Energy-saving yellow reactive dye as well as preparation method and application thereof
By combining bisbenzimidazole diamide with trifluorocyanide and linear ester, an energy-saving yellow reactive dye was developed, which solved the problem of high energy consumption in the dyeing and water washing of existing dyes, achieved energy-saving and environmentally friendly effects of low-temperature dyeing and room-temperature water washing, and improved color fastness and color fixation rate.
Patent Information
- Application Number
- CN202411984878.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-31
- Publication Date
- 2025-05-13
AI Technical Summary
The existing reactive dyes require higher temperatures during dyeing and washing, resulting in increased energy consumption and making it difficult to achieve energy-saving and environmentally friendly dyeing effects.
The energy-saving yellow reactive dye formed by combining the new intermediate bisbenzimidazole diamide with trifluorocyanide and linear ester can achieve efficient dyeing and room temperature washing under low temperature conditions, reducing energy consumption.
The energy-saving and environmentally friendly effect of dyeing at low temperature (40℃) and washing at room temperature (15-25℃), improves the dyeing rate and color fixation rate of the dye at low temperature, and ensures bright colors and high color fastness.
Smart Images
Figure CN119978847A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of reactive dyes, and in particular to an energy-saving yellow reactive dye and a preparation method and application thereof. Background Art
[0002] Reactive dyes, also known as reactive dyes, contain active groups that can react with hydroxyl groups in cellulose and amino groups in protein fibers. When dyeing, they form covalent bonds with fibers to form "dye-fiber" compounds. Reactive dyes have the characteristics of bright colors, good levelness, simple dyeing methods, high color fastness, complete color spectrum and low cost. They are mainly used in the dyeing and printing of fibers such as cotton, linen, viscose, silk and wool and their blended fabrics.
[0003] However, most of the reactive dyes currently used in China are based on single or double reactive groups of cyanuric chloride and para-ester or para-ester derivatives as the active groups of the dyes, with dyeing temperatures around 60°C and washing temperatures around 40°C. In today's era of energy crisis, energy conservation and environmental protection are issues that need to be addressed urgently. Summary of the invention
[0004] In order to solve at least one of the above technical problems, the present invention provides an energy-saving yellow reactive dye and a preparation method thereof. The dye is a combination of a novel intermediate bisbenzimidazole diamine with cyanuric fluoride and a linear ester, achieving the purpose of energy-saving and environmentally friendly dyeing at low temperature (40°C) and washing at room temperature (15-25°C).
[0005] The present application provides an energy-saving yellow reactive dye, the structure of which is shown in Formula I:
[0006]
[0007]
[0008] Wherein, R1 and R2 are independently selected from H and C1-C6 alkyl.
[0009] Through the above technical scheme, the energy-saving yellow reactive dye combines the novel intermediate bisbenzimidazole diamine with tricyandiamide and linear ester, introduces a heterocyclic structure into the parent structure, reduces the content of anionic groups in the dye structure, reduces the negative charge carried by the dye, and reduces the salt effect of the dye. At the same time, the dye molecule contains multiple active groups, which effectively improves the low-temperature dyeing rate and fixation rate of the dye, achieves the effect of low-temperature water washing, and has bright colors after dyeing, achieving the purpose of energy-saving and environmentally friendly dyeing of dyeing at low temperature (40°C) and washing at room temperature (15-25°C), and has good color fastness and high fixation rate.
[0010] Preferably, R1 and R2 are independently selected from H and C1-C3 alkyl.
[0011] Preferably, the energy-saving yellow reactive dye is selected from the following structures:
[0012]
[0013]
[0014] In a second aspect of the present application, the present application provides a method for preparing the above energy-saving yellow reactive dye, comprising the following steps:
[0015] Step 1): 3-amino 4-R1 substituted amino nitrobenzene and 3-amino 4-R2 substituted amino nitrobenzene react with oxalic acid to obtain bisbenzimidazole dinitro, and the reaction formula is as follows:
[0016]
[0017] Step 2): The bisbenzimidazole dinitro obtained in step 1) is subjected to a hydrogenation reduction reaction to obtain a bisbenzimidazole diamine color body. The reaction formula is shown below:
[0018]
[0019] Step 3): Add linear ester and cyanuric fluoride to the bisbenzimidazole diamine color body obtained in step 2), adjust the pH to 6.0-6.5, and react to obtain a reaction solution containing a condensate. The reaction formula is as follows:
[0020]
[0021] Step 4): The reaction solution containing the shrinkage product obtained in step 3) is heated to 20-25° C., the pH is adjusted to 7.5-8.0, reacted, the pH is adjusted to 6.5-7.0, purified, and the energy-saving yellow reactive dye is obtained. The reaction formula is as follows:
[0022]
[0023] Preferably, in the step 1), the reaction is carried out under reflux at 140-150° C. for 4-6 hours under the catalytic condition of tripolyphosphoric acid.
[0024] Preferably, in the step 2), the hydrogenation reduction reaction is carried out under the action of tin dichloride catalyst, the temperature of the hydrogenation reduction reaction is 70-80° C., and the time is 6-8 hours.
[0025] In the third aspect of the present application, the present application provides an energy-saving yellow reactive dye composition, characterized in that it comprises at least two of compound I-1, compound I-2 and compound I-3, and the structural formulas of compound I-1, compound I-2 and compound I-3 are as follows:
[0026]
[0027]
[0028] Preferably, the energy-saving yellow reactive dye composition comprises compound I-1 and compound I-2, and the weight ratio of compound I-1 to compound I-2 is 0.8-1.2:1.
[0029] In a fourth aspect of the present application, the present application provides the use of the above energy-saving yellow reactive dye and / or the energy-saving yellow reactive dye obtained by the above preparation method in textile dyeing.
[0030] Preferably, the textile is selected from one or more blends of cotton, linen, viscose, silk, silkworm silk and wool.
[0031] Preferably, the energy-saving yellow reactive dye is used in an amount of 0.5-12% owf.
[0032] In summary, the present invention includes at least one of the following beneficial technical effects:
[0033] 1. The present application provides an energy-saving yellow reactive dye, which combines a new intermediate bisbenzimidazole diamine with tricyandiamide and a linear ester. A heterocyclic structure is introduced into the parent structure to reduce the content of anionic groups in the dye structure and the negative charge carried by the dye, thereby reducing the salt effect of the dye. At the same time, the dye molecule contains multiple active groups, which effectively improves the low-temperature dyeing rate and fixation rate of the dye, achieves the effect of low-temperature water washing, and has bright colors after dyeing, achieving the energy-saving and environmentally friendly dyeing purpose of dyeing at low temperature (40°C) and washing at room temperature (15-25°C), and has good color fastness and high fixation rate.
[0034] 2. The present application provides a method for preparing the above-mentioned energy-saving yellow reactive dye, which has a simple process and is easy to industrialize.
[0035] 3. The present application also provides the use of the above energy-saving yellow reactive dye in textile dyeing. DETAILED DESCRIPTION
[0036] The present invention will be further described below in conjunction with specific examples, but the following examples are only used to illustrate the present invention and should not be considered to limit the scope of the present invention. In the following examples, if specific conditions are not specified, they are carried out according to normal conditions or conditions recommended by the manufacturer. The methods used are conventional methods known in the art unless otherwise specified, and the consumables and reagents used are commercially available unless otherwise specified. Unless otherwise specified, the professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. In addition, any method or material similar or equivalent to the recorded content may also be applied to the present invention.
[0037] Example 1
[0038] This embodiment provides an energy-saving yellow reactive dye, the structural formula of which is as follows:
[0039]
[0040] The preparation method of the energy-saving yellow reactive dye described in formula I-1 comprises the following steps:
[0041] Step 1): Preparation of bisbenzimidazole diamine chromophore:
[0042] 0.2 mol of 3,4-diaminonitrobenzene and 0.12 mol of oxalic acid are added to 400 ml of ethylene glycol solvent, mixed, 0.02 mol of tripolyphosphoric acid is added as a catalyst, and stirred for 4-6 hours under reflux conditions at 140-150° C. After the reaction is completed, the mixture is cooled to room temperature, the precipitate is filtered, washed three times with water, and dried to obtain bisbenzimidazole dinitro; under a nitrogen atmosphere, the dried bisbenzimidazole dinitro and 0.01 mol of hydrated tin dichloride are mixed in 200 mL of ethyl acetate, 0.4 mol of hydrogen is introduced, and stirred for 6-8 hours under 70-80° C. After the reaction is completed, it is neutralized with a 10% sodium carbonate solution, and after no bubbles are generated, it is washed with 100 mL of ethyl acetate solution, and the ethyl acetate is distilled off to obtain a bisbenzimidazole diamine color body;
[0043] The reaction formula is as follows:
[0044]
[0045] Step 2): shrinkage reaction
[0046] First step: add ice to the bisbenzimidazole diamine color body obtained in step 1) and cool it to 0-5°C, then add about 0.21 mol of linear ester HClNH2CH2CH2OCH2CH2SO2CH2CH2Cl at once, then add 0.20 mol of cyanuric fluoride over half an hour, while adding cyanuric fluoride, use 10% liquid caustic soda to maintain the pH at 6.0-6.5, and maintain the reaction for half an hour after the addition, the process temperature is 0-5°C, and the reaction is completed to obtain a reaction solution containing a first step;
[0047] The reaction formula is as follows:
[0048]
[0049] Step 3): Dicondensation reaction
[0050] Secondary condensation: the reaction solution containing the primary condensate obtained in step 2) is heated to 20-25°C, and the pH is adjusted to 7.5-8.0 with 10% liquid alkali. After the reaction is maintained for 2 hours, the pH is adjusted to 6.5-7.5 with 30% hydrochloric acid, and purified to obtain the energy-saving active yellow dye shown in formula I-1.
[0051] The reaction formula is as follows:
[0052]
[0053] Example 2
[0054] Embodiment 2 provides an energy-saving yellow reactive dye, the structural formula of which is as follows:
[0055]
[0056] The preparation method of the energy-saving yellow reactive dye described in formula I-2 comprises the following steps:
[0057] Step 1): Preparation of bisbenzimidazole diamine chromophore:
[0058] 0.2 mol of 3-amino-4-nitromethylnitrobenzene and 0.12 mol of oxalic acid are added to 400 ml of ethylene glycol solvent, mixed, 0.02 mol of tripolyphosphoric acid is added as a catalyst, and stirred for 4-6 hours under reflux conditions at 140-150° C. After the reaction is completed, the mixture is cooled to room temperature, the precipitate is filtered, washed three times with water, and dried to obtain bisbenzimidazole dinitro; under a nitrogen atmosphere, the dried bisbenzimidazole dinitro and 0.01 mol of hydrated tin dichloride are mixed in 200 ml of ethyl acetate, 0.4 mol of hydrogen is introduced, and stirred for 6-8 hours under the conditions of 70-80° C. After the reaction is completed, it is neutralized with a 10% sodium carbonate solution, and after no bubbles are generated, it is washed with 100 ml of ethyl acetate solution, and the ethyl acetate is distilled off to obtain a bisbenzimidazole diamine color body;
[0059] The reaction formula is as follows:
[0060]
[0061] Step 2): shrinkage reaction
[0062] First step: add ice to the bisbenzimidazole diamine color body obtained in step 1) and cool it to 0-5°C, then add about 0.21 mol of linear ester HClNH2CH2CH2OCH2CH2SO2CH2CH2Cl at once, then add 0.20 mol of cyanuric fluoride over half an hour, while adding cyanuric fluoride, use 10% liquid caustic soda to maintain the pH at 6.0-6.5, and maintain the reaction for half an hour after the addition, the process temperature is 0-5°C, and the reaction is completed to obtain a reaction solution containing a first step;
[0063]
[0064] Step 3): Dicondensation reaction
[0065] Secondary condensation: the reaction solution containing the primary condensate obtained in step 2) is heated to 20-25°C, and the pH is adjusted to 7.5-8.0 with 10% liquid alkali. After the reaction is maintained for 2 hours, the pH is adjusted to 6.5-7.5 with 30% hydrochloric acid, and purified to obtain the energy-saving active yellow dye shown in formula I-2.
[0066]
[0067] Example 3
[0068] Embodiment 3 provides an energy-saving yellow reactive dye, the structural formula of which is as follows:
[0069]
[0070] The preparation method of the energy-saving yellow reactive dye described in formula I-3 refers to Example 1, except that the equimolar amount of the raw material 3,4-diaminonitrobenzene is replaced by 3-amino-4-nitroethylnitrobenzene.
[0071] Example 4
[0072] The energy-saving yellow reactive dye represented by formula I-1 obtained in Example 1 and the energy-saving yellow reactive dye represented by formula I-2 obtained in Example 2 were mixed in a weight ratio of 1:1 to obtain a dye composition.
[0073] Dyeing performance test
[0074] Experiment 1: Fastness test of reactive dyes
[0075] 1. The energy-saving active yellow dye or dye composition obtained in Examples 1-4 above and the low-temperature active dye Yellow XR sample (CAS: 12226-45-8) widely used in the market were selected as Comparative Example 1.
[0076] 2. The reactive dyes of Examples 1-3 and Comparative Example 1 were respectively prepared according to the following conditions: cotton fabric: 5 g, sodium sulfate concentration: 20 g / L, bath ratio: 1:20, pH adjusted to 8.0 with soda ash, dye concentration: 4% (owf); dyeing and fixing were carried out by 40°C heating dyeing method, and then washed with water at room temperature (20-25 degrees Celsius), and cloth samples were obtained after post-treatment.
[0077] According to the national standards, rubbing color fastness GB / T 3920 2008, washing color fastness GB / T 39212008, the color fastness of the cotton fabric samples after dyeing was measured. The results are shown in Table 1. The results show that an energy-saving yellow reactive dye of the present application has excellent washing and rubbing fastness on cotton fabric.
[0078] Table 1 List of color fastness of cotton fabric dyeing when the dye concentration is 4% (owf)
[0079]
[0080] The data in Table 1 show that the dyes of Examples 1 and 2 have excellent fastness to washing and rubbing on cotton fabrics. In particular, compared with Reactive Dye Yellow XR, the fastness of Example 1 is greatly improved.
[0081] Experiment 2: Fixation rate test of reactive dyes
[0082] The energy-saving reactive yellow dye or dye composition obtained in the above Examples 1-4 and the low-temperature reactive dye yellow XR sample (CAS: 12226-45-8) which is widely used in the market are selected as Comparative Example 1.
[0083] The reactive dye liquors of Examples 1-4 and Comparative Example 1 were respectively prepared according to the following conditions: cotton fabric: 5 g, sodium sulfate concentration: 20 g / L, bath ratio 1:20, soda ash adjusted pH=8.0, dye concentration: 0.5-12% (owf); dyeing was carried out by 40°C heating dyeing method, and then the fixation rate was determined. The fixation rate test results are shown in Table 2.
[0084] Table 2 Fixation rate table
[0085]
[0086]
[0087] The results in Table 2 show that the energy-saving yellow reactive dye of the present application has a relatively excellent fixation rate on cotton fabrics during low-temperature dyeing, especially the fixation rate of the reactive dye prepared in Example 1 is increased by more than 7% over the basic fixation rate of traditional reactive dyes.
[0088] The above are all preferred embodiments of the present application, and the protection scope of the present application is not limited thereto. Therefore, any equivalent changes made according to the structure, shape, and principle of the present application should be included in the protection scope of the present application.
Claims
1. An energy-saving yellow reactive dye, characterized in that: The structure of the energy-saving yellow reactive dye is shown in Formula I: Wherein, R1 and R2 are independently selected from H and C1-C6 alkyl.
2. The energy-saving yellow reactive dye according to claim 1, characterized in that R1 and R2 are independently selected from H and C1-C3 alkyl.
3. The energy-saving yellow reactive dye according to claim 1, characterized in that: The energy-saving yellow reactive dye is selected from the following structures:
4. A method for preparing the energy-saving yellow reactive dye according to any one of claims 1 to 3, characterized in that: The steps include: Step 1): 3-amino 4-R1 substituted amino nitrobenzene and 3-amino 4-R2 substituted amino nitrobenzene react with oxalic acid to obtain bisbenzimidazole dinitro, and the reaction formula is as follows: Step 2): The bisbenzimidazole dinitro obtained in step 1) is subjected to a hydrogenation reduction reaction to obtain a bisbenzimidazole diamine color body. The reaction formula is shown below: Step 3): Add linear ester HClNH2CH2CH2OCH2CH2SO2CH2CH2Cl and cyanuric fluoride to the bisbenzimidazole diamine color body obtained in step 2), adjust the pH to 6.0-6.5, and react to obtain a reaction solution containing a condensate. The reaction formula is as follows: Step 4): The reaction solution containing the shrinkage product obtained in step 3) is heated to 20-25° C., the pH is adjusted to 7.5-8.0, and the reaction is carried out. The pH is adjusted to 6.5-7.0 to obtain the energy-saving yellow reactive dye. The reaction formula is as follows:
5. The method for preparing energy-saving yellow reactive dye according to claim 4, characterized in that: In the step 1), the reaction is carried out under reflux at 140-150° C. for 4-6 hours under the catalytic condition of tripolyphosphoric acid.
6. The method for preparing the energy-saving yellow reactive dye according to claim 4, characterized in that: In the step 2), the hydrogenation reduction reaction is carried out under the action of tin dichloride catalyst, the temperature of the hydrogenation reduction reaction is 70-80° C., and the time is 6-8 hours.
7. An energy-saving yellow reactive dye composition, characterized in that: It includes at least two of compound I-1, compound I-2 and compound I-3, and the structural formulas of compound I-1, compound I-2 and compound I-3 are as follows:
8. Use of the energy-saving yellow reactive dyes according to claims 1 to 3 and / or the energy-saving yellow reactive dyes obtained by the preparation methods according to claims 4 to 6 and / or the energy-saving yellow reactive dye composition according to claim 7 in textile dyeing.
9. The use according to claim 8, characterized in that: The textile is selected from one or more blends of cotton, linen, viscose, silk, silkworm silk and wool.
10. The use according to claim 8, characterized in that: The energy-saving yellow reactive dye is used in an amount of 0.5-12% owf.