the cyanuric chloride pulping liquid in the step 1) is obtained by adding cyanuric chloride and a dispersant into an ice water mixture for pulping. Preferably, the temperature is controlled to be 0-3 ℃ during the pulping treatment in the step 1). The dispersant is selected from sodium lignosulfonate, hydroxymethyl cellulose, dispersant NNO or dispersant MF. More preferably, the dispersant MF having excellent dispersing performance is selected as the dispersant.

In the step 2) and the step 3), para-ester and meta-ester are respectively fed with solid, so that the operation difficulty can be effectively reduced, the operation stability is improved, and the operation risk is reduced; if the para-ester is dissolved and then added into the cyanuric chloride, the para-ester is dissolved and then belongs to an alkaline solution, the cyanuric chloride is easily hydrolyzed when being added into the cyanuric chloride, and the first-condensation conversion rate is influenced finally, if the para-ester is dissolved and then added into the first-condensation solution for reaction, the volume is large, the material concentration is reduced, the reaction progress is influenced, byproducts are easily generated due to overlong reaction time, and finally the para-ester and the meta-double solid are selected for feeding, so that the reaction effect is improved.

The mass concentration of the mixed alkali solution in the step 2) is 10-15%; the mixed alkali is sodium carbonate and baking soda, and the mass ratio of the sodium carbonate to the baking soda is 1-2: 2; the condensation reaction is controlled at the temperature of 0-15 ℃; the molar ratio of the cyanuric chloride to the para-ester is 1: 0.95-1.02. Preferably, in the step 2), the ratio of the sodium carbonate to the baking soda is controlled to be 1.5:2, the condensation temperature is too low, the reaction speed is slow, the temperature is too high, cyanuric chloride is easy to hydrolyze, and the condensation reaction temperature is controlled to be 4-9 ℃. The molar ratio of cyanuric chloride to para-ester is easy to control to be a small excess of para-ester, for example, cyanuric chloride is excessive, a product of cyanuric chloride and m-bis independent condensation is easily generated in a secondary condensation process, the color fixing rate of a product is influenced, and preferably, the molar ratio of cyanuric chloride to para-ester is controlled to be 1: 1.01-1.02.

In the step 4), before diazotization is carried out after secondary condensation and cooling, a certain amount of auxiliary agent is added into the material, so that the fluidity of the material is improved, the diazonium salt is changed into a slurry with good fluidity from a viscous state, and the conversion rate of the diazonium salt is obviously improved; when the viscous diazonium salt is coupled with H acid, the material is viscous and difficult to react, local alkali neutrality is easy to cause over-strong, the diazonium salt is hydrolyzed, the acid couple conversion rate is influenced, the fluidity is obviously improved after the addition of the auxiliary agent, the diazonium salt is fully contacted with the H acid during coupling, the side reaction is obviously reduced, and the acid couple purity and the conversion rate are obviously improved.

Controlling the diazotization reaction temperature in the step 4) to be 0-8 ℃; in order to ensure that the diazo reacts quickly and does not decompose, the pH is controlled to be 1-1.5. Preferably, the diazotization reaction temperature is 2-5 ℃. The functional auxiliary agent is selected from demulsifier, inorganic salt or dispersant, etc. To prevent demulsifiers and inorganic salts from affecting dye appearance and performance, the adjuvant is preferably dispersant NNO. Preferably, the dosage of the dispersant NNO is 5-10% of the dosage of cyanuric chloride, so that the flowability of the diazo can be obviously improved, and the application performance of the dye cannot be influenced.

In the step 5), the acid coupling reaction temperature is 10-20 ℃, the adding time of the H acid solution is 1-5 hours, and the pH value of the acid coupling reaction is 2-4. Preferably, the dropping time of the H acid in the step 5) is controlled to be 2-3 hours, the H acid solution is alkaline after being dissolved by 30% solution alkali, the H acid solution cannot react with the di-condensed diazonium salt too quickly after being added, and the partial alkalinity is too strong to cause the decomposition of the diazonium salt or generate a coupling byproduct of the H acid and the diazonium alkali. Further preferably, the acid coupling reaction temperature is controlled to be 10-15 ℃, the pH is controlled to be 2.4-2.8, the temperature and the pH value are low, the reaction is difficult, and the diazonium salt is easy to decompose when the temperature and the pH value are too high.

In the step 6), diazo component 6-beta-ethyl sulfuryl sulfate-2-naphthylamine-1-sulfonic acid with active groups is introduced into the alkali couple, the dye structure is converted from the traditional double active groups into the triple active groups, the fixation rate of the dye is obviously improved by increasing the number of the active groups, the diazo component is still in a naphthalene structure, the dye quality is not influenced by light coloring during dyeing, the dye is more firmly combined with cellulose fibers during dyeing, the dyeing rate and the dyeing reproducibility are better, the chroma and COD (chemical oxygen demand) of the printed and dyed wastewater are obviously reduced, and the pressure for wastewater treatment is relieved.

In the step 6), the diazotization reaction is controlled at the temperature of 0-10 ℃ and the pH value is controlled at 1-1.5. Preferably, in the step 6), the temperature of 6-beta-ethylsulfonyl sulfate-2-naphthylamine-1-sulfonic acid diazo is controlled to be 2-5 ℃, and the pH value is controlled to be 1.2-1.5, so that the high conversion rate of diazo salt, quick reaction and no decomposition are ensured.

In the step 7), the temperature of the alkaline coupling reaction is controlled to be 5-15 ℃, and the pH value is 5-7. Preferably, in the step 7), the alkaline coupling temperature is controlled to be 8-12 ℃, and the pH value is controlled to be 6.5-7, so that the smooth reaction is ensured.

The invention also provides an application of the blue dye with three active groups prepared by the preparation method and a red dye in compounding as a red light blue active dye. The red dye structure selects benzene series, naphthalene series or anthraquinone series reactive dyes, and the mass ratio of the red dye to the blue dye with three reactive groups is 0.01-0.1: 0.99 to 0.9. According to the invention, the reactive red dye with excellent compatibility is selected for compounding according to the structure of the reactive blue dye, so that the obtained red light blue dye is bright and full in color and excellent in dye application performance.

Preferably, the red dye is selected from benzene dyes and naphthalene dyes with similar structures, and more preferably, the red dye is selected from three active groups with similar structures, and the structural formula is as follows:

preferably, the mass ratio of the red dye to the blue dye with the three active groups is 0.05-0.08: 0.95 to 0.92.

The dyeing method of the red light blue reactive dye during dyeing comprises the following steps: firstly, the temperature is raised to 60-65 ℃ for dyeing for the first time, and then the temperature is raised to 75-90 ℃ for dyeing for the second time. According to the coloring performance of the reactive dye, when the reactive dye is used, the vinyl sulfone group and the cellulose fiber of the textile are covalently bonded and attached to the textile at low temperature, and then the temperature is continuously increased to a higher temperature to bond the s-triazine chlorine atom with lower activity with the cellulose fiber, so that the color fixing rate of the dye can be effectively improved by 3-5 percent finally.

Preferably, when the red light blue reactive dye is used, the dyeing temperature is uniformly raised to 60-65 ℃ (primary temperature rise) for dyeing for 120 minutes, and then the temperature is raised to 70-90 ℃ (secondary temperature rise) for dyeing. Considering the reactivity and energy consumption of the third chlorine atom on s-triazine. Further preferably, the secondary heating is controlled at 75-80 ℃ for dyeing for 30 minutes, so that the fixation rate of the dye can be obviously improved, and the energy consumption is not too high due to overhigh temperature.

Compared with the prior art, the invention has the beneficial effects that:

(1) the cyanuric chloride, the para-ester and the meta-bis are all fed in solid, so that the operation stability can be effectively improved, the solid content of the dye can be improved, and the post-treatment cost can be reduced.

(2) In the invention, the dispersant NNO (sodium methylene dinaphthalene sulfonate) is added before the secondary condensate is used as the diazo, so that the flowability of the diazo material can be effectively improved, the conversion rate of the diazonium salt is increased, and the yield and the quality of the dye are obviously improved.

(3) According to the invention, 6-beta-ethyl sulfuryl sulfate-2-naphthylamine-1-sulfonic acid diazonium salt is introduced in the secondary coupling process, so that the active groups in the dye structure are increased, the dye uptake and the color fastness of the dye are obviously improved, the COD (chemical oxygen demand) and the chromaticity of the waste water after the dye is used are obviously reduced, the dyeing and sewage treatment costs are effectively reduced, and great economic benefits are achieved.

(4) The three-active-group red dye with good compatibility is selected to be compounded with the blue dye, the color light of the dye obtained by color matching is full and gorgeous, the lifting power, leveling property and alkali resistance of the dye are greatly improved, and the dye has good market potential.

(5) By utilizing the activity sequence of the vinyl sulfone and the chlorine atoms and adopting a dyeing method of firstly low temperature and then high temperature, the hydrolysis risk of the vinyl sulfone can be effectively reduced, the utilization rate of the chlorine atoms is improved, and the dyeing process with high color fixing rate and color fastness is obtained.

Detailed Description

The present invention will be further described with reference to specific examples.

Example 1

(1) By one-shot condensation

Weighing 20 g of cyanuric chloride and 0.3g of dispersing agent MF in a 1000mL beaker, pulping for 0.5h in an ice bath, adding 30.45 g of folded para-ester dry powder, supplementing a small amount of dispersing agent MF and crushed ice, continuously mixing and pulping for 1 h, adjusting the pH value of the material to 2.8-3.2 by using mixed alkali for about 1 h, keeping the temperature at 4-9 ℃, and reacting at the pH value of 2.8-3.2 to the end point.

(2) Second condensation of

At the end of the first condensation, adding 22.3 percent of solid sodium bicarbonate, adjusting the pH value to 5-5.5 by baking soda, heating to 20-25 ℃, maintaining the pH value of 5-5.5, and reacting for 3-4 hours until the end is reached.

(3) Diazo reaction of the two condensates

And after the secondary condensation is finished, cooling to below 5 ℃ in an ice bath, adding 1 g of dispersant NNO, stirring for 5 minutes, adding hydrochloric acid, continuously stirring for 5 minutes, adding sodium sulfite for 5-10 minutes, maintaining the temperature at 2-5 ℃ after the addition is finished, stirring for reaction for 1-1.5 hours, and removing excessive sodium nitrite by sulfamic acid for later use.

(4) Acid coupling

Weighing 32.96 g of folded H acid in a 500mL beaker, adding 150mL of water, adjusting the pH value of 6-6.5 by using 30% liquid caustic soda under stirring, slowly adding the H acid solution into the diazonium salt after dissolving, stirring after dripping for about 2-3H, maintaining the pH value of an acid couple at 2.4-2.8 by using sodium bicarbonate, keeping the temperature at 10-15 ℃, and reacting for 8-10H.

(5) 6-beta-ethylsulfonyl sulfate-2-naphthylamine-1-sulfonic acid diazo

Weighing 40.61 g of 6-beta-ethylsulfonyl sulfate-2-naphthylamine-1-sulfonic acid dry powder in percentage by weight in a 250mL beaker, pulping for 2h in ice bath, adding hydrochloric acid, stirring for 5 min, adding a sodium nitrite solution after 10-15 min, after the sodium nitrite is added, keeping the temperature for 2-5 ℃, and stirring for reaction for 1.5 h.

(6) Basic coupling

After the end point of 6-beta-ethyl sulfuryl sulfate-2-naphthylamine-1-sulfonic acid diazo is reached, sulfamic acid removes excessive sodium nitrite, diazo salt is quickly added into acid coupling liquid, the pH value is adjusted to 6.5-7.0 immediately after the addition, the temperature T is kept at 8-12 ℃, and the reaction is reached to the end point.

Example 2

(1) By one-shot condensation

Weighing 20 g of cyanuric chloride and 0.3g of dispersing agent MF in a 1000mL beaker, pulping for 0.5h in an ice bath, adding 30.6 g of folded para-ester dry powder, supplementing a small amount of dispersing agent MF and crushed ice, continuously mixing and pulping for 1 h, adjusting the pH value of the material to 2.8-3.2 by using mixed alkali for about 1 h, keeping the temperature at 4-9 ℃, and reacting at the pH value of 2.8-3.2 to the end point.

(2) Second condensation of

(3) Diazo reaction of the two condensates

(4) Acid coupling

(5) 6-beta-ethylsulfonyl sulfate-2-naphthylamine-1-sulfonic acid diazo

(6) Basic coupling

Example 3

(1) By one-shot condensation

(2) Second condensation of

(3) Diazo reaction of the two condensates

And after the secondary condensation is finished, cooling to below 5 ℃ in an ice bath, adding 1.4 g of dispersant NNO, stirring for 5 minutes, adding hydrochloric acid, continuously stirring for 5 minutes, adding sodium sulfite for 5-10 minutes, maintaining the temperature at 2-5 ℃ after the addition is finished, stirring for reaction for 1-1.5 hours, and removing excessive sodium nitrite by sulfamic acid for later use.

(4) Acid coupling

(5) 6-beta-ethylsulfonyl sulfate-2-naphthylamine-1-sulfonic acid diazo

(6) Basic coupling

Example 4

(1) By one-shot condensation

Weighing 20 g of cyanuric chloride and 0.3g of dispersing agent MF in a 1000mL beaker, pulping for 0.5h in an ice bath, adding 30.75 g of folded para-ester dry powder, supplementing a small amount of dispersing agent MF and crushed ice, continuously mixing and pulping for 1 h, adjusting the pH value of the material to 2.8-3.2 by using mixed alkali for about 1 h, keeping the temperature at 4-9 ℃, and reacting at the pH value of 2.8-3.2 to the end point.

(2) Second condensation of

(3) Diazo reaction of the two condensates

And after the secondary condensation is finished, cooling to below 5 ℃ in an ice bath, adding 2 g of dispersant NNO, stirring for 5 minutes, adding hydrochloric acid, continuously stirring for 5 minutes, adding sodium sulfite for 5-10 minutes, maintaining the temperature at 2-5 ℃ after the addition is finished, stirring for reaction for 1-1.5 hours, and removing excessive sodium nitrite by sulfamic acid for later use.

(4) Acid coupling

(5) 6-beta-ethylsulfonyl sulfate-2-naphthylamine-1-sulfonic acid diazo

(6) Basic coupling

Comparative example 1

Comparative example 1 a blue dye was synthesized according to the procedure provided in example 1 of application No. 200810154075.

The physical and chemical indexes and application performance of the dyes synthesized in examples 1-4 and comparative example 1 are compared, and the obtained results are shown in table 1:

TABLE 1 comparison of dye indices for examples 1-4 and comparative example 1

As can be seen from Table 1, the indexes of the reactive blue dye prepared in the examples 1-4, such as chromatic light, fixation rate and solubility, are superior to those of the reactive blue dye in the comparative example 1, the solubility of the dye is improved from 200g/L to about 300g/L, and the fixation rate, the yield of the sizing agent and the like are also greatly improved; in addition, as can be seen from the application performance data, the dyes prepared in examples 1 to 4 are more excellent in dry rubbing, wet rubbing and soaping cotton staining, and show certain superiority in fastness. The test methods referred to in the above tables all use national standards.

Application example 1

The blue dye synthesized in the example 1 and a three-active-group red dye with a similar structure are mixed according to a mass ratio of 0.99-0.9: and (3) performing color matching according to the proportion of 0.01-0.1 to obtain the red light blue reactive dyes with different specifications, and respectively obtaining a sample 1, a sample 2, a sample 3, a sample 4 and a sample 5.

The performance indexes of the red light blue reactive dye are shown in the table 2.

Table 2 performance index of red light blue reactive dye in application example 1

Remarking: the dye K/S values are all values at 2% proof of dyeing.

As can be seen from Table 2, with the addition of the red component, the color light of the dye is changed from slightly dark green to slightly green to more red and brilliant, the dark light gradually disappears, the color light of the dye becomes bright and full, meanwhile, the lifting power of the dye is obviously increased, the color and COD of the dyed wastewater are both low, and the dyeing wastewater is easy to treat; when the mass ratio of blue to red dye reaches 9:1, the color light is more red and bright, and the red light is too enough, so that the dyeing process has poor level-dyeing property and is easy to generate dyeing floras, and the dyeing effect is influenced, wherein the mass ratio of blue to red is 0.92-0.95: when the dye is 0.08-0.05, the dye is bright and full in color light, the wet milling fastness is improved to a certain extent, the dyeing reproducibility is good, and the market demand is met.

Application example 2

The dye sample 4 compounded in the application example 1 was dyed at different temperatures, and the performance indexes of the dye are shown in table 3.

Table 3 results of experiments using different dyeing temperature conditions for sample 4 of example 2

As can be seen from Table 3, the relative fixation rate of the dye can reach 102% by adopting the existing dyeing process, and the COD of the waste water is 1500 mg/L; when the dyeing temperature is reduced to 50-55 ℃, the speed of deesterifying the ethyl sulfone sulfate group into the vinyl sulfone is slow, and part of the ethyl sulfone structure still exists after two hours, so that the dye fixation rate is low; when the temperature is increased to 70-75 ℃ and 80-85 ℃, the fixation rate of the dye is respectively reduced to 96% and 90%, and at the moment, part of the ethyl sulfone sulfate is directly hydrolyzed, so that the fixation rate is greatly reduced; by adopting the dyeing process, one-step heating dyeing is added on the basis of the prior art, when the vinyl sulfone dyeing is finished, the temperature is continuously raised, so that the coloring capacity of the active chlorine can be effectively improved, the final color fixing rate is higher than that of the prior art by 3 percent, the COD (chemical oxygen demand) of the dye waste water is reduced to 1000mg/L, the color fastness to washing of the dye is improved to a certain extent, and the dyeing process has obvious advantages compared with the prior art.

The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only the most preferred embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.

Claims

1. The application of the complex formulation of the three-active-group blue dye and the red dye as the red light blue active dye is characterized in that the preparation method of the three-active-group blue dye comprises the following steps:

2) adding the solid para-ester into the pulping liquid obtained in the step 1), continuously pulping, adding a mixed alkali solution to adjust alkali, and carrying out primary condensation reaction to obtain a condensate; the mixed alkali is sodium carbonate and baking soda; the mass concentration of the mixed alkali solution is 10-15%; the mass ratio of the sodium carbonate to the baking soda is 1-2: 2;

4) adding crushed ice into the secondary condensate obtained in the step 3), cooling, adding a certain amount of auxiliary agent, and sequentially adding hydrochloric acid and sodium nitrite to obtain secondary condensate diazo liquid; the auxiliary agent is dispersant NNO, and the using amount of the dispersant NNO is 5-10% of the feeding amount of cyanuric chloride;

7) adding 6-beta-ethyl sulfuryl sulfate-2-naphthylamine-1-sulfonic acid diazonium salt into the acid coupling solution obtained in the step 5) to carry out alkaline coupling reaction to obtain a tri-active blue dye;

the structural formula of the red dye is as follows:

；

the mass ratio of the red dye to the blue dye with three active groups is 0.05-0.08: 0.95 to 0.92;

the dyeing method of the red light blue reactive dye during dyeing comprises the following steps: firstly, the temperature is raised to 60-65 ℃ for dyeing for the first time, and then the temperature is raised to 75-90 ℃ for dyeing for the second time.

2. The use of the blue tri-reactive dye in combination with a red dye as a red-light blue-reactive dye according to claim 1, wherein the dispersant in step 1) is selected from sodium lignosulfonate, hydroxymethyl cellulose, dispersant NNO or dispersant MF.

3. The application of the three-active-group blue dye and the red dye compounded together as the red-light blue active dye according to claim 1, characterized in that the condensation reaction in the step 2) is controlled at the temperature of 0-15 ℃; the molar ratio of the cyanuric chloride to the para-ester is 1: 0.95-1.02.

4. The application of the blue tri-active dye compounded with the red dye as the red light blue active dye in the claim 1 is characterized in that the diazotization reaction in the step 4) is controlled at the temperature of 0-8 ℃ and the pH value is controlled at 1-1.5.

5. The application of the blue three-active-group dye compounded with the red dye as the red blue active dye in the step 5) is characterized in that the acid coupling reaction temperature is 10-20 ℃, the adding time of the H acid solution is 1-5 hours, and the pH value of the acid coupling reaction is 2-4.

6. The application of the blue tri-active dye compounded with the red dye as the red blue active dye in the claim 1 is characterized in that the diazotization reaction in the step 6) is controlled at the temperature of 0-10 ℃ and the pH value is controlled at 1-1.5.

7. The application of the blue three-reactive group dye compounded with the red dye as the red blue reactive dye in the step 7) is characterized in that the temperature of the alkaline coupling reaction in the step 7) is controlled to be 5-15 ℃, and the pH value is 5-7.