Preparation method of reactive brilliant blue

Abstract

The invention discloses a preparation method of reactive brilliant blue, which comprises the following steps: S1, condensation reaction, S2, color base refining and dissolving, S3, primary condensation, S4, secondary condensation, S5, tertiary condensation, and S6, drying, the reactive dye has high reactivity, good fixation ability and excellent dyeing performance, and can realize low-alkali or alkali-free dyeing. Meanwhile, the reactive dye also has excellent high-temperature resistance, can be matched with a disperse dye for use, and can be used for simultaneously dyeing the T / R or T / C blended fabric at the temperature of 100 DEG C, so that a one-bath dyeing process is realized, the dyeing process is simplified, the dyeing time is shortened, and the discharge capacity, the labor cost and the energy consumption are greatly reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of dye technology, and in particular to a preparation method of reactive brilliant blue. BACKGROUND

[0002] At present, the common dyeing method for polyester-cotton blended fabric on the market is two-bath method, that is, first dyeing the fabric with disperse dyes, washing, and then dyeing with reactive dyes, washing. Although it has good color consistency and high fastness, the process is long and energy consumption is high, which is not conducive to energy saving and emission reduction and clean production of printing and dyeing enterprises, and with the extension of processing time, color difference and vat difference problems may occur in production, affecting product quality and efficiency. In order to solve these problems, many factories are exploring one-step one-bath dyeing process, but the existing reactive dyes still have poor high temperature resistance and can only be dyed at about 50℃, which is not suitable for one-step one-bath dyeing with disperse dyes. The disadvantages of the prior art are: 1. The traditional reactive dyes have poor high temperature stability and are not suitable for high temperature dyeing process. 2. The traditional reactive dyes need to add alkali agent for crosslinking and fixing with cotton fibers, and the amount of alkali agent added is generally 20g / l. 3. The dyeing process of traditional reactive dyes and disperse dyes for polyester-cotton blended fabric is usually two-bath method, which is long in process and high in energy consumption, and is not conducive to energy saving and emission reduction of enterprises.

[0003] Reactive brilliant blue is a kind of reactive dye widely used in dye industry, which has the advantages of high solubility and solubility, high color yield and dyeing fastness. However, the existing reactive brilliant blue has the problems of poor dyeing performance, complex process and environmental impact. SUMMARY

[0004] The purpose of the present application is to solve the technical problems of poor dyeing performance, complex process and environmental impact of the existing reactive brilliant blue.

[0005] In order to achieve the purpose of the present application, the following technical solutions are adopted:

[0006] A preparation method of reactive brilliant blue, comprising the following steps:

[0007] S1 condensation reaction: bromoamino acid is added to the reaction kettle, when the temperature reaches the set temperature, intermediate bis, defoaming agent and baking soda industrial product are added, the PH is measured to reach the specified value, the temperature is raised to the set temperature, and then the pre-prepared copper sulfate and stannous chloride mixed solution is slowly added, the disappearance of bromoamino acid is measured as the end point, then diluted, filter aid, light calcium and activated carbon are added and stirred, heated and filtered, and the filtrate is collected;

[0008] S2 color base refining and dissolution:

[0009] (a) Color base refining, the collected filtrate brine is cooled to below 10°C, hydrochloric acid is added, the PH is adjusted to the set value, and the reaction is carried out for 2-4 hours. The end point is determined by measuring the wet circle condition, and the end point is determined when there is no blue circle on the spot. Filter pressing is carried out, and after filter pressing is completed, the filter cake is rinsed with brine and blown dry.

[0010] (b) Color base refining, the collected filtrate brine is cooled to below 10°C, hydrochloric acid is added, the PH is adjusted to the set value, and the reaction is carried out for 2-4 hours. The end point is determined by measuring the wet circle condition, and the end point is determined when there is no blue circle on the spot. Filter pressing is carried out, and after filter pressing is completed, the filter cake is rinsed with brine and blown dry.

[0011] S3 One condensation:

[0012] (a) Dissolution of benzidine disulfonic acid

[0013] Add base water to the reaction kettle, add benzidine disulfonic acid solid, stir, slowly add liquid alkali to adjust the PH to 5.0-5.5, and stop stirring after the material is clarified.

[0014] (b) Condensation

[0015] Add base water and crushed ice to the cyanuric chloride kettle, add cyanuric chloride, and beat the pulp at 0°C. Slowly add the above-mentioned benzidine disulfonic acid, control the temperature to be 5-10°C during feeding, and the PH is less than or equal to 4.0. After the benzidine disulfonic acid is added, slowly adjust the PH to 3.0-3.5 with baking soda, and keep the temperature at 5-12°C. The reaction is carried out until the end point is reached.

[0016] S4 Second condensation

[0017] Add the above-mentioned color base liquid to the first condensate, stir evenly, and heat to 45-50°C while maintaining the PH at 5.5-6.0 with baking soda. The reaction is carried out for 5-6 hours, and the end point is determined by HPLC detection. The end point is reached when the color base is less than or equal to 1.5%.

[0018] S5, third condensation

[0019] Add nicotinic acid and promoter AL solid to the second condensate, stir, and detect the PH value of the material, which should be between 4.5 and 5.5. Adjust the PH to 5.0-5.5 with a small amount of liquid alkali, then heat, and detect the end point by HPLC. The end point is reached when the second condensate is less than or equal to 2%.

[0020] S6 Drying

[0021] After the third condensation is completed and the PH is re-measured to be 5.5 and stable, it is sent to the post-processing section for spray drying.

[0022] In some embodiments, in step S1, when the temperature of the reaction kettle reaches 85-90°C, bromoamino acid is added, and when the temperature reaches 80°C, m-bis is added.

[0023] In some embodiments, in step S1, baking soda is added, the PH is determined to be 9, the temperature is raised to 80 DEG C, and the pre-prepared copper sulfate and stannous chloride mixed solution is slowly added, after the addition is completed, the reaction kettle is maintained at 80 DEG C for 15 minutes, then slowly raised to 85 DEG C, and maintained at 85 DEG C for 3 hours, and the bromoamino acid disappearance is determined as the end point.

[0024] In some embodiments, in step S1, the dilution is divided into two times, the first time is to add 80 DEG C hot water to 2000L, and stir for 30 minutes; the second time is to add 80 DEG C hot water to 4000L, the temperature is 80 DEG C, 25Kg filter aid 25kg light calcium and 20 activated carbon are added, and stirred for 15 minutes, then heated and filtered, and the filtrate is collected.

[0025] In some embodiments, in step S1, after the purple paste filtration is completed, it is rinsed with 80 DEG C hot water, and blown dry, and during the whole reaction process, the material is seriously thickened, and an appropriate amount of 80 DEG C hot water can be added.

[0026] In some embodiments, in step S2, after the hydrochloric acid is added, the PH is adjusted to 0.5, and the reaction is carried out for 2-4 hours, and the circle is determined.

[0027] In some embodiments, in step S2, the color base filter cake is added under stirring, and half of the filter cake is added, and then the sodium carbonate is added.

[0028] In some embodiments, in step S5, after the PH is adjusted to 5.0-5.5, then the temperature is raised to 80-90 DEG C, and the temperature is maintained for 6-8 hours.

[0029] The preparation method of the reactive brilliant blue provided by the application has the following advantages:

[0030] The reactive dye provided by the application has high reactivity, good color fixing capacity and excellent dyeing performance, and can realize low-alkali or alkali-free dyeing. Meanwhile, the reactive dye provided by the application also has excellent high-temperature resistance, and can be used in cooperation with disperse dyes to simultaneously dye T / R or T / C blended fabrics at 100 DEG C, to realize one-bath dyeing process, which not only simplifies the dyeing process and shortens the dyeing time, but also greatly reduces the pollution discharge amount, labor cost and energy consumption. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical scheme and advantages of the embodiments of the application more clear, the technical scheme of the embodiments of the application will be clearly and completely described below, obviously, the described embodiments are part of the embodiments of the application, not all the embodiments.

[0032] The "several" and "multiple" in the embodiments refer to two or more than two. In the description of the present application, it should be pointed out that the orientation or position relationship indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer" and the like is only for the convenience of describing the present application and simplifying the description, and does not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application. In addition, the terms "first", "second", "third" are only for the purpose of description, and cannot be understood as indicating or implying relative importance.

[0033] In the description of the present application, it should be pointed out that unless otherwise explicitly specified and limited, the terms "mounting", "connection", "connection" should be understood broadly, for example, it can be fixed connection, or detachable connection, or integral connection; it can be mechanical connection, or electrical connection; it can be directly connected, or indirectly connected through intermediate medium, or the communication inside two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0034] The preparation method of the active brilliant blue provided by the embodiment comprises the following steps: 1, condensation in 2T reaction pot, put the bottom water 750L, heat to 85-90℃, add bromoamino acid 202Kg, beat for 1-2 hours, when the temperature is 80℃, add m-bis quantitative, add m-bis, add a little defoaming agent, immediately slowly add baking soda industrial product 202kg, pay attention to foam, after adding baking soda, measure the PH value should be 9, heat to 80℃, start to slowly add the mixed solution of copper sulfate and stannous chloride prepared in advance (T≥60℃), pay attention to defoaming in time, after adding, maintain 80℃ in the pot for 15 minutes, then slowly heat to 85℃, record the time, keep 85℃, react for 3 hours, measure the disappearance of bromoamino acid as the end point, then dilute twice, first add 80℃ hot water to 2000L, stir for 30 minutes; secondly add 80℃ hot water to 4000L, temperature 80, add 25kg filter aid 25kg light calcium and 20 activated carbon, stir for 15 minutes, heat filtration, collect the filtrate. After filtration, rinse with 750L, 80℃ hot water, and blow dry. If the material is thick during the whole reaction process, a proper amount of 80℃ hot water can be added, generally the added amount should not exceed 100kg, so as to ensure the fluidity of the material, and the volume should be strictly controlled within 1500-1600L, and should not exceed 1600L.

[0035] 2, color base refining and dissolving

[0036] (1) Collecting filtrate brine cooling 10 ℃ or less, with hydrochloric acid 330Kg or so (not too slow to add, to not boil over, control 20 minutes, add complete), at this time a large number of foam generated, to prevent overflow, adjust PH = 0.5 or so, PH good, reaction 2-4 hours, measured circle, no blue spot for the end point, filter pressing, filter pressing complete with salt water rinse (water 1000L, salt 100Kg all solution), blow dry. (Rinse end with p-nitroaniline diazonium salt test pink end, otherwise affect the next step cyanuric chloride dosage).

[0037] (2) Color base dissolution

[0038] 700L, add soda 12 kg under stirring, add color base filter cake, add half of the filter cake, then add soda 10 kg, after adding all the filter cake, adjust PH = 6.6-7.5 with soda, generally soda dosage is about 25 kg, heat to 30-35 ℃, stir for 1-2 hours, ensure that the color base is completely dissolved, measure the volume V = 1700-2000 L, calculate the yield by chemical analysis.

[0039] 3, primary condensation

[0040] (1) Dissolution of benzidine disulfonic acid

[0041] In the dissolution kettle, add 1000L of bottom water, add benzidine disulfonic acid solid, stir for 10 minutes, slowly add liquid alkali to adjust PH = 5.0-5.5, stir until the material is clear, then stop stirring and wait.

[0042] (2) Condensation

[0043] In the cyanuric chloride kettle, add 500L of bottom water, 600 kg of crushed ice, and add cyanuric chloride, and beat the slurry at 0 ℃ for 1 hour. Slowly add the above-mentioned benzidine disulfonic acid, control the temperature at 5-10 ℃ during feeding, and PH ≤ 4.0. After the addition of benzidine disulfonic acid is complete, slowly adjust PH = 3.0-3.5 with baking soda, and keep the temperature at 5-12 ℃, and react until the end point. The volume is ≤ 2500 L.

[0044] 4, secondary condensation

[0045] Add the above-mentioned color base liquid to the primary condensate, stir uniformly, heat to 45-50 ℃, and at the same time, maintain PH = 5.5-6.0 with baking soda, and react for 5-6 hours, and detect the end point by HPLC, and the color base is ≤ 1.5% for the end point. The volume is ≤ 4500 L.

[0046] 5, tertiary condensation

[0047] Nicotinic acid and promoter AL solid were added into the di-condensed liquid, stirred for 10 minutes, the material PH value should be between 4.5-5.5, a small amount of liquid alkali was used to adjust the PH to 5.0-5.5, then heated to 80-90℃, keep the temperature for 6-8 hours, HPLC detection end point, di-condensed substance ≤2% as the end point. Volume 4800-5000L.

[0048] 6、Drying

[0049] After the third condensation was completed, the PH was re-measured to be 5.5, and after stabilization, the product was sent to the post-treatment section for spray drying.

[0050] The active brilliant blue ingredient table of this example (0.5 mol)

[0051]

[0052]

[0053] The chemical structure of the active brilliant blue TCR-SP of this example:

[0054]

[0055] The dyeing agent prepared by the preparation method of the active brilliant blue provided in this example is compared with the comparative example as follows.

[0056] The active dyes of this example and the comparative example (commercial brilliant X-BR) were each prepared into a dyeing liquid with a dyeing depth of 2% o.w.f, a sodium sulfate dosage of 60g / l, and a bath ratio of 1:10, for standby.

[0057] I. Dyeing process (pure cotton)

[0058] The dyeing process of this example was used: the dyeing liquid prepared by the active dye of this example was heated, and pure cotton was dyed, washed, and soaped, to complete the dyeing.

[0059] The dyeing process of the dyeing liquid of the comparative example was used: the dyeing liquid prepared by the active dye of the comparative example was heated, and soda ash (dosage 20g / l) was added, and pure cotton was dyed, washed, and soaped, to complete the dyeing.

[0060] II. Determination of optimal dyeing temperature

[0061] The dyeing liquids prepared by the active dyes of this example and the comparative example were respectively dyed at 60℃, 80℃, 100℃, 110℃, 120℃, and 130℃, and the color yield of the 12 pieces of dyed pure cotton was measured, and the color yield at 130℃ was taken as the reference standard, and the relative color yield of the pure cotton at 60℃, 80℃, 100℃, 110℃, and 120℃ was calculated, and the results are shown in Table 1.

[0062] Table 1 compares the optimal coloring temperatures of the reactive dyes in the examples with those in the comparative examples.

[0063]

[0064] As can be seen from Table 1, the optimal coloring temperature for the reactive dyes in the examples is 100–130°C.

[0065] As can be seen from the above, the optimal dyeing temperature for the reactive dyes in this embodiment of the invention is 100–130°C, which is consistent with the dyeing temperature (110–130°C) of disperse dyes. Therefore, they can be mixed with disperse dyes for co-bath dyeing. Furthermore, when dyeing with the reactive dyes in this embodiment of the invention, it is not necessary to add soda ash for color fixing.

[0066] The optimal coloring temperature for existing common reactive dyes is around 60℃. They cannot be used in the same bath as disperse dyes. Furthermore, soda ash needs to be added during dyeing for color fixation, which not only increases the dyeing cost but also the cost of wastewater and sludge treatment.

[0067] III. Tests for light resistance, washability, perspiration resistance, abrasion resistance, heat and pressure resistance, and solubility.

[0068] 1) The dyeing solution prepared using the reactive dye in the example is heated to 100°C and dyed on pure cotton for 40 minutes. After cooling, the cotton is washed with water and soaped to complete the dyeing process.

[0069] 2) The dyeing solution prepared by the proportion of reactive dyes is heated to 60℃ to dye pure cotton. Soda ash (20g / l) is added for color fixation. The solution is kept warm for 40 minutes, then cooled, washed with water, and soaped to complete the dyeing process.

[0070] The performance of the dyed pure cotton fabric was tested, and the results are shown in Table 2. Table 2 shows the performance tests of the reactive dye red in the examples and comparative examples.

[0071]

[0072] As shown in Table 2, the reactive dyes of this invention, when dyeing at 100°C, exhibit fastness comparable to or even superior to that of existing reactive dyes dyeing at 60°C. In contrast, as shown in Table 1 above, existing reactive dyes show very poor dyeing performance when dyeing at 100°C.

[0073] The above performance tests adopted the following standards:

[0074] 1) Color fastness to rubbing: GB / T 3920-2008

[0075] 2) Color fastness to perspiration: GB / T 3922-2013

[0076] 3) Lightfastness: GB / T 8427-2008. Method 3

[0077] 4) Wash fastness: GB / T 3921-2008. Method 3

[0078] 5) Heat resistance 200℃: GB / T6152-1997.

[0079] 6) Solubility: GB / T21879-2015.

[0080] Therefore, the reactive dyes of this invention possess high reactivity, good color-fixing ability, and excellent dyeing performance, and can achieve low-alkali or alkali-free dyeing. Simultaneously, the reactive dyes of this invention also exhibit excellent high-temperature resistance, and can be used in conjunction with disperse dyes to simultaneously dye T / R or T / C blended fabrics at 100°C, achieving a one-bath dyeing process. This not only simplifies the dyeing process and shortens dyeing time but also significantly reduces wastewater discharge, labor costs, and energy consumption.

[0081] The technical principles of the present invention have been described above in conjunction with specific embodiments. However, it should be noted that these descriptions are merely for explaining the principles of the present invention and should not be construed as limiting the scope of protection of the present invention in any way. Based on this explanation, those skilled in the art can conceive of other specific embodiments or equivalent substitutions of the present invention without creative effort, and all such embodiments will fall within the scope of protection of the present invention.

Claims

1. A method for preparing reactive brilliant blue, characterized in that, Includes the following steps: S1 condensation reaction: Add bromoamino acid to the reaction vessel. When the temperature reaches the set temperature, add methyl methacrylate, defoamer and industrial sodium bicarbonate. Measure the pH to reach the specified value, raise the temperature to the set temperature, and slowly add the pre-prepared mixture of copper sulfate and stannous chloride. The endpoint is determined by the disappearance of bromoamino acid. Then dilute, add filter aid, light calcium and activated carbon, stir, filter while hot, and collect the filtrate. S2 chromogen refining and dissolution: (a) Color base purification: Cool the collected filtrate brine to below 10°C, add hydrochloric acid, adjust the pH to the set value, react for 2-4 hours, measure the luster of the spot, and the endpoint is when the spot has no blue circle. Filter by pressure, rinse with brine after filtration, and blow dry. (b) Dissolve the color base: Add soda ash to the bottom water and stir. Add the color base filter cake and adjust the pH to 6.6-7.5 with soda ash. Heat to 30-35℃ and stir to ensure that the color base is completely dissolved. S3 one-time condensation: (a) Dissolution of benzidine disulfonic acid Add water to the reactor, add benzidine disulfonic acid solid, stir, slowly add liquid alkali to adjust the pH to 5.0-5.5, stir until the material is clear, then stop stirring and set aside for use. (b) condensation Add water and crushed ice to the cyanuric chloride reactor, add cyanuric chloride, and slurry at 0°C. Slowly add the benzidine disulfonic acid, controlling the temperature at 5-10°C and the pH at ≤4.0 during the addition. After the benzidine disulfonic acid is added, slowly adjust the pH to 3.0-3.5 with baking soda, keep the temperature at 5-12°C, and react to the endpoint. S4 secondary condensation Add the above-mentioned chromogen solution to a concentrated solution, stir evenly, heat to 45-50℃, and maintain the pH at 5.5-6.0 with baking soda. React for 5-6 hours, and detect the endpoint by HPLC. The endpoint is defined as chromogen ≤1.5%. S5, triple condensation Add nicotinic acid and solid accelerator AL to the condensate solution, stir, and check that the pH value of the material is between 4.5 and 5.

5. Adjust the pH to 5.0-5.5 with a small amount of liquid alkali, then heat and determine the endpoint by HPLC. The endpoint was defined as ≤2% of dicondensate. S6 drying After three condensation cycles are completed and the pH is stabilized at 5.5, the product is sent to the post-processing section for spray drying.

2. The method for preparing reactive brilliant blue according to claim 1, characterized in that, In step S1, bromoamino acid is added when the temperature in the reactor reaches 85-90℃, and meta-bisamine is added when the temperature reaches 80℃.

3. The method for preparing reactive brilliant blue according to claim 2, characterized in that, In step S1, after the addition of baking soda is completed, the pH should be 9. The temperature is raised to 80°C, and the pre-prepared mixture of copper sulfate and stannous chloride is slowly added. After the addition is complete, the reaction vessel is kept at 80°C for 15 minutes. Then the temperature is slowly raised to 85°C and kept at 85°C for 3 hours. The endpoint is determined by the disappearance of bromoamino acid.

4. The method for preparing reactive brilliant blue according to claim 3, characterized in that, In step S1, the dilution is performed in two stages. For the first stage, add 80°C hot water to 2000L and stir for 30 minutes. For the second stage, add 80°C hot water to 4000L. At 80°C, add 25Kg of filter aid, 25kg of light calcium carbonate, and 20g of activated carbon, stir for 15 minutes, filter while hot, and collect the filtrate.

5. The method for preparing reactive brilliant blue according to claim 4, characterized in that, In step S1, after the purple filter is finished, rinse with 80°C hot water and blow dry. The material becomes very thick during the entire reaction process, so an appropriate amount of 80°C hot water can be added.

6. The method for preparing reactive brilliant blue according to claim 1, characterized in that, In step S2, after adding hydrochloric acid, adjust the pH to 0.5, react for 2-4 hours, and measure the shedding pattern.

7. The method for preparing reactive brilliant blue according to claim 1, characterized in that, In step S2, add soda ash and stir before adding the color base filter cake. Add soda ash after adding half of the filter cake.

8. The method for preparing reactive brilliant blue according to claim 1, characterized in that, In step S5, after adjusting the pH to 5.0-5.5, the temperature is raised to 80-90℃ and maintained for 6-8 hours.

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