Preparation method and application of environment-friendly bright liquid dispersed turquoise blue dye

Abstract

The invention relates to the field of dyes, in particular to a preparation method and application of an environment-friendly bright liquid dispersed turquoise blue dye. The preparation method comprises the following steps: preparing a copper complex from a first compound and a copper salt; wherein the first compound is selected from a compound of which the structure comprises phenyl, hydroxyl and carbonyl; reacting the copper complex with a second compound containing an acyl chloride group to obtain a modified copper complex; the nitrogen-containing compound is selected from a compound of which the structure comprises at least two of a primary amine group, a secondary amine group and a tertiary amine group; and finally, mixing the prepared modified copper complex, a nitrogen-containing compound and an auxiliary agent to obtain the liquid dispersed turquoise blue dye.

Description

Technical Field

[0001] The invention relates to the field of dyes, and in particular to a preparation method and application of an environmentally friendly bright liquid dispersed turquoise blue dye. Background Art

[0002] Blue disperse dyes are very commonly used, with disperse turquoise blue being particularly widely used in the printing and dyeing industry. Current disperse turquoise blue dyes on the market still suffer from issues such as a lack of vibrant color and poor washing, sublimation, and rubbing fastness. Furthermore, turquoise blue dyes often use copper phthalocyanine complexes, the production of which produces significant amounts of waste gas and wastewater. For example, acid boiling, filter pressing, and washing processes generate acidic waste gas and wastewater containing heavy metals. These pollutants, if not properly treated, can cause serious environmental pollution. Phthalocyanine pigment wastewater contains significant amounts of copper ions and aniline compounds, making it challenging to treat. Without effective wastewater treatment, these pollutants can enter water bodies and harm aquatic ecosystems. Furthermore, phthalocyanine itself is toxic, and long-term exposure or accumulation could pose a potential threat to ecosystems and human health. Therefore, a new, environmentally friendly turquoise blue dye is urgently needed. Summary of the Invention

[0003] The purpose of the present invention is to provide a preparation method of an environmentally friendly and bright liquid dispersed turquoise blue dye and its application, so as to solve the deficiencies in the related art.

[0004] According to a first aspect of the embodiments of the present disclosure, a method for preparing an environmentally friendly and bright liquid disperse turquoise blue dye is provided, the method comprising the following steps: Step 1: providing a copper salt and a first compound, and preparing a copper complex by using the first compound and the copper salt; wherein the first compound is selected from compounds containing a phenyl group, a hydroxyl group, and a carbonyl group in the structure; Step 2: reacting the copper complex with a second compound containing an acyl chloride group to obtain a modified copper complex; Step 3: preparing a nitrogen-containing compound, wherein the nitrogen-containing compound is selected from a compound containing at least two of a primary amine group, a secondary amine group, and a tertiary amine group in its structure; Step 4: mixing the prepared modified copper complex, nitrogen-containing compound, and auxiliary agent to obtain the liquid dispersed turquoise blue dye.

[0005] In one aspect of the embodiments of the present disclosure, step 1 includes: Step 1-1: dissolving a first compound in a first organic solvent to form a first solution, and dissolving a copper salt in a second organic solvent to form a second solution; Step 1-2: slowly adding the first solution to the stirred second solution to obtain a mixed solution; after the addition is complete, stirring is continued for 10-60 minutes; then the pH value of the mixed solution is adjusted to 9.0-10.5, stirring is continued for 12-24 hours, and then centrifugation is performed to obtain a precipitate; Step 1-3: The precipitate is washed and dried to obtain the copper complex.

[0006] In one aspect of the embodiments of the present disclosure, the first compound is selected from the following compound A-1 or compound A-2: In one aspect of the embodiments of the present disclosure, preferably, the first compound is selected from Compound A-2.

[0007] In one aspect of the embodiments of the present disclosure, the compound A-2 is prepared by the following steps: Step 5-1: preparing hesperetin intermediate via hesperetin-7-rhamnosyl glucoside; Among them, rha is a rhamnose group and glu is a glucose group; Step 5-2: Preparation of compound A-2 via hesperetin intermediate: In one aspect of the embodiments of the present disclosure, step 2 includes: Step 2-1: dissolving the copper complex in a third organic solution to form a third solution, and dissolving the second compound containing an acyl chloride group in a fourth organic solution to form a fourth solution; Step 2-2: placing the third solution under inert gas protection, then adding a catalyst, and after the catalyst is added, slowly adding the fourth solution; continuing stirring for 3-8 hours to obtain a mixed solution; Step 2-3: subjecting the mixed solution to rotary evaporation and freeze-drying to obtain a modified copper complex.

[0008] In one aspect of the presently disclosed embodiments, the second compound is selected from the following compound B-1: In one aspect of the embodiments of the present disclosure, the nitrogen-containing compound is selected from the following compound C-1: In one aspect of the disclosed embodiments, compound C-1 is prepared by the following steps: Step 3-1: adding tetraethylenepentamine to the fifth organic solution to form a fifth solution, and adding tosylaziridine to the sixth organic solution to form a sixth solution; Step 3-2: adding the sixth solution dropwise to the fifth solution, stirring at room temperature for 8-16 hours, then concentrating under reduced pressure, adding HBr / AcOH mixed solution, and reflux reaction for 12-24 hours; Step 3-3: The mixed solution obtained in step 3-2 is subjected to reduced pressure distillation to obtain a precipitate; the precipitate is collected and dissolved in dichloromethane, and then the pH value is adjusted to 11.0-12.0, and then the organic layer is separated, and the compound C-1 is obtained by rotary evaporation and drying.

[0009] In one aspect of the embodiments of the present disclosure, the copper salt is selected from at least one of the following: copper sulfate, copper chloride, copper nitrate, copper citrate, copper chlorate, copper perchlorate or a hydrate thereof; preferably, the copper salt is selected from copper chloride or a hydrate thereof.

[0010] In one aspect of the embodiments of the present disclosure, the first organic solvent is selected from ethanol, acetone, methanol or acetonitrile; preferably, the first organic solvent is selected from methanol.

[0011] In one aspect of the embodiments of the present disclosure, the second organic solvent is selected from ethanol, acetone, methanol or acetonitrile; preferably, the second organic solvent is selected from methanol.

[0012] In one aspect of the embodiments of the present disclosure, in step 1-2, the centrifugation process is centrifugation at a centrifugal rate of 2500-4500 r / min for 3-10 min.

[0013] In one aspect of the embodiments of the present disclosure, the third organic solvent is selected from acetonitrile, dimethyl sulfoxide, dimethylformamide or n-hexane; preferably, the third organic solvent is selected from dimethyl sulfoxide.

[0014] In one aspect of the embodiments of the present disclosure, the fourth organic solvent is selected from acetonitrile, dimethyl sulfoxide, dimethylformamide or n-hexane; preferably, the fourth organic solvent is selected from dimethyl sulfoxide.

[0015] In one aspect of the embodiments of the present disclosure, in step 2-2, the inert gas is selected from nitrogen.

[0016] In one aspect of the embodiments of the present disclosure, in step 2-2, the catalyst is selected from 4-dimethylaminopyridine or triethylamine.

[0017] In one aspect of the embodiments of the present disclosure, the fifth organic solvent is selected from ethanol, acetone, methanol or acetonitrile; preferably, the fifth organic solvent is selected from ethanol.

[0018] In one aspect of the embodiments of the present disclosure, the sixth organic solvent is selected from ethanol, acetone, methanol or acetonitrile; preferably, the sixth organic solvent is selected from ethanol.

[0019] In one aspect of the embodiments of the present disclosure, in the HBr / AcOH mixed solution, the volume percentage of HBr is selected from 15%-35%.

[0020] In one aspect of an embodiment of the present disclosure, the auxiliary agent is selected from at least one of a naphthalenesulfonic acid formaldehyde condensate, an alkylnaphthalenesulfonic acid formaldehyde condensate, a polycarboxylic acid compound, a naphthalenesulfonic acid formaldehyde condensate, a benzylnaphthalenesulfonic acid formaldehyde condensate, or sodium lignin sulfonate. Preferably, the naphthalenesulfonic acid formaldehyde condensate is dispersant NNO, dispersant CNF, or dispersant MF, and the polycarboxylic acid compound is dispersant 550S, dispersant Sokalan HP, or dispersant Tersperse 2735. Specifically, the auxiliary agent used in the present disclosure is dispersant MF.

[0021] According to a second aspect of the embodiments of the present disclosure, there is provided an application of the liquid dispersed turquoise blue dye prepared by the aforementioned preparation method, wherein the application is for printing and dyeing fibers or textiles.

[0022] Compared with the prior art, the beneficial effects of the present invention are: the present disclosure provides an environmentally friendly preparation process for turquoise blue dye, which uses natural plant extracts as raw materials, has mild reaction conditions, uses less strong acids and strong bases, and also reduces the use of raw materials such as aniline, which is more economical and green. DETAILED DESCRIPTION

[0023] To make the purpose, technical solutions, and advantages of this application more clear, the technical solutions of this application will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of this application, rather than all the embodiments. The relevant embodiments described herein are illustrative and are used to provide a basic understanding of this application. The embodiments of this application should not be interpreted as limiting this application.

[0024] For the sake of clarity, only some numerical ranges are specifically disclosed herein. However, any lower limit may be combined with any upper limit to form an unspecified range; and any lower limit may be combined with other lower limits to form an unspecified range, and similarly, any upper limit may be combined with any other upper limit to form an unspecified range. In addition, each individually disclosed point or single value may itself serve as a lower limit or upper limit and be combined with any other point or single value, or with other lower limits or upper limits, to form an unspecified range.

[0025] As used herein, the terms "comprises," "comprising," or any other variations thereof are intended to encompass non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus. In the absence of further limitations, an element defined by the phrase "comprising a ..." does not preclude the presence of additional identical elements in the process, method, article, or apparatus that includes the element.

[0026] In the description herein, unless otherwise specified, “above” and “below” include the number itself.

[0027] Unless otherwise specified, the terms used in this disclosure have the commonly understood meanings commonly understood by those skilled in the art. Unless otherwise specified, the numerical values of the various parameters mentioned in this disclosure can be measured using various measurement methods commonly used in the art (for example, they can be tested according to the methods given in the examples of this disclosure).

[0028] The term "about" is used to describe and illustrate small changes. When used in conjunction with an event or situation, the term may refer to an example in which the event or situation occurs precisely and an example in which the event or situation occurs very approximately. For example, when used in conjunction with a numerical value, the term may refer to a variation range of less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. In addition, amounts, ratios, and other numerical values are sometimes presented in this article in a range format. It should be understood that such range formats are for convenience and brevity, and should be flexibly understood to include not only numerical values explicitly designated as range limits, but also all individual numerical values or subranges encompassed within the range, as if each numerical value and subrange were explicitly designated.

[0029] A list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms can mean any combination of the listed items. For example, if items A and B are listed, the phrase "at least one of A and B" means only A; only B; or A and B. In another example, if items A, B, and C are listed, the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A can contain a single component or multiple components. Item B can contain a single component or multiple components. Item C can contain a single component or multiple components.

[0030] In the present disclosure, in the preparation of the copper complex, the oxygen in the carbonyl group and the hydroxyl group of the first compound coordinates with the copper ion; in a specific embodiment of the present disclosure, the 4-keto group and the 5-hydroxyl group of compound A-2 coordinate with the copper ion to form a copper complex, as shown in the following formula: In the present disclosure, in the process of preparing the modified copper complex, the copper complex is reacted with a second compound containing an acyl chloride group; in a specific embodiment of the present disclosure, the copper complex formed by compound A-2 and a copper salt is reacted with compound B-1 to obtain a modified copper complex having the following structural formula (the structural formula of the lower half of the copper complex is not shown): In the present disclosure, hesperetin-7-rhamnosyl glucoside (also known as hesperidin) has the following structural formula: Wherein, rha is a rhamnose group and glu is a glucose group. The structural formula of hesperetin-7-rhamnosyl glucoside can also be expressed as follows: In the present disclosure, hesperetin-7-rhamnosyl glucoside (hesperidin) can be obtained commercially or prepared from raw materials such as navel orange peel according to literature, without limitation thereto.

[0031] The present invention will be further described below by way of specific examples. The various chemical reagents used in the examples disclosed herein were obtained through conventional commercial channels unless otherwise specified. Unless otherwise specified, the contents described below are all by weight. Unless otherwise specified, the experiments are performed at room temperature.

[0032] Example 1 The first embodiment includes the following steps: 1. Preparation of compound A-2: Hesperetin-7-rhamnosyl glucoside (hesperidin) was dissolved in anhydrous ethanol, and concentrated sulfuric acid (5% by mass of hesperidin) was added, and stirred at room temperature for 3 hours. After separation and purification, the hesperetin intermediate product was obtained.

[0033] Sodium hydroxide was dissolved in water to prepare a 2 mol / L solution. The prepared hesperetin intermediate was added to the sodium hydroxide solution, and then dimethyl sulfate was added dropwise (the amount added was 50% of the mass of the hesperetin intermediate). After the addition was complete, stirring was continued for 2 hours. After separation and purification, compound A-2 was obtained.

[0034] 2. Preparation of copper complex: Weigh compound A-2 and dissolve it in methanol. Weigh copper chloride dihydrate and dissolve it in an equal volume of methanol (the molar amount of copper chloride dihydrate added is 1 / 2 of the molar amount of compound A-2 added). Keep the methanol solution of copper chloride in a stirring state (300 r / min) and slowly add the methanol solution of compound A-2 dropwise. At this time, the solution is blue-green. After the addition is completed, continue stirring for 50 minutes; then adjust the pH value of the mixed solution to 9.5, continue stirring for 16 hours, at this time the solution is turquoise blue, and then centrifuge to obtain a precipitate. After washing and drying, the precipitate is obtained to obtain the copper complex of Example 1.

[0035] 3. Modification of copper complex: The copper complex prepared above was dissolved in dimethyl sulfoxide, and commercially available 3,5-di-tert-butyl-4-hydroxybenzoyl chloride was dissolved in an equal volume of dimethyl sulfoxide (the mass of 3,5-di-tert-butyl-4-hydroxybenzoyl chloride added was 1 / 3 of the mass of the copper complex); the dimethyl sulfoxide solution containing the copper complex was placed under nitrogen protection, and the catalyst 4-dimethylaminopyridine was added (the mass of the catalyst was 2% of the mass of the copper complex), and then the dimethyl sulfoxide solution containing 3,5-di-tert-butyl-4-hydroxybenzoyl chloride was slowly added, and then stirring was continued for 5 hours to obtain a mixed solution; the mixed solution was subjected to rotary evaporation and freeze-dried to obtain the modified copper complex of Example 1.

[0036] 4. Preparation of compound C-1: Tetraethylenepentamine was added to ethanol, and tosylaziridine was added to the ethanol, wherein the molar amount of tosylaziridine was three times the molar amount of tetraethylenepentamine, and the volume of ethanol in which the tosylaziridine was dissolved was 30% of the volume of the ethanol in which the tetraethylenepentamine was dissolved. The ethanol solution containing tosylaziridine was added dropwise to the ethanol solution containing tetraethylenepentamine, stirred at room temperature for 12 hours, then concentrated under reduced pressure, and then a 30% HBr / AcOH mixed solution was added, and the mixture was refluxed for 16 hours. The resulting mixed solution was subjected to reduced pressure distillation to obtain a precipitate. The precipitate was collected and dissolved in dichloromethane, and the pH was adjusted to 11.5. The organic layer was separated, rotary evaporated, and dried to obtain compound C-1.

[0037] 5. Preparation of turquoise blue dye: 100 parts by weight of the modified copper complex prepared in Example 1, 15 parts by weight of compound C-1, 70 parts by weight of dispersant MF, and 40 parts by weight of sodium lignin sulfonate were dissolved in 800 parts by weight of water, ground and dispersed, and spray-dried to obtain the finished product of Example 1.

[0038] Example 2 The second embodiment includes the following steps: 1. Preparation of Hesperetin Product: Hesperetin-7-rhamnosyl glucoside (hesperidin) was dissolved in anhydrous ethanol, and concentrated sulfuric acid (5% by mass of hesperidin) was added, stirred at room temperature for 3 hours, and the hesperetin product was obtained through separation and purification.

[0039] 2. Preparation of copper complex: The hesperetin product was weighed and dissolved in methanol. Copper chloride dihydrate was weighed and dissolved in an equal volume of methanol (the molar amount of copper chloride dihydrate added was 1 / 2 the molar amount of the hesperetin product added). The methanol solution of copper chloride was stirred at 300 rpm and the methanol solution of the hesperetin product was slowly added dropwise. The solution was then blue-green. After the addition was complete, stirring was continued for 50 minutes. The pH of the mixed solution was then adjusted to 9.5 and stirring was continued for 16 hours. The solution was then turquoise blue and centrifuged to obtain a precipitate. The precipitate was washed and dried to obtain the copper complex of Example 2.

[0040] 3. Modification of copper complex: The copper complex prepared above was dissolved in dimethyl sulfoxide, and commercially available 3,5-di-tert-butyl-4-hydroxybenzoyl chloride was dissolved in an equal volume of dimethyl sulfoxide (the mass of 3,5-di-tert-butyl-4-hydroxybenzoyl chloride added was 1 / 3 of the mass of the copper complex); the dimethyl sulfoxide solution containing the copper complex was placed under nitrogen protection, and the catalyst 4-dimethylaminopyridine was added (the mass of the catalyst was 2% of the mass of the copper complex), and then the dimethyl sulfoxide solution containing 3,5-di-tert-butyl-4-hydroxybenzoyl chloride was slowly added, and then stirring was continued for 5 hours to obtain a mixed solution; the mixed solution was subjected to rotary evaporation and freeze-dried to obtain the modified copper complex of Example 2.

[0041] 4. Preparation of compound C-1: Tetraethylenepentamine was added to ethanol, and tosylaziridine was added to the ethanol, wherein the molar amount of tosylaziridine was three times the molar amount of tetraethylenepentamine, and the volume of ethanol in which the tosylaziridine was dissolved was 30% of the volume of the ethanol in which the tetraethylenepentamine was dissolved. The ethanol solution containing tosylaziridine was added dropwise to the ethanol solution containing tetraethylenepentamine, stirred at room temperature for 12 hours, then concentrated under reduced pressure, and then a 30% HBr / AcOH mixed solution was added, and the mixture was refluxed for 16 hours. The resulting mixed solution was subjected to reduced pressure distillation to obtain a precipitate. The precipitate was collected and dissolved in dichloromethane, and the pH was adjusted to 11.5. The organic layer was separated, rotary evaporated, and dried to obtain compound C-1.

[0042] 5. Preparation of turquoise blue dye: 100 parts by weight of the modified copper complex prepared in Example 2, 15 parts by weight of compound C-1, 70 parts by weight of dispersant MF, and 40 parts by weight of sodium lignin sulfonate were dissolved in 800 parts by weight of water, ground and dispersed, and spray-dried to obtain the finished product of Example 2.

[0043] Comparative Example 1 Comparative Example 1 comprises the following steps: 1. Preparation of compound A-2: Hesperetin-7-rhamnosyl glucoside (hesperidin) was dissolved in anhydrous ethanol, and concentrated sulfuric acid (5% by mass of hesperidin) was added, and stirred at room temperature for 3 hours. After separation and purification, the hesperetin intermediate product was obtained.

[0044] Sodium hydroxide was dissolved in water to prepare a 2 mol / L solution. The prepared hesperetin intermediate was added to the sodium hydroxide solution, and then dimethyl sulfate was added dropwise (the amount added was 50% of the mass of the hesperetin intermediate). After the addition was complete, stirring was continued for 2 hours. After separation and purification, compound A-2 was obtained.

[0045] 2. Preparation of copper complex: Weigh compound A-2 and dissolve it in methanol. Weigh copper chloride dihydrate and dissolve it in an equal volume of methanol (the molar amount of copper chloride dihydrate added is 1 / 2 of the molar amount of compound A-2 added). Keep the methanol solution of copper chloride in a stirring state (300 r / min) and slowly add the methanol solution of compound A-2 dropwise. At this time, the solution is blue-green. After the addition is completed, continue stirring for 50 minutes; then adjust the pH value of the mixed solution to 9.5, continue stirring for 16 hours, at this time the solution is turquoise blue, and then obtain a precipitate by centrifugation; after washing and drying the precipitate, obtain the copper complex of Comparative Example 1.

[0046] 3. Preparation of compound C-1: Tetraethylenepentamine was added to ethanol, and tosylaziridine was added to the ethanol, wherein the molar amount of tosylaziridine was three times the molar amount of tetraethylenepentamine, and the volume of ethanol in which the tosylaziridine was dissolved was 30% of the volume of the ethanol in which the tetraethylenepentamine was dissolved. The ethanol solution containing tosylaziridine was added dropwise to the ethanol solution containing tetraethylenepentamine, stirred at room temperature for 12 hours, then concentrated under reduced pressure, and then a 30% HBr / AcOH mixed solution was added, and the mixture was refluxed for 16 hours. The resulting mixed solution was subjected to reduced pressure distillation to obtain a precipitate. The precipitate was collected and dissolved in dichloromethane, and the pH was adjusted to 11.5. The organic layer was separated, rotary evaporated, and dried to obtain compound C-1.

[0047] 4. Preparation of turquoise blue dye: 100 parts by weight of the copper complex prepared in Comparative Example 1, 15 parts by weight of compound C-1, 70 parts by weight of dispersant MF, and 40 parts by weight of sodium lignin sulfonate were dissolved in 800 parts by weight of water, ground and dispersed, and spray-dried to obtain the finished product of Comparative Example 1.

[0048] Comparative Example 2 Comparative Example 2 comprises the following steps: 1. Preparation of compound A-2: Hesperetin-7-rhamnosyl glucoside (hesperidin) was dissolved in anhydrous ethanol, and concentrated sulfuric acid (5% by mass of hesperidin) was added, and stirred at room temperature for 3 hours. After separation and purification, the hesperetin intermediate product was obtained.

[0049] Sodium hydroxide was dissolved in water to prepare a 2 mol / L solution. The prepared hesperetin intermediate was added to the sodium hydroxide solution, and then dimethyl sulfate was added dropwise (the amount added was 50% of the mass of the hesperetin intermediate). After the addition was complete, stirring was continued for 2 hours. After separation and purification, compound A-2 was obtained.

[0050] 2. Preparation of copper complex: Weigh compound A-2 and dissolve it in methanol. Weigh copper chloride dihydrate and dissolve it in an equal volume of methanol (the molar amount of copper chloride dihydrate added is 1 / 2 of the molar amount of compound A-2 added). Keep the methanol solution of copper chloride in a stirring state (300 r / min) and slowly add the methanol solution of compound A-2 dropwise. At this time, the solution is blue-green. After the addition is completed, continue stirring for 50 minutes; then adjust the pH value of the mixed solution to 9.5, continue stirring for 16 hours, at this time the solution is turquoise blue, and then centrifuge to obtain a precipitate; after washing and drying the precipitate, obtain the copper complex of Comparative Example 2.

[0051] 3. Modification of copper complex: The copper complex prepared above was dissolved in dimethyl sulfoxide, and commercially available 3,5-di-tert-butyl-4-hydroxybenzoyl chloride was dissolved in an equal volume of dimethyl sulfoxide (the mass of 3,5-di-tert-butyl-4-hydroxybenzoyl chloride added was 1 / 3 of the mass of the copper complex); the dimethyl sulfoxide solution containing the copper complex was placed under nitrogen protection, and the catalyst 4-dimethylaminopyridine was added (the mass of the catalyst was 2% of the mass of the copper complex), and then the dimethyl sulfoxide solution containing 3,5-di-tert-butyl-4-hydroxybenzoyl chloride was slowly added, and then stirring was continued for 5 hours to obtain a mixed solution; the mixed solution was subjected to rotary evaporation and freeze-drying to obtain the modified copper complex of Comparative Example 2.

[0052] 4. Preparation of turquoise blue dye: 100 parts by weight of the modified copper complex prepared in Example 1, 70 parts by weight of dispersant MF, and 40 parts by weight of sodium lignin sulfonate were dissolved in 800 parts by weight of water, ground and dispersed, and spray-dried to obtain the finished product of Comparative Example 2.

[0053] Comparative Example 3 The steps of Comparative Example 3 are the same as those of Example 1, except that aniline is used instead of compound C-1.

[0054] Performance testing: 35 mL of each sample of the embodiment and the comparative example was taken, the pH value of the sample was adjusted to 5.0 with acetic acid, and then the temperature was raised to 60° C., and 3 g of polyester fiber was added to each sample for dyeing. The temperature was raised to 130° C. within 35 minutes, kept warm for 45 minutes, cooled to 80° C., and sampling was performed. The dye strength was measured according to GB / T6688-2008, the sublimation fastness was measured according to GB / T5718, the light fastness was measured according to GB / T8427, and the rubbing fastness was measured according to GB / T3920. The measurement results are shown in Table 1.

[0055] Table 1 As can be seen from Table 1, the addition of compound C-1 can significantly increase the rubbing fastness and sublimation fastness. This is because compound C-1 is interwoven into a network structure and is rich in amino groups, which can form coordination with the free copper ions in the dye, thereby increasing the sublimation fastness and rubbing fastness. Methylation of the 6-hydroxyl group of hesperetin and substitution of the 3-hydroxyl group with 3,5-di-tert-butyl-4-hydroxybenzoyl chloride can significantly improve its light fastness and enhance its weather resistance.

[0056] Those skilled in the art will readily appreciate other embodiments of the present disclosure after considering the specification and practicing the disclosure disclosed herein. This disclosure is intended to cover any variations, uses, or adaptations of the present disclosure that follow the general principles of the present disclosure and include common knowledge or customary techniques in the art not disclosed herein.

Claims

1. A method for preparing an environmentally friendly and bright liquid dispersed turquoise blue dye, characterized in that: The preparation method comprises the following steps: Step 1: providing a copper salt and a first compound, and preparing a copper complex by using the first compound and the copper salt; wherein the first compound is selected from compounds containing a phenyl group, a hydroxyl group, and a carbonyl group in the structure; Step 2: reacting the copper complex with a second compound containing an acyl chloride group to obtain a modified copper complex; Step 3: preparing a nitrogen-containing compound, wherein the nitrogen-containing compound is selected from a compound containing at least two of a primary amine group, a secondary amine group, and a tertiary amine group in its structure; Step 4: mixing the prepared modified copper complex, nitrogen-containing compound, and auxiliary agent to obtain the liquid dispersed turquoise blue dye.

2. The preparation method according to claim 1, characterized in that Step 1 includes: Step 1-1: dissolving a first compound in a first organic solvent to form a first solution, and dissolving a copper salt in a second organic solvent to form a second solution; Step 1-2: slowly adding the first solution to the stirred second solution to obtain a mixed solution; after the addition is complete, stirring is continued for 10-60 minutes; then the pH value of the mixed solution is adjusted to 9.0-10.5, stirring is continued for 12-24 hours, and then centrifugation is performed to obtain a precipitate; Step 1-3: The precipitate is washed and dried to obtain the copper complex.

3. The preparation method according to claim 1, characterized in that The first compound is selected from the following compound A-1 or compound A-2: 。 4. The preparation method according to claim 3, characterized in that The compound A-2 is prepared by the following steps: Step 5-1: preparing hesperetin intermediate via hesperetin-7-rhamnosyl glucoside; Among them, rha is a rhamnose group and glu is a glucose group; Step 5-2: Preparation of compound A-2 via hesperetin intermediate: 。 5. The preparation method according to claim 1, characterized in that Step 2 includes: Step 2-1: dissolving the copper complex in a third organic solution to form a third solution, and dissolving the second compound containing an acyl chloride group in a fourth organic solution to form a fourth solution; Step 2-2: placing the third solution under inert gas protection, then adding a catalyst, and after the catalyst is added, slowly adding the fourth solution; continuing stirring for 3-8 hours to obtain a mixed solution; Step 2-3: subjecting the mixed solution to rotary evaporation and freeze-drying to obtain a modified copper complex.

6. The preparation method according to claim 5, characterized in that The second compound is selected from the following compound B-1: 。 7. The preparation method according to claim 1, characterized in that The nitrogen-containing compound is selected from the following compound C-1: 。 8. The preparation method according to claim 1, characterized in that Compound C-1 was prepared by the following steps: Step 3-1: adding tetraethylenepentamine to the fifth organic solution to form a fifth solution, and adding tosylaziridine to the sixth organic solution to form a sixth solution; Step 3-2: adding the sixth solution dropwise to the fifth solution, stirring at room temperature for 8-16 hours, then concentrating under reduced pressure, adding HBr / AcOH mixed solution, and reflux reaction for 12-24 hours; Step 3-3: distilling the mixed solution obtained in step 3-2 under reduced pressure to obtain a precipitate; The precipitate was collected and dissolved in dichloromethane, and then the pH value was adjusted to 11.0-12.

0. The organic layer was then separated, and the mixture was subjected to rotary evaporation and drying to obtain compound C-1.

9. The preparation method according to any one of claims 1 to 8, characterized in that The preparation method satisfies at least one of the following conditions: (1) The copper salt is at least one selected from the group consisting of copper sulfate, copper chloride, copper nitrate, copper citrate, copper chlorate, copper perchlorate, or a hydrate thereof; (2) The first organic solvent is selected from ethanol, acetone, methanol or acetonitrile; (3) The second organic solvent is selected from ethanol, acetone, methanol or acetonitrile; (4) In step 1-2, the centrifugation process is performed at a centrifugal rate of 2500-4500 rpm for 3-10 min; (5) The third organic solvent is selected from acetonitrile, dimethyl sulfoxide, dimethylformamide or n-hexane; (6) The fourth organic solvent is selected from acetonitrile, dimethyl sulfoxide, dimethylformamide or n-hexane; (7) In step 2-2, the inert gas is selected from nitrogen; (8) In step 2-2, the catalyst is selected from 4-dimethylaminopyridine or triethylamine; (9) The fifth organic solvent is selected from ethanol, acetone, methanol or acetonitrile; (10) The sixth organic solvent is selected from ethanol, acetone, methanol or acetonitrile; (11) In the HBr / AcOH mixed solution, the volume percentage of HBr is selected from 15% to 35%; (12) The auxiliary agent is selected from at least one of naphthalenesulfonic acid formaldehyde condensate, lignin sulfonate, alkylnaphthalenesulfonic acid formaldehyde condensate, naphthalenesulfonic acid formaldehyde condensate, polycarboxylic acid compound, benzylnaphthalenesulfonic acid formaldehyde condensate or sodium lignin sulfonate.

10. Use of the liquid disperse turquoise blue dye prepared by the preparation method according to any one of claims 1 to 9, characterized in that: Used for printing and dyeing fibers or textiles.

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