride in the step (1) for 1h under the ice-water bath condition. Accurately weighing 5.04g of 2, 4-diaminobenzene sulfonic acid sodium salt (m-bis) to prepare a 15% solution, adjusting the pH value to 6-6.5, dropwise adding the solution into uniformly pulped copper phthalocyanine sulfonyl chloride, and adding a proper amount of pyridine as a catalyst. Reacting for 7 hours under the conditions that the pH value is 6.5-7 and the temperature is 15-20 ℃, heating to 30-35 ℃, adding 1.03mL of ammonia water for reacting for 5 hours, then heating the pH value to 9-10, heating to 40-45 ℃, reacting for 3 hours, and detecting the reaction end point by utilizing thin layer chromatography.
(3) Preparation of turquoise blue base condensate: weighing 5.11g of cyanuric chloride to prepare a 20% solution, and pulping for 1 hour in ice water at the temperature of 0-2 ℃. And (3) cooling the turquoise blue base solution obtained in the step (2) to below 5 ℃, reducing the pH value to 6, dropwise adding into cyanuric chloride, reacting at the temperature of 0-10 ℃, at the pH value of 4-5 for 12h, and detecting the reaction end point by using thin-layer chromatography.
(4) Preparation of the second condensate: and (3) adding 5.04g of 2, 4-diaminobenzene sulfonic acid sodium salt dry powder into the primary condensed liquid obtained in the step (3), heating to 35-40 ℃, raising the pH to 7-8, reacting for 7 hours, and detecting the reaction end point by using a thin layer chromatography.
(5) Preparation of diazonium salt: and (3) cooling the secondary condensate obtained in the step (4) to below 5 ℃ in an ice water bath, adding 5.20g of concentrated hydrochloric acid solution with the mass fraction of 36.5%, slowly dripping 1.82g of 30% aqueous solution prepared from sodium nitrite in 1h, and reacting for 1.5h at the temperature of-5-0 ℃.
(6) Preparation of 1-hydroxy-7-amino-3-naphthalenesulfonic acid condensates and condensates: while the reaction is carried out, 5.11g of cyanuric chloride is weighed to prepare a 20% solution, and the solution is pulped in ice water for 30min at the temperature of 0-2 ℃. Preparing 15% solution from 6.52g of 1-amino-8-naphthol-3, 6-disulfonic acid, adjusting the pH value to 5.8-6.0, dropwise adding into cyanuric chloride, reacting for 1.5h at 0-5 ℃ and under the condition that the pH value is 3-3.5, and detecting the reaction end point by using thin-layer chromatography. And after the first condensation reaches the reaction end point, adding 7.62g of 4-beta-ethyl sulfuryl sulfate aniline dry powder into the first condensation, heating to 30-35 ℃, adjusting the pH value to 4-4.5, reacting for 7h, and detecting the reaction end point by using thin layer chromatography.
(7) Coupling reaction: cooling the second condensate in the step (6) to 5 ℃,and (3) adding the diazonium salt prepared in the step (5), reacting for 7 hours at the temperature of 10-15 ℃ and under the condition that the pH value is 5.5-6.5, and detecting the reaction end point by utilizing thin-layer chromatography. And drying the obtained product at the temperature of 65 ℃ to obtain the reactive dye with high fixation rate. The yield was 58.45%. Salting out the dye, DMF-CH2Cl2Recrystallization purification, and its infrared spectrum is shown in FIG. 3.
The dye is 3319.56cm-1The strong broad peak of (A) is a broad peak formed by stretching vibration of N-H and OH; at 2986.91 and 2921.82cm-1The weak absorption peak is CH2The stretching vibration absorption peak of (1); 1548.60cm-1The absorption of (a) is C ═ N stretching vibration absorption peak; 1482.58cm-1The absorption of (a) is a characteristic absorption peak of the benzene ring; 1391.75cm-1The absorption of (a) is a C-N telescopic vibration absorption peak on the isoindole ring; 1137.76, 1087.76cm-1And 1050.90cm-1Characteristic absorption peak of phthalocyanine ring; 740.58cm-1Is the stretching vibration peak of C-S and C-Cl; 904.12cm-1Is a Cu-N vibration absorption peak.
Example 4
The reactive dyes with high fixation ratios in examples 1, 2 and 3 were respectively prepared to have a concentration of 1.83X 10-5mol/L、1.92×10-5mol/L、1.92×10-5The ultraviolet-visible absorption spectrum curve of each dye was measured for a mol/L aqueous solution, and the results are shown in fig. 4, and the molar extinction coefficients thereof were calculated, and the results are shown in table 1 below:
Figure GDA0002623225560000081
example 5
The reactive dyes with high fixation rates in the embodiments 1, 2 and 3 are used for printing cotton fabrics, and can respectively provide purple, brownish green and dark purple hues for the fabrics.
5 parts of urea, 1 part of anti-dyeing salt, 2.5 parts of baking soda, 5 parts of sodium alginate and 86.5 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 and 2 were mixed uniformly with 49.5 parts (1%), 1 part (2%), 2 parts (4%), 3 parts (6%) and 4 parts (8%) of the above printing pastes, respectively, to prepare a printing paste, and the printing paste was printed on cotton cloth with a 200-mesh printing screen, baked at 80 ℃ for 4min and steamed at 105 ℃ for 8 min. Then washing with a large amount of cold water, soaping, washing with hot water, washing with cold water, and drying. The color fixing rate of each concentration printing is tested, as shown in figure 5, the apparent color depth Integ value is tested, as shown in figure 6, the color yield is gradually improved along with the increase of the dye concentration when the turquoise blue dye is printed, and the excellent promotion performance and the deep dyeing property are realized.
Example 6
The printed cotton fabric of example 4 with a dye concentration of 4% was subjected to various color fastness tests, the reference standards for this example being: the rubbing color fastness ISO 105-X12(2001), the color fastness to washing ISO 105-C03(2010), and the color fastness to light ISO 105-B02(2013), and the test results are shown in Table 2.
TABLE 2
Figure GDA0002623225560000091

Claims (9)

1. A phthalocyanine azo group double-color body reactive dye with high fixation rate is characterized in that: the general structural formula is as follows:
Figure FDA0002623225550000011
in the formula, x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 2, z is more than 0 and less than or equal to 2, and x + y + z is 3.5-4.
2. A preparation method of phthalocyanine azo-based double-color body reactive dyes with high fixation rate comprises the following steps:
(1) adding chlorosulfonic acid into a reaction container at room temperature, adding copper phthalocyanine under stirring at room temperature, performing sulfonation reaction, adding thionyl chloride for chlorination reaction after the reaction is finished, adding a reaction system into ice water, and performing suction filtration to obtain copper phthalocyanine sulfonyl chloride; wherein the molar ratio of the copper phthalocyanine to the chlorosulfonic acid to the thionyl chloride is 1-2: 40-50: 20-25;
(2) preparing the copper phthalocyanine sulfonyl chloride in the step (1) into a solution, pulping, adding a 2, 4-diaminobenzene sodium sulfonate solution and pyridine for reaction, and adding ammonia water for continuous reaction to obtain a turquoise blue base solution; wherein the molar ratio of the copper phthalocyanine sulfonyl chloride to the 2, 4-diaminobenzene sulfonic acid sodium salt to the ammonia water is 1: 1-2: 1-3;
(3) preparing cyanuric chloride into a solution, pulping, adding the turquoise blue base solution obtained in the step (2), and stirring for reaction to obtain a condensate; wherein the molar ratio of the turquoise blue group to the cyanuric chloride is 1: 1.02-2.04;
(4) adding 2, 4-diaminobenzene sulfonic acid sodium into the first condensate solution in the step (3), and stirring for reaction to obtain a second condensate; wherein the molar ratio of the condensate to the 2, 4-diaminobenzene sulfonic acid sodium salt is 1: 1-2;
(5) cooling the secondary condensate solution in the step (4) in an ice water bath, adding concentrated hydrochloric acid, dropwise adding a sodium nitrite solution, and keeping the temperature of-5-0 ℃ for continuous reaction for 1.5-2 hours after the dropwise adding is finished to obtain diazonium salt; wherein the molar ratio of the second condensate to the concentrated hydrochloric acid to the sodium nitrite is 1: 2-3: 1-2;
(6) preparing cyanuric chloride into solution, pulping, adding Rn1Solution reaction to obtain Rn1A condensate is added with Rn after the reaction is finished2Dry powder to obtain Rn1A second condensate; wherein Rn1Cyanuric chloride and Rn2In a molar ratio of 1:1.02: 1; wherein Rn1Is 1-amino-8-naphthol-3, 6-disulfonic acid sodium salt, 2-amino-5-hydroxy-7-naphthalenesulfonic acid or 1-hydroxy-7-amino-3-naphthalenesulfonic acid; rn2Is 4-beta-ethyl sulfuryl sulfate aniline or 3-beta-ethyl sulfuryl sulfate aniline;
(7) cooling the secondary condensate in the step (6), adding the secondary condensate into the diazonium salt in the step (5), and performing coupling reaction; wherein the molar ratio of the diazonium salt to the polycondensate in the step (6) is 1: 1-2.
3. A process for the preparation of reactive dyes according to claim 2, characterized in that: the sulfonation temperature in the step (1) is 130-140 ℃, and the sulfonation time is 3-6 h; the chlorination temperature is 90-105 ℃, and the chlorination time is 1-3 h.
4. A process for the preparation of reactive dyes according to claim 2, characterized in that: the mass fraction of the copper phthalocyanine sulfonyl chloride solution in the step (2) is 10-20%, the pulping temperature is 0-5 ℃, and the time is 50-70 min; the mass fraction of the 2, 4-diaminobenzene sulfonic acid sodium salt solution is 10-20%.
5. A process for the preparation of reactive dyes according to claim 2, characterized in that: the mass fraction of the cyanuric chloride solution in the step (3) is 10-20%, the pulping temperature is 0-2 ℃, and the pulping time is 20-40 min; pre-cooling the turquoise blue base solution to below 5 ℃, and reducing the pH value to 6; the reaction temperature is 0-10 ℃, the pH value is adjusted to 3-5, and the reaction time is 10-12 h.
6. A process for the preparation of reactive dyes according to claim 2, characterized in that: the reaction temperature in the step (4) is 35-40 ℃, the pH value is adjusted to 7-9, and the reaction time is 7-12 h.
7. A process for the preparation of reactive dyes according to claim 2, characterized in that: the mass fraction of the cyanuric chloride solution in the step (6) is 10-20%, the pulping temperature is 0-2 ℃, and the pulping time is 20-40 min; the first condensation reaction temperature is 0-5 ℃, the reaction pH value is 3-3.5, and the reaction time is 1-2 h; the temperature of the secondary condensation reaction is 30-35 ℃, the pH value of the reaction is 4-4.5, and the reaction time is 5-6 h.
8. A process for the preparation of reactive dyes according to claim 2, characterized in that: the coupling reaction temperature in the step (7) is 10-15 ℃, the pH value is 5.5-6.5, and the reaction time is 6-7 h.
9. The use of the phthalocyanine azo-based dichromatic reactive dyes with high fixation according to claim 1, wherein: the dry powder product is prepared after spray drying treatment.
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