High-fastness disperse dye as well as preparation method and application thereof

Abstract

The invention relates to the field of dyes, and particularly discloses a high-fastness disperse dye as well as a preparation method and application thereof. The dye has a structure shown in a general formula I, and R1 is selected from phenyl substituted by nitryl, cyano, halogen and the like or benzothiazolyl substituted by nitryl. Aromatic amine with a specific structure is prepared into diazonium salt through diazotization reaction, then the diazonium salt and a specific 1, 3-dicarbonyl compound derivative are subjected to coupling reaction, and the dye is prepared. The molecular structure of the dye contains a strong polar group and an expanded conjugated system, and the intermolecular force between the dye and polyester fibers is remarkably enhanced, so that the dye has excellent sublimation fastness and washing fastness on polyester fabrics, and can meet the strict requirements of high-end fields such as automotive trim and outdoor fabric on heat resistance.

Description

Technical Field

[0001] This application relates to the field of dyes, and more specifically, to a high-fastness disperse dye and a method for preparing the same. Background Technology

[0002] In recent years, with the continuous upgrading of the global textile industry and the increasing demands of the consumer market for textile quality, the application of high-performance synthetic fibers, represented by polyester, has become increasingly widespread. Correspondingly, the performance requirements for disperse dyes, as key coloring materials for these fibers, have become increasingly stringent, especially in terms of heat resistance. High sublimation fastness disperse dyes can effectively resist color migration during high-temperature setting, ironing, and other finishing processes, which is crucial for ensuring the long-lasting stability of textile colors and enhancing product added value.

[0003] However, the domestic market still heavily relies on imports for high-end, high-sublimation-fastness disperse dyes. This not only leads to a significant increase in production costs, restricting the profit margins of domestic textile printing and dyeing enterprises, but also poses potential risks to the supply of key materials in the industrial chain. Therefore, developing high-performance disperse dyes with independent intellectual property rights and breaking the foreign technological monopoly is of great strategic significance for enhancing the overall competitiveness of my country's textile industry, ensuring industrial security, and promoting the industry's development towards high-end products.

[0004] Meanwhile, the application areas of disperse dyes are continuously expanding into industrial textiles such as automotive interiors, outdoor equipment, and home décor. These emerging fields place more comprehensive and stringent demands on dye performance, such as maintaining color stability under long-term heat and light conditions, and meeting higher environmental and ecological standards. Traditional disperse dyes often struggle to simultaneously meet the needs of these high-end applications in terms of sublimation fastness, wash fastness, and the balance of various fastness properties. Therefore, developing a new generation of disperse dyes that combine excellent sublimation fastness, good wash fastness, and other application properties has become an urgent technical challenge in the field of dye chemistry and a clear trend in industry development. Summary of the Invention

[0005] To address the aforementioned issues, this application provides a high-fastness disperse dye, its preparation method, and its application.

[0006] The technical solution adopted in this application is as follows: In a first aspect, this application provides a high-fastness disperse dye compound as shown in general formula I: In the formula, n is 0, 1 or 2, and m is 0, 1 or 2; R1 is selected from any of the structures shown in the following formula: (a) A phenyl group that is substituted by one or more substituents independently selected from nitro, cyano, halogen, C1-C4 alkyl; (b) Benzothiazolyl group substituted with one or more nitro groups.

[0007] Furthermore, n is 1 or 2, and m is 0.

[0008] Furthermore, R1 is a phenyl or benzothiazolyl group substituted with one or two nitro groups.

[0009] Further, R1 is a phenyl group substituted with one or two nitro groups, and the phenyl group is further substituted with any one of cyano, halogen or methyl.

[0010] Furthermore, R1 is a benzothiazolyl group substituted with one or two nitro groups.

[0011] Furthermore, the structure of the dye compound is shown below: Secondly, this application provides a method for preparing the above-mentioned high-fastness disperse dye compound, comprising: Aromatic amines with the R1-NH2 structure are dissolved in hydrochloric acid or sulfuric acid, and sodium nitrite or nitrosyl sulfuric acid solution is added dropwise at a temperature of 0-15℃ to carry out a diazotization reaction, yielding a diazonium salt solution. The diazonium salt solution was coupled with the coupling component under conditions of 0-10℃ and pH 4-7 to obtain the dye compound represented by general formula (Ⅰ). The chemical structure of the coupling component is as follows: The n can be 0, 1, or 2; m can be 0, 1, or 2.

[0012] Furthermore, the mass concentration of the sodium nitrite or nitrosyl sulfuric acid solution is 30%-50%, and the holding time for the diazotization reaction is 4-10 hours.

[0013] In this technical solution, the conditions for the diazotization reaction are divided into the following two types: (1) First, dissolve or suspend the amine compound in dilute hydrochloric acid or dilute sulfuric acid, then slowly add an aqueous solution of sodium nitrite at a low temperature (usually 0-5℃). The principle is that sodium nitrite (NaNO2) reacts with an acid (such as HCl) in aqueous solution to produce reactive nitrous acid (HNO2) or nitrosyl chloride (NOCl), which immediately reacts with the amine to form a diazonium salt. Its advantages are: relatively simple and safe operation, low cost, and applicability to most water-soluble or water-dispersible aromatic amines.

[0014] (2) First, dissolve or suspend the amine compound in concentrated sulfuric acid, and then slowly add nitrosyl sulfuric acid solution at low temperature (usually 0-5℃). This method is mainly applicable to: some amine compounds that are insoluble in dilute acid aqueous solutions, and the diazonium salts generated are "water-insoluble diazonium salts". These diazonium salts are extremely unstable and decompose rapidly when exposed to water. They must be generated and stored in an anhydrous environment.

[0015] Thirdly, this application provides a high-fastness disperse dye composition comprising the dye compound or a mixture thereof as described above.

[0016] Fourthly, this application provides the use of the high-fastness disperse dye compound or high-fastness disperse dye composition as described above in the dyeing or printing of polyester fibers or fabrics.

[0017] In summary, this application has the following beneficial effects: The dye compound of general formula I provided by this invention significantly increases the molecular weight, polarity, and conjugated system of the dye molecule by introducing strongly polar groups (such as nitro, cyano, halogen, etc.) and / or benzothiazole heterocycles into its molecular structure and coupling specific coupling components. This structural design comprehensively enhances the van der Waals forces, dipole-dipole interactions, and potential hydrogen bonding between the dye molecule and polyester fiber. Therefore, the dye of this invention exhibits excellent sublimation fastness on polyester and can withstand high-temperature setting and ironing treatments above 180°C, effectively solving the color migration and staining problems that are prone to occur in traditional dyes during high-temperature processing. At the same time, this structure also endows the dye with excellent wash fastness, enabling the dyed fabric to maintain its bright color for a long time during daily use and repeated washing. Attached Figure Description

[0018] Figure 1 This is the MS spectrum of the red dye of formula I-2 provided in Example 4 of this application; Figure 2 It is the red dye of formula I-2 provided in Embodiment 4 of this application. 1 H-NMR spectrum; Figure 3 This is the MS spectrum of the blue dye of formula I-3 provided in Example 5 of this application; Figure 4This is the MS spectrum of the purple dye of formula I-4 provided in Example 6 of this application; Figure 5 It refers to the dyeing process used in the dyeing test of this application; Figure 6 This is part of the staining evaluation results of this application. Detailed Implementation

[0019] The embodiments of the present invention will be described in detail below with reference to the examples. However, those skilled in the art will understand that the following examples are only for illustrating the present invention and should not be regarded as limiting the scope of the present invention. Specific conditions not specified in the examples shall be carried out according to conventional conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0020] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0021] Example 1 This embodiment provides a coupling component as shown in Formula II-a, the preparation method of which includes: 21.2 parts of compound III, 60 parts of methyl chloroacetate, and 15 parts of dry soda ash powder were mixed and heated to 120°C and maintained for about 10 hours. After the reaction was completed, excess methyl chloroacetate was recovered under negative pressure. The residual solution was dissolved in 120 parts of acetic acid to obtain the coupling component shown in II-a, which was used for subsequent dye synthesis.

[0022] Example 2 This embodiment provides a coupling component as shown in Formula II-b, the preparation method of which includes: 21.2 parts of compound III, 45 parts of methyl acrylate, 25 parts of acetic acid, and 0.2 parts of hydroquinone were mixed and heated to 120°C and maintained for about 10 hours. After the reaction was completed, excess methyl acrylate was recovered under negative pressure. The residual solution was dissolved in 100 parts of acetic acid to obtain the coupling component shown in II-a, which was used for subsequent dye synthesis.

[0023] Example 3 This embodiment provides a dye compound of formula I-1, the preparation method of which is as follows: Add 13.8 parts of p-nitroaniline to 100 parts of water and 31 parts of 30% hydrochloric acid. Heat until the material dissolves, then cool down and add an appropriate amount of ice. At T=0-5℃, add sodium nitrite solution (7 parts of sodium nitrite dissolved in 30 parts of water) dropwise and maintain for 1 hour after the addition is complete.

[0024] The acetic acid solution obtained in Example 1 was cooled down, and the above-mentioned diazo solution was added dropwise at T = 0-5℃. After the addition was completed, the solution was kept at the temperature for 2 hours to carry out the coupling reaction. After the coupling was completed, 500 parts of water were added, the product was precipitated and filtered, and the filter cake was washed with water until neutral to obtain 50.5 parts of Formula I-1 dye.

[0025] Example 4 This embodiment provides a dye compound of formula I-2, the preparation method of which is as follows: Dissolve 16.3 parts of 2-cyano-4-nitroaniline in 30 parts of concentrated sulfuric acid, and slowly add 33 parts of 40% nitrosyl sulfuric acid solution at T = 5-10℃. After keeping warm for 8 hours, use it for coupling.

[0026] The acetic acid solution obtained in Example 1 was cooled down, and the above-mentioned diazo solution was added dropwise at T = 5-10℃. After the addition was completed, the temperature was maintained for 2 hours to carry out the coupling reaction. After the coupling was completed, 800 parts of water were added, the product was precipitated and filtered, and the filter cake was washed with water until neutral to obtain 47.7 parts of Formula I-2 red dye.

[0027] The mass spectrum of the I-2 red dye is as follows: Figure 1 As shown; the proton nuclear magnetic resonance spectrum is as follows: Figure 2 As shown.

[0028] Example 5 This embodiment provides a dye compound of formula I-3, the preparation method of which is as follows: Dissolve 19.5 parts of 5-nitro-3-aminobenzisothiazole in 30 parts of concentrated sulfuric acid and 10 parts of phosphoric acid. Slowly add 33 parts of 40% nitrosylsulfuric acid solution at T = 0-5℃. After the addition is complete, keep warm for 8 hours before using for coupling.

[0029] The acetic acid solution obtained in Example 1 was cooled down, and the above-mentioned diazo solution was added dropwise at T = 0-5℃. After the addition was completed, the solution was kept at the temperature for 2 hours to carry out the coupling reaction. After the coupling was completed, 800 parts of water were added, the product was precipitated and filtered, and the filter cake was washed with water until neutral to obtain 48 parts of Formula I-3 blue dye.

[0030] The mass spectrum of the I-3 blue dye is as follows: Figure 3 As shown.

[0031] Example 6 This embodiment provides a dye compound of formula I-4, the preparation method of which is as follows: Dissolve 26.2 parts of 2,4-dinitro-6-bromoaniline in 30 parts of concentrated sulfuric acid, and slowly add 33 parts of concentrated sulfuric acid dropwise at T = 10-15℃. A 40% nitrosylsulfuric acid solution was used for coupling after being dripped and kept at a warm temperature for 8 hours.

[0032] The acetic acid solution obtained in Example 1 was cooled down, and the above-mentioned diazo solution was added dropwise at T = 10-15℃. The mixture was kept at this temperature for 2 hours to carry out the coupling reaction. After the coupling was completed, 1000 parts of water were added, the product was precipitated and filtered, and the filter cake was washed with water until neutral to obtain 62.9 parts of Formula I-4 dye.

[0033] The mass spectrum of the I-4 dye is as follows: Figure 4 As shown.

[0034] Example 7 This embodiment provides a dye compound of formula I-5, the preparation method of which is as follows: Dissolve 16.3 parts of 2-cyano-4-nitroaniline in 30 parts of concentrated sulfuric acid, and slowly add 33 parts of 40% nitrosyl sulfuric acid solution at T = 5-10℃. After keeping warm for 8 hours, use it for coupling.

[0035] The acetic acid solution obtained in Example 2 was cooled down, and the above-mentioned diazo solution was added dropwise at T = 5-10℃. After the addition was completed, the solution was kept at the temperature for 2 hours to carry out the coupling reaction. After the coupling was completed, 800 parts of water were added, the product was precipitated and filtered, and the filter cake was washed with water until neutral to obtain 55.8 parts of Formula I-5 dye.

[0036] Example 8 This embodiment provides a dye compound of formula I-6, the preparation method of which is as follows: Dissolve 19.5 parts of 5-nitro-3-aminobenzisothiazole in 30 parts of concentrated sulfuric acid and 10 parts of phosphoric acid. Slowly add 33 parts of 40% nitrosylsulfuric acid solution at T = 0-5℃. After the addition is complete, keep warm for 8 hours before using for coupling.

[0037] The acetic acid solution obtained in Example 2 was cooled down, and the above-mentioned diazo solution was added dropwise at T = 0-5℃. After the addition was completed, the solution was kept at the temperature for 2 hours to carry out the coupling reaction. After the coupling was completed, 800 parts of water were added, the product was precipitated and filtered, and the filter cake was washed with water until neutral to obtain 59 parts of Formula I-6 dye.

[0038] Example 9 This embodiment provides a dye compound of formula I-7, the preparation method of which is as follows: Dissolve 26.2 parts of 2,4-dinitro-6-bromoaniline in 30 parts of concentrated sulfuric acid, and slowly add 33 parts of concentrated sulfuric acid dropwise at T = 10-15℃. A 40% nitrosylsulfuric acid solution was used for coupling after being dripped and kept at a warm temperature for 8 hours.

[0039] The acetic acid solution obtained in Example 2 was cooled down, and the above-mentioned diazo solution was added dropwise at T = 10-15℃. The mixture was kept at this temperature for 2 hours to carry out the coupling reaction. After the coupling was completed, 1000 parts of water were added, the product was precipitated and filtered, and the filter cake was washed with water until neutral to obtain 65.7 parts of Formula I-7 purple dye.

[0040] Example 10 This embodiment provides a dye compound of formula I-8, the preparation method of which is as follows: Add 13.8 parts of p-nitroaniline to 100 parts of water and 31 parts of 30% hydrochloric acid. Heat until the material dissolves, then cool and add an appropriate amount of ice. At T=0-5℃, add sodium nitrite solution (7 parts of sodium nitrite dissolved in 30 parts of water) dropwise.

[0041] The acetic acid solution obtained in Example 2 was cooled down, and the above-mentioned diazo solution was added dropwise at T = 0-5℃. After the addition was completed, the solution was kept at the temperature for 2 hours to carry out the coupling reaction. After the coupling was completed, 500 parts of water were added, the product was precipitated and filtered, and the filter cake was washed with water until neutral to obtain 50 parts of Formula I-8 dye.

[0042] Example 11 This embodiment provides a dye compound of formula I-9, the preparation method of which is as follows: Add 17.2 parts of 2-chloro-4-nitroaniline to 250 parts of water and 30 parts of 30% hydrochloric acid, slurry for 3 hours and cool down. At T=0-5℃, add sodium nitrite solution (7 parts of sodium nitrite dissolved in 30 parts of water) dropwise and maintain for 3 hours for coupling.

[0043] The acetic acid solution obtained in Example 1 was cooled down, and the above-mentioned diazo solution was added dropwise at T = 0-5℃. After the addition was completed, the solution was kept at the temperature for 2 hours to carry out the coupling reaction. After the coupling was completed, 800 parts of water were added, the product was precipitated and filtered, and the filter cake was washed with water until neutral to obtain 53 parts of Formula I-9 dye.

[0044] Example 12 This embodiment provides a dye compound of formula I-10, the preparation method of which is as follows: Dissolve 18.3 parts of 2,4-dinitroaniline in 35 parts of concentrated sulfuric acid. At T = 5-10℃, slowly add 33 parts of 40% nitrosylsulfuric acid solution. After the addition is complete, keep warm for 2 hours before using for coupling.

[0045] The acetic acid solution obtained in Example 1 was cooled down, and the above-mentioned diazo solution was added dropwise at T = 5-10℃. After the addition was completed, the solution was kept at the temperature for 2 hours to carry out the coupling reaction. After the coupling was completed, 800 parts of water were added, the product was precipitated and filtered, and the filter cake was washed with water until neutral to obtain 55 parts of Formula I-10 dye.

[0046] Example 13 This embodiment provides a dye compound of formula I-11, the preparation method of which is as follows: At T = 20-25℃, 21.7 parts of 2,4-dinitro-6-chloroaniline were added to a mixture of 30 parts concentrated sulfuric acid and 33 parts 40% nitrosyl sulfuric acid solution. After the addition was complete... After being kept at 20-25℃ for 5 hours, it is used for coupling.

[0047] The acetic acid solution obtained in Example 1 was cooled down, and the above-mentioned diazo solution was added dropwise at about T=15℃. After the addition was completed, the solution was kept at the temperature for 2 hours to carry out the coupling reaction. After the coupling was completed, 1000 parts of water were added, the product was precipitated and filtered, and the filter cake was washed with water until neutral to obtain 56 parts of Formula I-11 dye.

[0048] Example 14 This embodiment provides a dye compound of formula I-12, the preparation method of which is as follows: Dissolve 20.7 parts of 2,6-dichloro-4-nitroaniline in 35 parts of 98% sulfuric acid, cool to 0-5℃, and slowly add 33 parts of [unclear text - possibly a specific ingredient or solution] dropwise. A 40% nitrosylsulfuric acid solution was added dropwise and left to remain for about 5 hours to allow for coupling.

[0049] The acetic acid solution obtained in Example 1 was cooled down, and the above-mentioned diazo solution was added dropwise at T = 0-5℃. After the addition was completed, the solution was kept at the temperature for 2 hours to carry out the coupling reaction. After the coupling was completed, 1000 parts of water were added, the product was precipitated and filtered, and the filter cake was washed with water until neutral to obtain 55 parts of Formula I-12 dye.

[0050] Example 15 This embodiment provides a dye compound of formula I-13, the preparation method of which is as follows: Dissolve 24.2 parts of 2-cyano-4-nitro-6-bromoaniline in 50 parts of concentrated sulfuric acid. At T = 10-15℃, slowly add 33 parts of 40% nitrosyl sulfuric acid solution. After the addition is complete, keep warm for 8 hours before using for coupling.

[0051] The acetic acid solution obtained in Example 1 was cooled, and the above-mentioned diazo solution was added dropwise at T = 10-15℃. The mixture was kept at this temperature for 2 hours to carry out the coupling reaction. After the coupling was completed, 1000 parts of water were added, the product was precipitated and filtered, and the filter cake was washed with water until neutral to obtain 62 parts. Formula I-13 dye.

[0052] Performance testing I. Staining Test use Figure 5 The conventional disperse dyeing method shown was used to dye the fabric to be dyed (50D / 72F DTY polyester + 20D spandex jersey). The red dye I-2, blue dye I-3, and purple dye I-4 provided in the example were used as test samples, while the conventional disperse dyes S-5BL (commercially available) and SW-4B (commercially available) were used as control dyes.

[0053] The sublimation fastness rating was compared with that in GB 250-2008 (Gray Chart for Assessing Color Change) and ISO 105 / A02-1993 (Gray Chart for Assessing Color Change) to evaluate its color change.

[0054] The results are as follows Figure 6 As shown in Table 2: Table 2. 210℃*30s 180℃*30s 180℃*240s Sublimation durability PET staining PET staining PET staining S-5BL 3 4-5 3 SW-4B 3-4+ 4-5 3-4+ I-2 Red Dye 4-5 5 4-5 I-3 Blue Dye 4-5 5 4-5 I-4 Purple Dye 4-5 5 4-5 As shown in Table 2, compared with the commercially available S-5BL and SW-4B, the I-2 red dye, I-3 blue dye, and I-4 purple dye provided in this application all have excellent sublimation fastness.

[0055] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A high-fastness disperse dye compound as shown in general formula I: In the formula, n is 0, 1 or 2, and m is 0, 1 or 2; R1 is selected from any of the structures shown in the following formula: (a) A phenyl group that is substituted by one or more substituents independently selected from nitro, cyano, halogen, C1-C4 alkyl; (b) Benzothiazolyl group substituted with one or more nitro groups.

2. The high-fastness disperse dye compound according to claim 1, characterized in that, n is 1 or 2, and m is 0.

3. The high-fastness disperse dye compound according to claim 2, characterized in that, R1 is a phenyl or benzothiazolyl group substituted with one or two nitro groups.

4. The high-fastness disperse dye compound according to claim 3, characterized in that, R1 is a phenyl group substituted with one or two nitro groups, which is further substituted with any one of cyano, halogen, or methyl.

5. The high-fastness disperse dye compound according to claim 3, characterized in that, R1 is a benzothiazolyl group substituted with one or two nitro groups.

6. The high-fastness disperse dye compound according to any one of claims 1-5, characterized in that, The structure of the dye compound is shown below: A method for preparing a high-fastness disperse dye compound according to any one of claims 1-6, characterized in that it comprises: Aromatic amines with the R1-NH2 structure are dissolved in hydrochloric acid or sulfuric acid, and sodium nitrite or nitrosyl sulfuric acid solution is added dropwise at a temperature of 0-15℃ to carry out a diazotization reaction, yielding a diazonium salt solution. The diazonium salt solution was coupled with the coupling component under conditions of 0-10℃ and pH 4-7 to obtain the dye compound represented by general formula (Ⅰ). The chemical structure of the coupling component is as follows: The n can be 0, 1, or 2; m can be 0, 1, or 2.

7. The method for preparing the high-fastness disperse dye compound according to claim 7, characterized in that, The mass concentration of the sodium nitrite or nitrosyl sulfuric acid solution is 30%-50%, and the holding time for the diazotization reaction is 4-10 hours.

8. A high-fastness disperse dye composition, characterized in that, It comprises a dye compound or a mixture thereof as described in any one of claims 1-6.

9. The use of a high-fastness disperse dye compound as described in any one of claims 1-6 or a high-fastness disperse dye composition as described in claim 9 in the dyeing or printing of polyester fibers or fabrics.

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