High fixation monochlorotriazine-vinylsulfone bis-active active dyes, and preparation method and application thereof

Abstract

This invention provides a high-fixation-rate monochlorotriazine-vinyl sulfone dual-reactive dye, its preparation method, and its application. The raw materials for preparing the dual-reactive dye include monochlorotriazine-vinyl sulfone type dual-reactive dye filter cake, sodium nicotinate, and sodium N-methyltaurate. This invention provides the application of the monochlorotriazine-vinyl sulfone dual-reactive dye in the dyeing or printing of cellulose fiber materials. This invention solves the technical problems of easy hydrolysis of the vinyl sulfone group, significantly low fixation rate, and severe mismatch of the two groups' reactivity in the long-term high-temperature water environment of dual-reactive dye immersion dyeing process. It significantly improves the fixation rate under immersion dyeing conditions, while being compatible with conventional processes such as pad dyeing, roll dyeing, and printing, achieving an upgrade in dyeing performance across all scenarios; it is fully adaptable to existing commercial dye filter cake production lines, with a simple process, controllable cost, and strong industrial applicability; and it significantly improves the dye's storage stability and extends the product's shelf life.

Description

Technical Field

[0001] This invention belongs to the field of commercial processing technology of reactive dyes, specifically relating to a monochlorotriazine-vinyl sulfone bis-reactive dye, its preparation method, and its application. Background Technology

[0002] Monochlorotriazine-vinyl sulfone composite dual-reactive dyes are currently the most widely used and applicable reactive dyes in the textile printing and dyeing industry. They combine the advantages of good stability of the monochlorotriazine group and high reactivity of the vinyl sulfone group, making them suitable for dyeing and printing cellulose fibers such as cotton and viscose.

[0003] However, existing commercial processing techniques only involve conventional pulping, desalination, drying, and blending of dye synthesis filter cakes, achieving only standardization of dye formulations without precise control over the reactivity of the two reactive groups. The monochlorotriazine group exhibits relatively weak reactivity and a slow reaction rate; the vinyl sulfone group is highly reactive but easily hydrolyzed and deactivated, and is greatly affected by temperature, readily hydrolyzing at elevated temperatures. Existing commercial auxiliaries are mostly conventional excipients such as sodium sulfate, dispersants, and dust suppressants, which can only adjust dye strength and dispersion performance, failing to specifically control and synergistically match the reactivity of the two reactive groups. With the increasing cost of chemical raw materials, improving the utilization rate of corresponding dyes has received widespread attention; however, research on controlling dyes from the perspective of the reactivity of their reactive groups has not yet been conducted. Summary of the Invention

[0004] To overcome the shortcomings of the prior art, this invention provides a high fixation rate dual-reactive-group reactive dye, its preparation method and application. The process is simple to operate, has a wide range of applications, is low in cost, has low equipment requirements, and is energy-efficient.

[0005] In a first aspect, the present invention provides a monochlorotriazine-vinyl sulfone dual-reactive dye, wherein the raw materials for preparing the dual-reactive dye include a monochlorotriazine-vinyl sulfone dual-reactive dye filter cake, sodium nicotinate, and sodium N-methyltaurate, and the mass ratio of the monochlorotriazine-vinyl sulfone dual-reactive dye filter cake, sodium nicotinate, and sodium N-methyltaurate is 50-70:15-25:15-25.

[0006] In the raw materials for preparing the monochlorotriazine-vinyl sulfone dual reactive dye of the present invention, sodium nicotinate and sodium N-methyltaurate are used as functional auxiliaries. By introducing sodium nicotinate and sodium N-methyltaurate, the reactivity of the reactive groups can be controlled during the dyeing process. Sodium nicotinate improves the reactivity of the monochlorotriazine group, and sodium N-methyltaurate can react with vinyl sulfone to generate an intermediate. The intermediate can react with the groups on the fiber, thereby effectively reducing the hydrolysis reaction of the vinyl sulfone structure.

[0007] The monochlorotriazine-vinyl sulfone type dual reactive dye filter cake described in this invention can be a wet filter cake obtained by salting out, pressure filtration and water washing after dye synthesis, without high-temperature drying treatment, and its moisture content is generally 20-40%. In this invention, the mass of the reactive dye filter cake is based on its dry weight.

[0008] The monochlorotriazine-vinyl sulfone type dual reactive dye of the present invention is selected from at least one of the red, yellow and blue monochlorotriazine-vinyl sulfone type reactive dyes, wherein the red series includes CI Reactive Red 194, CI Reactive Red 195, etc., the yellow series includes CI Reactive Yellow 145, CI Reactive Yellow 176, etc., and the blue series includes CI Reactive Blue 194, CI Reactive Blue 222, etc.

[0009] The sodium nicotinate described in this invention is food-grade or industrial-grade high-purity sodium nicotinate with a purity ≥99%, free from impurity precipitation, and does not affect the color and dyeing performance of the dye. The sodium N-methyltaurate described is high-purity synthetic-grade sodium N-methyltaurate with a purity ≥98%, exhibiting excellent water solubility and completely soluble in water-based dye pastes at room temperature.

[0010] The raw materials for preparing the monochlorotriazine-vinyl sulfone bireactive dye of the present invention may also include commercially available conventional auxiliaries for reactive dyes. The conventional auxiliaries include at least one of dispersants, dust suppressants, sodium sulfate, and water softeners. The total amount of conventional auxiliaries added shall not exceed 8% of the total mass of the dye, and shall not react with sodium nicotinate or sodium N-methyl taurate, and shall not affect the dye's color-fixing performance and storage stability.

[0011] The monochlorotriazine-vinyl sulfone bis-reactive dye of the present invention can be prepared by referring to the commercial preparation route of conventional reactive dyes, which generally includes: filter cake pretreatment - functional auxiliaries compounding - commercial post-treatment.

[0012] In a second aspect, the present invention provides a method for preparing the monochlorotriazine-vinyl sulfone bis-reactive dye described in the first aspect, comprising the following steps: (1) Pretreatment of filter cake: The filter cake of monochlorotriazine-vinyl sulfone type reactive dye (usually wet filter cake) is coarsely crushed, and deionized water is added and stirred to disperse, so as to prepare a uniform and stable dye slurry. (2) Functional additive compounding: Add measured amounts of sodium nicotinate and sodium N-methyl taurate to the dye paste in sequence to completely dissolve the additives and fully compound them with the dye molecules; (3) The composite dye paste is processed for commercialization to obtain the finished product of monochlorotriazine-vinyl sulfone bireactive dye.

[0013] In step (1) of this invention, the solid content of the dye paste is generally 25% to 35%. The solid content mentioned in this invention refers to the mass percentage of solid substances (non-volatile substances) in the dye paste, which is usually determined by the drying and weighing method (oven method) at an oven temperature of 105°C.

[0014] In step (2) of this invention, the auxiliary agent can be completely dissolved and fully compounded with the dye molecules by means of stirring. In some embodiments, after adding the functional auxiliary agent in step (2), the stirring temperature is 20-30°C and the stirring time is 30-60 min, so that the auxiliary agent is completely dissolved and fully compounded with the dye molecules.

[0015] The post-processing steps for commercialization described in step (3) of this invention generally include: grinding, homogenization, spray drying, powder blending and standardization, testing, and sealing and packaging. The particle size of the dye particles in the ground slurry is generally controlled to be between 0.5 and 8 μm. Homogenization requires controlling the particle size of the dye particles in the slurry to be between 0.5 and 5 μm. The inlet temperature of the spray dryer is 180–220°C, and the outlet temperature is 85–100°C.

[0016] The finished dye prepared by this invention has a room temperature sealed storage stability of ≥6 months, and the dyeing fixation rate of fabrics is increased by 9% to 16% compared with conventional dyes of the same type.

[0017] Thirdly, the present invention provides the application of the monochlorotriazine-vinyl sulfone bireactive dye described in the first aspect in the dyeing or printing of cellulose fiber materials.

[0018] The cellulose fiber material can be cotton fabric, viscose cellulose fiber fabric, etc., and the applicable dyeing processes include pad dyeing, roll dyeing, dip dyeing, etc.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention is the first to adopt a synergistic system of sodium nicotinate and sodium N-methyltaurate, which specifically addresses the core pain points of the dual reactive dye industry, especially solving the technical problems of easy hydrolysis of vinyl sulfone groups, significantly low fixation rate, and severe mismatch of the activities of the two groups in the long-term high-temperature water environment of the immersion dyeing process. Through the bidirectional regulation mechanism of sodium N-methyltaurate pre-modifying vinyl sulfone to generate a high-temperature reactive and stable intermediate and sodium nicotinate catalyzing the activation of monochlorotriazine groups, ineffective hydrolysis loss is reduced from the root, and the fixation rate of immersion dyeing is greatly improved. At the same time, it is compatible with conventional processes such as pad dyeing, roll dyeing, and printing, realizing the upgrade of dyeing performance in all scenarios. The fixation improvement effect is significant and has non-obvious synergistic benefits. 2. It is fully compatible with existing commercial dye filter cake production lines, without the need to add dye production and synthesis steps. The process is simple, the cost is controllable, and it has strong industrial applicability. 3. Significantly improves the storage stability of dyes, extends product shelf life, and reduces enterprise storage losses. Detailed Implementation

[0020] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0021] The CI Reactive Red 195 wet filter cake (32% moisture content) used in all embodiments and comparative examples of this invention are the same product, as are the CI Reactive Blue 222 wet filter cake (34% moisture content) and CI Reactive Yellow 176 wet filter cake (35% moisture content).

[0022] The sodium nicotinate used in the embodiments of the present invention has a purity of ≥99%; the sodium N-methyl taurate has a purity of ≥98%, excellent water solubility, and can be completely dissolved in water-based dye pastes at room temperature.

[0023] The parts mentioned in the embodiments and comparative examples of this invention are all parts by mass.

[0024] Example S1

[0025] Take 30 parts of CI Reactive Red 195 wet filter cake (moisture content 32%), crush them and add deionized water to prepare a slurry with a solid content of 30%; add 6 parts of sodium nicotinate and 6 parts of sodium N-methyl taurate, stir at room temperature for 40 minutes until completely uniform; grind with sand mill until the dye particle size is 1-8μm, homogenize under high pressure until the dye particle size is 2-5μm, and then spray dry at an inlet temperature of 190℃ and an outlet temperature of 90℃. After cooling, perform standardized blending to obtain the finished dye.

[0026] Example S2

[0027] The finished dye was prepared by replacing the CI Reactive Yellow 176 wet filter cake (35% moisture content) in Example S1 with the CI Reactive Red 195 wet filter cake, and keeping all other aspects the same as in Example S1.

[0028] Example S3

[0029] Take 50 parts of CI Reactive Blue 222 wet filter cake (moisture content 34%), 15 parts of sodium nicotinate, and 15 parts of sodium N-methyl taurate, and prepare the finished dye according to the same process as in Example S1.

[0030] Examples S4 to S7

[0031] Take CI Reactive Red 195 wet filter cake (32% moisture content), CI Reactive Blue 222 wet filter cake (34% moisture content), and CI Reactive Yellow 176 wet filter cake (35% moisture content), and prepare reactive dye wet filter cakes according to the formulas shown in Table 1: S4: Red 195 + Blue 222 (mass ratio 1:1); S5: Red 195 + Yellow 176 (mass ratio 1:1); S6: Yellow 176 + Blue 222 (mass ratio 1:1); S7: Red 195 + Yellow 176 + Blue 222 (mass ratio 1:1:1); All mass ratios are based on the dry weight of the wet filter cake.

[0032] Take 42 parts of wet filter cake of reactive dye, 10 parts of sodium nicotinate, and 10 parts of sodium N-methyl taurate; prepare the finished dye according to the same process as in Example S1.

[0033] Comparative Examples D1-1 to D1-7 (traditional commercial dyes, without functional auxiliaries)

[0034] Comparative Examples D1-1 to D1-7 were compared with Examples S1 to S7, using the same reactive dye wet filter cake, but without the addition of sodium nicotinate and sodium N-methyltaurate, only conventional commercial auxiliaries (sodium sulfate, dispersant) were added. The specific preparation steps are as follows: According to Examples S1-S7, wet filter cakes of reactive dyes were crushed and deionized water was added to prepare a slurry with a solid content of 30%. 5 grams of sodium sulfate and 3 grams of dispersant MF were added, and the mixture was stirred at room temperature for about 40 minutes until completely homogeneous. The mixture was then ground by sand mill until the dye particle size was 1-8 μm, and homogenized under high pressure until the dye particle size was 2-5 μm. After spray drying, the inlet temperature was 190℃ and the outlet temperature was 90℃. After cooling, the mixture was standardized and blended to obtain a traditional commercial dye, which served as a basic blank control group.

[0035] Comparative examples D2-1 to D2-3 (commercially available finished dyes of the same type)

[0036] The following commercially available dual-reactive dyes of the same type and model were selected from the market: Kehua Red 3BSN (CI Reactive Red 195, D2-1), Kehua Blue BRF (CI Reactive Blue 222, D2-2), and Kehua Yellow 3RS (CI Reactive Yellow 176, D2-3) produced by Shanghai Kehua Dyestuff Industry Co., Ltd. These are high-end commercial dyes commonly used in the industry and were selected to benchmark the differences in application performance of the products of this invention.

[0037] Comparative Example D2-4 (commercially available finished dye of the same type)

[0038] The mainstream commercial dual-reactive dyes of the same type and model produced by Shanghai Kehua Dyestuff Industry Co., Ltd., namely Kehua Red 3BSN (CI Reactive Red 195), Kehua Blue BRF (CI Reactive Blue 222), and Kehua Yellow 3RS (CI Reactive Yellow 176), were selected and dry-mixed in a 1:1:1 ratio to compare the differences in application performance of the products of this invention.

[0039] Application Example 1

[0040] The finished dyes obtained in the above embodiments and comparative examples were all made from 100% pure cotton plain weave fabric (100g / m²). 2 Parallel control experiments were conducted using both immersion dyeing and conventional pad dyeing processes. All test environments, auxiliary agent dosages, and post-treatment processes were identical. Specific process parameters and color fixation rate data are as follows: 1. Dyeing process parameters (patented key adaptation process) The dyeing concentration was uniformly 2% (owf), the liquor ratio was 1:20, the sodium sulfate was 50g / L, and the soda ash was 15g / L. The fabric was placed at room temperature, the temperature was increased at a rate of 1℃ / min, the temperature was increased to 60℃ and held for 40min, the color was fixed for 30min, and then washed with hot water, soaped, washed with cold water, and dried.

[0041] 2. Pad dyeing process parameters

[0042] Two dips and two nips. The dye concentration for immersion and nipping is 50 g / L, the nip rate is 70%, and the pre-drying is carried out at 100℃ for 2 min. The alkali concentration is: sodium sulfate 200 g / L, alkali substitute 5 g / L, liquid alkali 3 g / L, the nip rate is 70%, the baking is carried out at 105℃ for 3 min, followed by washing, soaping, boiling, and drying.

[0043] To accurately quantify the technical advantages of this invention, each embodiment and comparative sample was uniformly numbered. Referring to the methods described in GB / T2391-2024 (immersion dyeing fixation rate) and GB / T 27592-2023 (pad dyeing fixation rate), fixation rate data and performance improvement of each group were obtained. The specific results are shown in Table 1 below.

[0044] Table 1

[0045] It can be seen from Table 1 above: 1. Color fixation rate of the dyeing process: The color fixation rate of the products in each embodiment of the present invention is 11% to 16% higher than that of Comparative Example D1 (traditional self-made dye) and 5% to 10% higher than that of Comparative Example D2 (commercially available dye). It can effectively solve the pain points of high-temperature hydrolysis of vinyl sulfone groups, large loss of effective dye, and poor color fixation efficiency in the dyeing process of traditional dyes.

[0046] 2. Color fixation rate of the pad-drying-steaming process: The color fixation rate of the products in each embodiment of the present invention is 9% to 13% higher than that of comparative example D1 and 6% to 10% higher than that of comparative example D2. It can be seen that it still maintains significant performance advantages under high-end continuous pad-drying-steaming conditions, with better fabric uniformity and color stability, and is suitable for industrialized large-scale high-quality dyeing processing.

[0047] In summary, the modified dyes of this invention exhibit stable and significant advantages in color fixation enhancement and hydrolysis resistance for red, yellow, and blue monochromatic systems, any two-color blending systems, and three-color compound blending systems. In the three monochromatic systems of red, yellow, and blue, as well as various blending systems, the color fixation rates of the immersion dyeing and pad-dry-pad-steam processes of this invention are significantly better than those of the blank control dyes and commercially available dyes in the same system. Among these, the three-color blending system shows the best synergistic effect and the largest improvement in color fixation, proving that the dual-auxiliary compounding system of this invention can effectively solve industry pain points such as imbalance of group activity, severe high-temperature hydrolysis during immersion dyeing, color deviation, and uneven color fixation when blending multiple dyes. The uniform and stable performance and balanced improvement in the three monochromatic systems fully verify that the technical solution of this invention has universality for mainstream red, yellow, and blue reactive dye systems, with no compatibility shortcomings, and can stably achieve a significant improvement in color fixation rate for all color systems and blending conditions.

[0048] Application Example 2: Additional Stability Tests for Dyes

[0049] After the finished dyes obtained from the above examples and comparative examples were stored at room temperature in sealed containers for 6 months, the fixation rate of the dual-process dyeing was retested according to the method of Application Example 1. The results showed that the fixation rate of the products in Examples S1 to S7 of the present invention decreased by ≤1.5%, with no color shift and no powder agglomeration; while the fixation rate of the dyes in Comparative Examples D1-1 to D1-7 and Comparative Examples D2-1 to D2-4 decreased by 5% to 8%, and the color deviation of the dyeing process was particularly obvious.

Claims

1. A monochlorotriazine-vinyl sulfone bireactive dye, characterized in that: The raw materials for preparing the monochlorotriazine-vinyl sulfone dual-reactive dye include monochlorotriazine-vinyl sulfone type dual-reactive dye filter cake, sodium nicotinate, and sodium N-methyltaurate. The mass ratio of the monochlorotriazine-vinyl sulfone type dual-reactive dye filter cake, sodium nicotinate, and sodium N-methyltaurate is 50-70:15-25:15-25.

2. The monochlorotriazine-vinyl sulfone bis-reactive dye as described in claim 1, characterized in that: The monochlorotriazine-vinyl sulfone type dual reactive dye is selected from at least one of the red, yellow, and blue monochlorotriazine-vinyl sulfone type reactive dyes.

3. A method for preparing a monochlorotriazine-vinyl sulfone bis-reactive dye as described in claim 1 or 2, characterized in that: The preparation method includes the following steps: (1) Pretreatment of filter cake: The filter cake of monochlorotriazine-vinyl sulfone reactive dye is coarsely crushed, and deionized water is added and stirred to disperse, so as to prepare a uniform and stable dye slurry. (2) Functional additive compounding: Add measured amounts of sodium nicotinate and sodium N-methyl taurate to the dye paste in sequence to completely dissolve the additives and fully compound them with the dye molecules; (3) The composite dye paste is processed for commercialization to obtain the finished product of monochlorotriazine-vinyl sulfone bireactive dye.

4. The preparation method according to claim 3, characterized in that: In step (1), the solid content of the dye paste is 25% to 35%.

5. The preparation method according to claim 3, characterized in that: The post-commercial processing described in step (3) includes: grinding, homogenization, spray drying, powder blending standardization, testing, and sealing packaging.

6. The preparation method according to claim 5, characterized in that: In step (3), the particle size of the dye particles in the slurry after grinding is made to be 0.5 to 8 μm, and the particle size of the dye particles in the slurry after homogenization is made to be 0.5 to 5 μm.

7. The preparation method according to claim 5, characterized in that: In step (3), the inlet temperature of the spray dryer is 180-220°C and the outlet temperature is 85-100°C.

8. The application of the monochlorotriazine-vinyl sulfone bis-reactive dye as described in claim 1 or 2 in the dyeing or printing of cellulose fiber materials.

Images