Non-photosensitive golden yellow dye and synthesis method thereof
By introducing large conjugated structures and specific synthesis methods into azo-type dyes, a non-photosensitive golden dye was prepared, which solved the problem that existing dyes were prone to fading under light irradiation, and achieved the effect of high sun-sun fastness and color fastness.
Patent Information
- Application Number
- CN202411902047.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-23
- Publication Date
- 2025-03-21
AI Technical Summary
Existing azo dyes are prone to photosensitization under light exposure, causing the fabric to become lighter and fade, affecting the sun fastness and service life.
A non-photosensitive golden dye is prepared by a specific synthetic method, and its structure contains a large conjugated structure. By adjusting the reaction conditions and steps, the structural stability of the dye under ultraviolet light is ensured.
It effectively improves the sun and color fastness of the dye. The dye still maintains a good color for 36 hours in a strong sun-dried environment, is not easy to fade, and has high dye permeability and market value.
Smart Images
Figure CN119662041A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of textile printing and dyeing, and more specifically, to a non-photosensitive golden yellow dye and a synthesis method thereof. Background Art
[0002] Under light irradiation, dye molecules absorb photons and transition from the ground state to the excited state, generating electron-hole pairs. Due to the interaction between dye molecules, excited state electrons will migrate to adjacent ground state dye molecules, causing some excited state dye molecules to decompose or undergo photochemical reactions, causing the dye chromophore to change or be destroyed, resulting in fabric discoloration or fading, and even causing fabric degradation and brittleness, affecting the appearance and service life of outdoor textiles. This phenomenon is called photosensitization of dyes.
[0003] The light fastness of textiles is affected by many factors, and the dye structure is the main influencing factor. Dyes with different structures have different fading mechanisms under the action of light. For example, the azo group in the azo dye molecule can participate in oxidation and reduction reactions under different environments, break chemical bonds, destroy the conjugated system in the dye molecular structure, affect the light fastness of the dye and the fabric, and then cause the dyed fabric to change color and fade after exposure to the sun. Summary of the invention
[0004] In order to improve the light fastness of azo dyes, the present application provides a non-photosensitive golden yellow dye and a synthesis method thereof.
[0005] In the first aspect, the present application provides a non-photosensitive golden yellow dye, which adopts the following technical solution: A non-photosensitive golden yellow dye, the structural formula is as follows: Formula Ⅰ.
[0006] In a second aspect, the present application provides a method for preparing a non-photosensitive golden yellow dye, using the following technical solution: A method for synthesizing a non-photosensitive golden yellow dye comprises the following preparation steps: S1: adding cyanuric chloride to a para-ester aqueous solution at 0-5°C, then adjusting the solution pH to between 5.0 and 5.5, stirring the solution to react, and obtaining a condensed solution containing the compound of formula IV; S2: adding a solution containing the compound of formula IV to a 40-50° C. aqueous solution of 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid, adjusting the pH of the solution to between 6.0 and 7.0, and stirring the reaction to obtain a solution containing the compound of formula III; S3: adding the para-ester to water, then hydrochloric acid, adjusting the temperature between 0 and 5°C, adding sodium nitrite, stirring and reacting to obtain a diazotized solution containing the compound of formula II; S4: adding the diazotized solution containing the compound of formula II to the dicondensed solution containing the compound of formula III, then adjusting the solution temperature between 15 and 20° C., stirring for reaction, and then adjusting the solution pH to between 3.0 and 4.0, passing through a film, and spray drying to obtain the non-photosensitive golden yellow dye shown in formula I; The synthesis method of the above-mentioned non-photosensitive golden yellow dye has a synthesis process route of: .
[0007] Preferably, in S1, the molar ratio of cyanuric chloride to para-ester is 1:(1.0-1.03).
[0008] Preferably, in S2, the molar ratio of the compound of formula IV to 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid is 1:(0.98-1.01).
[0009] Preferably, in S3, the molar ratio of the para-ester, hydrochloric acid and sodium nitrite is 1:(1.9-2.01):(0.98-1.02).
[0010] Preferably, in S4, the molar ratio of the compound of formula II to the compound of formula III is 1:(0.99-1.02).
[0011] In summary, this application has the following beneficial effects: 1. The dye compound of the present application has excellent stability through the unique large conjugated structure in its chromophore, which can prevent the dye from tautomerism and reduce the proportion of structural changes of the dye under ultraviolet light, thereby effectively resisting the damage of ultraviolet light and maintaining color stability. After being treated in a strong sunlight environment for 36 hours, the dye still maintains a good color and is not easy to fade. It has high sunlight stability and fastness index, so it can be used as a non-photosensitive dye for outdoor or sun-resistant fabrics; 2. The dye compound of the present application has a relatively large structure, relatively more hydrophilic groups, and high water solubility. During the dyeing process, it can enter the fiber with water to achieve a softer and more natural dyeing effect, effectively improving the color light stability and fastness index of the dyed fabric. Therefore, the dye compound has a high dyeing penetration, which can effectively improve the levelness of the dyed fabric, is not easy to produce color flowers, and can also be applied to dyeing processes such as dip dyeing and pad dyeing, and has a wider dyeing process; 3. The dye compound of the present application, as the yellow component of the three primary colors, can be combined with dyes of other colors to enrich the dye color, so it has both good dyeing performance and economic performance, and has a wide range of applications and high market value; 4. The synthesis method of the dye compound of the present application has a short synthesis process route, mild synthesis conditions, low raw material cost, high purity of the synthesized product, high commercial value, and is conducive to large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Figure 1 It is a dyeing process flow chart in this application. DETAILED DESCRIPTION
[0013] The present application is further described in detail below in conjunction with the accompanying drawings and embodiments. Example Example 1
[0014] A non-photosensitive golden yellow dye, the structural formula of which is shown in Formula I: Formula Ⅰ.
[0015] The synthesis method of the above-mentioned non-photosensitive golden yellow dye has a synthesis process route of: .
[0016] The synthesis method of the above-mentioned non-photosensitive golden yellow dye comprises the following preparation steps: S1: Add the para-ester (28.1 g, 0.1 mol) into ice water (500 mL) and fully dissolve to obtain an aqueous solution of the para-ester; Add cyanuric chloride (18.5 g, 0.1 mol) to a para-ester aqueous solution at 0-5°C, then adjust the pH of the solution to between 5.0 and 5.5 (5.0 in the present embodiment), stir and react for 2 hours to obtain a condensed solution containing the compound of formula IV; S2: Add 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid (26.0 g, 0.1 mol) into water (200 mL) and fully dissolve to obtain an aqueous solution of 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid; A solution containing the compound of formula IV (40.8 g, 0.1 mol) was added to a 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid aqueous solution at 40-50° C. (40° C. in the present embodiment), and then the pH of the solution was adjusted to between 6.0 and 7.0 (6.0 in the present embodiment) with sodium carbonate, and the reaction was stirred for 2 hours to obtain a solution containing the compound of formula III; S3: Add the para-ester (28.1 g, 0.1 mol) into ice water (500 mL) and fully dissolve to obtain an aqueous solution of the para-ester; 30% hydrochloric acid (26 mL, 0.2 mol) was added to the para-ester aqueous solution, and then the solution temperature was adjusted between 0 and 5°C, and 10% sodium nitrite (70 mL, 0.1 mol) was added, and the reaction was stirred for 0.5 h to obtain a diazotized solution containing a compound of formula II; S4: Add the diazotized solution (32.8 g, 0.1 mol) containing the compound of formula II to the dicondensed solution (63.2 g, 0.1 mol) containing the compound of formula III, then adjust the solution temperature between 15 and 20°C, stir and react for 0.5 h, then adjust the solution pH between 3.0 and 4.0 (3.0 in the embodiment of the present application), stir and react for 0.5 h, pass through a membrane, spray dry, and obtain a non-photosensitive golden yellow dye (87.3 g, purity 91.3%, yield 90.3%).
[0017] Comparative Example 1 A golden yellow dye, which is different from Example 1 in that its structural formula is: .
[0018] Comparative Example 2 A golden yellow dye, which is different from Example 1 in that its structural formula is: .
[0019] Comparative Example 3 A golden yellow dye, which is different from Example 1 in that its structural formula is: .
[0020] The golden yellow dye compounds prepared in the examples and comparative examples are first selected as test objects for standby use, and then their color fastness is tested and rated after dyeing according to the following specific dyeing method. The specific dyeing method and corresponding test steps and conditions are as follows: Fabric to be dyed, specifically cotton double-sided knitted fabric; Staining method, see Figure 1 , the specific steps are as follows: 1) providing a dye bath containing the golden yellow dye compound prepared in the example or comparative example for standby use, wherein the amount of the golden yellow dye compound used is 0.5%, 1.0%, 2.0%, and 4.0% owf (dye relative to fabric weight), respectively; 2) Immerse the fabric to be dyed in the dye bath in 1) at a constant temperature of 60°C at a bath ratio of 1:50; 3) After 10 minutes of immersion, slowly add 20g / L sodium chloride while stirring. After 30 minutes of reaction, slowly add 30g / L sodium carbonate while stirring. Continue to react for 45-60 minutes. Then wash with water, soap, wash with water, and dry at 70℃ to complete the dyeing.
[0021] Then the dyed fabric is tested for light fastness. The specific method is as follows: 1) Use standard blue wool to dry to the specified grade of the gray card and determine the specific time; 2) Determine the shape and size of the sample according to the sample holder and cut the sample to the appropriate size; 3) Install the test sample and the standard material on different mounting cards; 4) Keep the cover in close contact with the sample without causing unnecessary compression to the sample; 5) Place the dyed fabric samples and standard materials in a test room with the same experimental conditions for testing; 6) After the test is completed, the tested samples are placed in a dark environment for at least 24 hours, and then the color change is digitally rated according to ISO 105-A02 against the gray scale.
[0022] The golden yellow dye compounds in the above-mentioned Example 1 and Comparative Examples 1-3 were extracted, and the color fastness rating test results of the to-be-dyed fabrics at different concentrations were tested respectively, and the average values were recorded in Tables 1-4.
[0023] Table 1: Fastness performance test results of Example 1 and Comparative Examples 1-3 at 0.5% owf depth Table 2: Fastness performance test results of 1.0% owf Example 1 and Comparative Examples 1-3 Table 3: Fastness performance test results of 2.0% owf Example 1 and Comparative Examples 1-3 Table 4: Fastness performance test results of 4.0%owf Example 1 and Comparative Examples 1-3 As can be seen from Tables 1 to 4, the fabric samples dyed with the dye compound prepared in Example 1 have excellent color fastness, wherein the light fastness when dyed with 0.5% owf is above level 4 to 5, indicating that the non-photosensitivity of the dye structure itself can keep the fabric with good color stability under sunlight. At the same time, the washing fastness, perspiration color fastness and film fastness of Example 1 can all remain stable at different dosages, but the comparative examples 1 to 3 have certain fluctuations at high concentrations, indicating that different chromophore structures have certain effects on the combination of dye and fiber.
[0024] In summary, the various properties of Example 1, namely, color stability and fastness, are improved to varying degrees compared to Comparative Examples 1 to 3. Combining the above data, the following conclusions and analyses can be drawn: Only the non-photosensitive golden yellow dye compound with a specific structure provided in the present application has excellent sunlight-resistant color stability; in contrast, Comparative Example 1, Comparative Example 2 and Comparative Example 3, which have very similar main structures, still do not have the corresponding color stability. As can be seen from the embodiments, the conditions and steps for their synthesis are also relatively simple, and the purity and yield of the obtained product are high, and there are basically no by-products, which is conducive to large-scale production.
[0025] Embodiments 2 to 4 A non-photosensitive golden yellow dye, which is different from Example 1 in that in step S1, the molar ratio of cyanuric chloride and para-ester and the purity of the compound of synthetic formula IV are as shown in Table 5.
[0026] Table 5: Molar ratio of cyanuric chloride and para-ester in Examples 1 to 4 and purity of compound of formula IV Group Molar ratio of cyanuric chloride and para-ester Purity of the compound of formula IV Example 1 The molar ratio of cyanuric chloride to para-ester is 1:1.0 90.3% Example 2 The molar ratio of cyanuric chloride to para-ester is 1:1.01 91.3% Example 3 The molar ratio of cyanuric chloride to para-ester is 1:1.02 90.6% Example 4 The molar ratio of cyanuric chloride to para-ester is 1:1.03 89.7% By analyzing the data in the above table, it can be seen that the para-ester and cyanuric chloride condense at low temperatures. Since cyanuric chloride is easily hydrolyzed, in order to complete the condensation reaction once, the reaction molar ratio is often to increase the amount of cyanuric chloride by 2% to 3%. However, excessive cyanuric chloride will condense with multiple para-esters to generate side reactions, affecting the purity of the compound of formula IV. Therefore, appropriately reducing the concentration of cyanuric chloride can effectively reduce the formation of by-products.
[0027] Embodiments 5 to 7 A non-photosensitive golden yellow dye, which is different from Example 1 in that in step S2, the molar ratio of the compound of formula IV and 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid and the purity of the compound of formula III are shown in Table 6.
[0028] Table 6: Molar ratio of compound IV and 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid and purity of compound III in Examples 1, 5 to 7 Group The molar ratio of the compound of formula IV to 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid is Purity of the compound of formula III Example 1 The molar ratio of the compound of formula IV to 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid is 1:1 90.3% Example 5 The molar ratio of the compound of formula IV to 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid is 1:0.98 85.5% Example 6 The molar ratio of the compound of formula IV to 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid is 1:0.99 89.1% Example 7 The molar ratio of the compound of formula IV to 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid is 1:1.01 88.1% By analyzing the data in the above table, it can be seen that when the molar ratio of the compound of formula IV to 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid is controlled at 1:1, the purity of the final product is the highest. If the content of one component is too high, the synthesis reaction will not be completed, thereby affecting the purity of the final dye.
[0029] Embodiments 8 to 11 A non-photosensitive golden yellow dye, which is different from Example 1 in that in step S3, the molar ratio of the para-ester, 30% hydrochloric acid and sodium nitrite and the purity of the compound of synthetic formula II are as shown in Table 7.
[0030] Table 7: Molar ratio of para-ester, 30% hydrochloric acid and sodium nitrite in Examples 1, 8 to 11 and purity of compound of formula II Group The molar ratio of para-ester, 30% hydrochloric acid and sodium nitrite Purity of the compound of formula II Example 1 The molar ratio of para-ester, 30% hydrochloric acid and sodium nitrite is 1:2:1 90.3% Example 8 The molar ratio of para-ester, 30% hydrochloric acid and sodium nitrite is 1:1.9:1 84.6% Example 9 The molar ratio of para-ester, 30% hydrochloric acid and sodium nitrite is 1:2.01:1 89.1% Example 10 The molar ratio of para-ester, 30% hydrochloric acid and sodium nitrite is 1:2:0.98 88.1% Embodiment 11 The molar ratio of para-ester, 30% hydrochloric acid and sodium nitrite is 1:2:1.02 89.4% By analyzing the data in the above table, it can be seen that the purity of the compound of formula II obtained in Examples 8, 9, 10, and 11 is as high as 90.3% compared with Example 1. This shows that in the synthesis process of the non-photosensitive golden yellow dye of the present application, controlling the molar ratio of the para-ester, 30% hydrochloric acid, and sodium nitrite to be 1:2:1 can improve the purity of the compound of formula II obtained.
[0031] Embodiments 12 to 14 A non-photosensitive golden yellow dye, which is different from Example 1 in that in step S4, the molar ratio of the compound of formula II and the compound of formula III and the purity of the synthesized non-photosensitive golden yellow dye are as shown in Table 5.
[0032] Table 8: Molar ratio of compound II and compound III in Examples 1, 12 to 14 and purity of non-photosensitive golden yellow dye Group Molar ratio of diazotization liquid and dicondensation liquid Non-photosensitive golden yellow dye purity Example 1 The molar ratio of the compound of formula II to the compound of formula III is 1:1 90.3% Example 12 The molar ratio of the compound of formula II to the compound of formula III is 1:0.99 82.6% Embodiment 13 The molar ratio of the compound of formula II to the compound of formula III is 1:1.01 83.3% Embodiment 14 The molar ratio of the compound of formula II to the compound of formula III is 1:1.02 81.7% By analyzing the data in the above table, it can be seen that the non-photosensitive golden yellow dye compounds prepared in Examples 1 and 12 to 14 all have a high purity, which is above 81.7%. The synthesis path of the dye is simple, and the purity of the dye can be greatly guaranteed. There are basically no by-products, which is suitable for large-scale production.
[0033] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.
Claims
1. A non-photosensitive golden yellow dye, characterized in that: The structural formula is shown in Formula I: Formula Ⅰ.
2. The method for synthesizing the non-photosensitive golden yellow dye according to claim 1, characterized in that: The following steps are involved: Add the diazotized solution containing the compound of formula II to the dicondensed solution containing the compound of formula III, then adjust the solution temperature to between 15 and 20° C., stir to react, then adjust the solution pH to between 3.0 and 4.0, stir to react, pass through a film, and spray dry to obtain the non-photosensitive golden yellow dye shown in formula I; The reaction scheme of the above-mentioned preparation steps is as follows: 。 3. The method for synthesizing the non-photosensitive golden yellow dye according to claim 2, characterized in that: The molar ratio of the compound of formula II to the compound of formula III is 1:(0.99-1.02).
4. The method for synthesizing the non-photosensitive golden yellow dye according to claim 2, characterized in that: The method for synthesizing the dicondensate containing the compound of formula III comprises the following steps: S1: adding cyanuric chloride to a para-ester aqueous solution at 0-5°C, then adjusting the solution pH to between 5.0 and 5.5, stirring the solution to react, and obtaining a condensed solution containing the compound of formula IV; S2: adding a solution containing the compound of formula IV to a 40-50° C. aqueous solution of 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid, adjusting the pH of the solution to between 6.0 and 7.0, and stirring the reaction to obtain a solution containing the compound of formula III; The reaction scheme of the above-mentioned preparation steps is as follows: 。 5. The method for synthesizing the non-photosensitive golden yellow dye according to claim 4, characterized in that: The molar ratio of cyanuric chloride to para-ester is 1:(1.0-1.03).
6. The method for synthesizing the non-photosensitive golden yellow dye according to claim 4, characterized in that: The molar ratio of the compound of formula IV to 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid is 1:(0.98-1.01).
7. The method for synthesizing the non-photosensitive golden yellow dye according to claim 2, characterized in that: The method for synthesizing the diazotized liquid containing the compound of formula II comprises the following steps: Add the para-ester to water, then add hydrochloric acid at a temperature between 0 and 5°C, then add sodium nitrite, and stir to react to obtain a diazotized solution containing the compound of formula II; The reaction scheme of the above-mentioned preparation steps is as follows: 。 8. The method for synthesizing the non-photosensitive golden yellow dye according to claim 7, characterized in that: The molar ratio of the para-ester, hydrochloric acid and sodium nitrite is 1:(1.9-2.01):(0.98-1.02).
9. The method for synthesizing the non-photosensitive golden yellow dye according to claim 2, characterized in that: The following steps are involved: S1: adding cyanuric chloride to a para-ester aqueous solution at 0-5°C, then adjusting the solution pH to between 5.0 and 5.5, stirring the solution to react, and obtaining a condensed solution containing the compound of formula IV; S2: adding a solution containing the compound of formula IV to a 40-50° C. aqueous solution of 2-(2-carboxyethylamino)-4-aminobenzenesulfonic acid, adjusting the pH of the solution to between 6.0 and 7.0, and stirring the reaction to obtain a solution containing the compound of formula III; S3: adding the para-ester to water, then hydrochloric acid, adjusting the temperature between 0 and 5°C, adding sodium nitrite, stirring and reacting to obtain a diazotized solution containing the compound of formula II; S4: adding the diazotized solution containing the compound of formula II to the dicondensed solution containing the compound of formula III, then adjusting the solution temperature between 15 and 20° C., stirring for reaction, and then adjusting the solution pH to between 3.0 and 4.0, passing through a film, and spray drying to obtain the non-photosensitive golden yellow dye shown in formula I; The synthesis method of the above-mentioned non-photosensitive golden yellow dye has a synthesis process route of: 。