Dispersing agent composition solution and application thereof in preparation of liquid disperse dye

Abstract

The invention discloses a dispersant composition solution and application thereof in preparation of a liquid disperse dye. The dispersant composition comprises a graft copolymer A, a wetting agent B and a defoaming agent C. Wherein the grafted copolymer A is a beta-sodium naphthalene sulfonate or methyl sodium naphthalene sulfonate grafted polymer of sodium lignin sulfonate. The high-efficiency dispersing agent composition solution provided by the invention can be applied to preparation of a liquid disperse dye, the mass ratio of the dispersing agent composition to the disperse dye is (1: 2)-(1: 10), and the solid content of the liquid disperse dye is 30%-50%. Compared with a traditional dispersing agent, the dispersing agent composition has the advantages that the color depth value is obviously reduced, and the contamination to fibers is reduced. The liquid disperse dye prepared by using the dispersant composition shows excellent performance in the aspects of grinding efficiency, reduction hydrolysis rate, high-temperature dispersion stability and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of dispersants, and particularly relates to a high-efficiency dispersant composition solution and application of the dispersant composition solution in preparation of liquid disperse dyes. BACKGROUND

[0002] Polyester fiber has become the highest-yield synthetic fiber in the world due to its excellent wearability. Disperse dyes, as special dyes for dyeing polyester fiber, have also seen a significant increase in production. At present, powdered disperse dyes are still the mainstream dosage form in the market due to their good storage stability and convenient transportation. However, this dosage form has outstanding problems such as high energy consumption, serious dust pollution and large wastewater discharge in the preparation and application process, which has a significant impact on the environment.

[0003] As early as the 1960s, international manufacturers began to develop liquid disperse dyes. Compared with traditional powdered dyes, the liquid dosage form has multiple advantages: no dust pollution, excellent dispersing performance, not easy to caking, less additive dosage, easy to prepare nano-sized particles, high dye utilization rate. In addition, liquid dyes save the processes of spray drying and materializing, greatly simplify the production process and significantly reduce the wastewater discharge. However, liquid dyes still have technical bottlenecks such as poor storage stability and easy sedimentation and stratification, and their application performance has not achieved a qualitative breakthrough, which restricts the market promotion process.

[0004] In recent years, the requirements for energy saving and emission reduction in the printing and dyeing industry are increasingly strict. With the continuous development and application of new surfactants, liquid disperse dyes are becoming the mainstream direction of the development of the industry technology due to their significant advantages. In the preparation process of liquid disperse dyes, the grinding process is the basic link to improve the performance of the dyes, and the selection of grinding aids is the key factor to determine the grinding efficiency. At present, the commonly used dispersants in China mainly include naphthalene sulfonate formaldehyde condensate and sodium lignosulfonate. However, naphthalene sulfonate formaldehyde condensate has the problem of excessive free formaldehyde, which not only has poor ecological environmental protection and is difficult to degrade, but also reduces and hydrolyzes part of the dyes in the dyeing process; and the bio-based dispersant sodium lignosulfonate has the defects of strong foaming, poor wetting, insufficient dispersion stability and serious fiber staining in the liquid dye system. Obviously, the traditional naphthalene sulfonate formaldehyde condensate and sodium lignosulfonate dispersants cannot meet the performance requirements of modern liquid disperse dyes. SUMMARY

[0005] The present application provides a dispersant composition solution and its application in the preparation of liquid disperse dyes. Through graft copolymerization and compounding technology, a new high-efficiency dispersant composition is developed, which shows excellent performance in dispersibility, fiber staining, reduction and hydrolysis rate and high-temperature dispersion stability.

[0006] A dispersant composition solution comprising a graft copolymer A, a wetting agent B, and an antifoaming agent C in a mass ratio of 10:1:(0.01~0.02)~1:1:(0.01~0.02), and the solid content of the dispersant composition solution is 20%~50%.

[0007] The application of a dispersant composition solution in the preparation of liquid disperse dyes includes the following steps: after thoroughly mixing the dispersant composition solution and deionized water, the pH of the solution is adjusted to 5-6; disperse dye filter cake and zirconia beads are added to the prepared solution, and the solution is pre-dispersed using ultrasound, and then ground in a planetary ball mill for 6-10 hours; after the process, the zirconia beads are separated by filtration through a sieve to obtain the liquid disperse dye. This invention provides a modified sodium lignosulfonate dispersant composition solution, in which the components exhibit excellent synergistic effects, improving the wettability and dispersibility of the product. Furthermore, the component graft copolymer A obtained by modifying sodium lignosulfonate through molecular grafting technology generally outperforms sodium lignosulfonate in terms of color depth and fiber staining resistance. When this dispersant composition aqueous solution is applied to the preparation of liquid disperse dyes, the mass ratio of the dispersant composition to the disperse dye is 1:2 to 1:10, and the solid content of the liquid disperse dye is 30% to 50%. Simultaneously, this liquid dye exhibits good application performance in terms of reduction hydrolysis rate and high-temperature dispersion stability.

[0008] The beneficial effects of this invention are: 1. Compared with traditional sodium lignosulfonate, this invention significantly reduces the color depth value, thereby reducing its staining on fibers. Its application in the preparation of liquid disperse dyes is beneficial to improving problems such as dyeing rate differences, color spots and color variations in subsequent dyeing processes, and improving the uniformity of dyeing polyester fibers, thereby reducing the wastewater treatment burden caused by dispersant residue.

[0009] 2. This invention combines the advantages of sodium lignosulfonate's good thermal stability and naphthalenesulfonic acid formaldehyde condensate's good wettability and dispersibility, thereby improving the grinding efficiency and high-temperature dispersion stability of the dispersant. When applied to the preparation of liquid disperse dyes, it reduces the reduction hydrolysis rate during the dyeing process, thus enabling the wider application of liquid disperse dyes in polyester fiber dyeing.

[0010] 3. Compared with traditional dispersants, the dispersant composition of the present invention significantly reduces the color depth value and reduces the staining effect on fibers. Liquid disperse dyes prepared using this dispersant composition exhibit excellent performance in terms of grinding efficiency, reduction hydrolysis rate, and high-temperature dispersion stability. Detailed Implementation

[0011] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments and comparative examples. The purpose of this description is to provide a detailed understanding of the content of the present invention, rather than to limit the present invention.

[0012] The testing method used in this invention is as follows: (1) Color depth value test Prepare a dispersant aqueous solution with a dispersant concentration of 0.5 g / L, scan the sample at medium speed using a UV spectrophotometer, and compare the absorbance value A of the sample at 450 nm.

[0013] (2) Fiber staining test Prepare a 3.0 g / L dispersant aqueous solution (without adding dye; the dispersant aqueous solution serves as the dye bath). Adjust the pH of the dye bath to 4.5–5.0 using HAC. Add 0.5 g of polyester fiber. Place the dye bath in a high-temperature, high-pressure dyeing machine, raise the temperature to 130°C within 50 minutes, and then maintain the temperature for 40 minutes. Cool the dye bath to 80°C and remove it. Simultaneously, prepare a blank sample of water without dispersant. After drying and ironing, measure the apparent color depth value (K / S) of the polyester using a Datacolor 1100 colorimeter.

[0014] (3) Particle size test Take 0.1g of the ground dye, dilute it 100 times, use a laser particle size analyzer to test its particle size distribution, and record the particle size Mv, D90 and D50 of the liquid dye.

[0015] (4) Reduction hydrolysis rate test Prepare a 20 mL dye bath with a dye concentration of 0.05 g / L. Adjust the pH of the dye bath to 4.5-5.0 using HAC. Place the dye bath in a high-temperature, high-pressure dyeing machine and heat it to 130°C within 30-40 minutes. Then maintain the temperature for 30 minutes. Cool the dye bath to 80-90°C and remove it. Add 30 mL of acetone to dilute the dye bath to 0.02 g / L. Measure the UV absorbance (At) at the maximum absorption wavelength. Calculate its reductive hydrolysis rate. Reduction hydrolysis rate / % =

[0016] In the formula, A t The absorbance of the dye solution after high temperature is the maximum absorption wavelength. (5) High temperature dispersion stability test Follow the procedure outlined in AATCC 146-2018, "Double-Layer Filter Paper Filtration Method". The high-temperature dispersion stability of disperse dyes is expressed as "filtration time level / residue level".

[0017] A dispersant composition solution comprising a graft copolymer A, a wetting agent B, and an antifoaming agent C in a mass ratio of 10:1:(0.01~0.02)~1:1:(0.01~0.02), and the solid content of the dispersant composition solution is 20%~50%.

[0018] Furthermore, the graft copolymer A of the present invention is selected from one of the graft copolymer A1 of sodium lignosulfonate and sodium β-naphthalenesulfonate of formula (I) and the graft copolymer A2 of sodium lignosulfonate and sodium 1-methylnaphthalenesulfonate of formula (II). (I) (II)

[0019] Furthermore, the method for preparing graft copolymer A according to the present invention includes the following steps: Step (1) Add industrial naphthalene or methyl naphthalene into a three-necked flask, wherein the industrial naphthalene needs to be heated to melt; Step (2) After the temperature in the three-necked flask is raised to 130°C, concentrated sulfuric acid is added dropwise. The dropwise addition time of concentrated sulfuric acid is 40 min to 50 min. When the dropwise addition is completed, the reaction temperature is controlled at 165°C and kept warm for sulfonation for 4 h to obtain naphthalene sulfonic acid or methyl naphthalene sulfonic acid. After sulfonation in step (3), the temperature is lowered to 120°C, distilled water is added to the reaction system, and the hydrolysis reaction is carried out for 40 minutes. After the reaction is completed, a sample is taken to analyze the acidity of the reaction solution and the acidity of the reaction solution is controlled at around 30. After the total acidity in step (4) reaches the required level, the temperature is lowered to 105°C. Formaldehyde is added dropwise while stirring. The dropwise addition time of formaldehyde should be controlled at 35~45 minutes. After the formaldehyde dropwise addition is completed, sodium lignosulfonate is added for condensation reaction for 4 hours. After the reaction in step (5) is completed, add NaOH solution to adjust the pH to 7-9, and the graft copolymer A is obtained.

[0020] Further, the molar ratio of concentrated sulfuric acid to industrial naphthalene or methylnaphthalene in step (2) is 1:1 to 1.5:1.

[0021] Further, the molar ratio of distilled water to naphthalene or methylnaphthalene in step (3) is 1:1 to 1:3.2.

[0022] Furthermore, the molar ratio of formaldehyde to naphthalene or methylnaphthalene in step (4) is 1:1 to 1:2.

[0023] Further, the mass ratio of sodium lignosulfonate to industrial naphthalene and methyl naphthalene in step (4) is 1:0.16 to 1:0.48.

[0024] Furthermore, the wetting agent B of the present invention is selected from at least one of the following: wetting agent B1, a styrene-maleic anhydride copolymer; wetting agent B2, an acrylic block copolymer solution containing amine pigment affinity groups; and wetting agent B3, an aqueous solution of a methacrylate block copolymer.

[0025] Furthermore, the defoamer C of the present invention is selected from at least one of defoamer C1 polyoxypropylene ethylene glycerol ether and defoamer C2 polyether modified silicone. The application of a dispersant composition solution in the preparation of liquid disperse dyes includes the following steps: after thoroughly mixing the dispersant composition solution and deionized water, the pH of the solution is adjusted to 5-6; disperse dye filter cake and zirconia beads are added to the prepared solution, and the solution is pre-dispersed using ultrasound, and then ground in a planetary ball mill for 6-10 hours; after the process, the zirconia beads are separated by filtration through a sieve to obtain the liquid disperse dye. Furthermore, the mass ratio of the dispersant composition to the dye filter cake used in this invention is 1:10 to 1:2, and the solid content of the liquid disperse dye is 30% to 50%.

[0026] Furthermore, the zirconia beads used in this invention account for 50% to 70% of the total liquid volume, and the mass ratio of zirconia beads of various specifications is 5:3:2 to 5:2:1.

[0027] Furthermore, the zirconia beads used in this invention account for 70% of the total liquid volume, and the mass ratio of zirconia beads of various specifications is 5:3:2.

[0028] The preparation of graft copolymer A according to the present invention includes sulfonation reaction of industrial naphthalene or 1-methylnaphthalene, hydrolysis reaction of α-naphthalenesulfonic acid, and graft copolymerization reaction of sodium lignin sulfonate, specifically: Sulfonation of industrial naphthalene or 1-methylnaphthalene Industrial naphthalene or methylnaphthalene is added to a three-necked flask, with the industrial naphthalene requiring melting upon heating. After raising the temperature inside the reaction flask to 130°C, concentrated sulfuric acid is added dropwise. The molar ratio of concentrated sulfuric acid to industrial naphthalene or methylnaphthalene is 1.2:1. The addition time of the concentrated sulfuric acid should be controlled at 40-50 minutes. After the addition is complete, the reaction temperature is maintained at 165°C, and sulfonation is carried out for 4 hours to obtain naphthalenesulfonic acid or methylnaphthalenesulfonic acid. The chemical equation for the reaction is as follows: .

[0029] Hydrolysis of α-naphthalenesulfonic acid After sulfonation, the temperature was lowered to 120℃, and distilled water was added to the reaction system. The molar ratio of distilled water to naphthalene or methylnaphthalene was 1:2.2. The hydrolysis reaction was carried out for 40 minutes. After the reaction, a sample was taken to analyze the acidity of the reaction solution, and the acidity of the reaction solution was controlled at around 30. The chemical equation for the reaction is as follows: .

[0030] graft copolymerization of sodium lignosulfonate After the total acidity reaches the required level, the temperature is lowered to 105℃, and formaldehyde is added dropwise with stirring. The molar ratio of formaldehyde to naphthalene or methylnaphthalene is 1:1.5, and the dropping time of formaldehyde should be controlled at 35~45 min. After the formaldehyde is added, sodium lignosulfonate is added, with a mass ratio of sodium lignosulfonate to industrial naphthalene and methylnaphthalene of 1:0.32. The condensation reaction is carried out for 4 h. After the reaction is completed, NaOH solution is added to adjust the pH to 7~9, thus obtaining graft copolymer A. The chemical equation for the reaction is as follows:

[0031] .

[0032] Compositions 1-12 The components of the high-efficiency dispersant composition solution described in this invention are shown in Table 1 by mass.

[0033] Table 1. Mass parts of components in the dispersant composition

[0034] To verify the performance of the high-efficiency dispersant composition solution described in this invention, compositions 1-12 were mixed with sodium lignosulfonate (LS), naphthalenesulfonate formaldehyde condensate (NNO), and methylnaphthalenesulfonate formaldehyde condensate (MF) for color depth and fiber staining properties determination. The test results are shown in Table 2. Table 2. Color depth and fiber staining test data of dispersant compositions.

[0035] Example 1 Take 30g (dry weight) CI Disperse Blue 79, 3g (dry weight) of Composition 1 shown in Table 1, 70g of zirconia beads, and 100g of total liquid volume. The order of addition is: dispersant → deionized water → adjust pH to 5-6 using CH3COOH / NaHCO3 → dye → zirconia beads. Then, add the mixture to a planetary ball mill and mechanically grind for 6 hours at a speed of 450 rad / min. After grinding, filter the mixture through a sieve and collect the resulting dye dispersion to obtain the finished product.

[0036] Examples 2-12 By using the mass ratios of compositions 2-12 and dyes shown in Table 3, and following the method described in Example 1, the finished product can be obtained.

[0037] Table 3 Weight ratio of dispersant composition to disperse dye

[0038] Comparative Example 1 Take 30g (dry weight) CI Disperse Blue 79, 6g (dry weight) sodium lignosulfonate, 70g zirconium oxide beads, and 100g of total liquid volume. The order of addition is: dispersant → deionized water → adjust pH to 5-6 using CH3COOH / NaHCO3 → dye → zirconium beads. Then, add this mixture to a planetary ball mill and mechanically grind for 6 hours at 450 rad / min. After grinding, filter the mixture through a sieve and collect the resulting dye dispersion to obtain the finished product.

[0039] Comparative Examples 2-6 By using the commonly used dispersant and dye mass ratios shown in Table 4 and following the method described in Comparative Example 1, the finished product can be obtained.

[0040] Table 4 Weight ratio of commonly used dispersants and disperse dyes

[0041] To verify the performance of the liquid dispersed dye prepared from the high-efficiency dispersant composition solution described in this invention, particle size, reductive hydrolysis rate, and high-temperature dispersion stability were tested in Examples 1-12 and Comparative Examples 1-6. The test results are shown in Tables 5, 6, and 7. Table 5. Particle size test data for liquid disperse dyes

[0042] Table 6. Test data on the reductive hydrolysis rate of liquid disperse dyes

[0043] Table 7. High-Temperature Dispersion Stability Test Data for Liquid Disperse Dyes

[0044] According to the test results of compositions 1-12 with sodium lignosulfonate (LS), naphthalenesulfonate formaldehyde condensate (NNO), and methylnaphthalenesulfonate formaldehyde condensate (MF), it can be seen that the color depth value of the solution of the high-efficiency dispersant composition of the present invention is significantly reduced, thereby reducing its staining on the fiber and improving the dyeing performance of the subsequently prepared liquid disperse dye.

[0045] A comparison of the test results of Examples 1-20 and Comparative Examples 1-6 shows that the high-efficiency dispersant composition solution described in this invention, when applied to the preparation of liquid disperse dyes, exhibits significantly improved grinding efficiency, reduction hydrolysis rate, and high-temperature dispersion stability compared to commonly used dispersants such as sodium lignosulfonate (LS) and naphthalenesulfonate formic acid condensate (NNO, MF), and can meet the preparation requirements of most liquid disperse dyes.

[0046] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A dispersant composition solution characterized in that, The dispersant composition solution comprises graft copolymer A, wetting agent B and defoaming agent C in a mass ratio of 10:1:(0.01-0.02) 1:1:(0.01-0.02), and the solid content of the dispersant composition solution is 20%-50%.

2. The dispersant composition solution of claim 1, wherein, The graft copolymer A is selected from one of graft copolymer A1 of sodium lignosulfonate and sodium β-naphthalene sulfonate of formula (I) and graft copolymer A2 of sodium lignosulfonate and sodium 1-methylnaphthalene sulfonate of formula (II). (Ⅰ) (Ⅱ)。 3. The dispersant composition solution of claim 2, wherein, The method for preparing the graft copolymer A comprises the following steps: Step (1), industrial naphthalene or methyl naphthalene is put into a three-necked flask, wherein the industrial naphthalene needs to be heated and melted; Step (2), after the temperature in the three-necked flask is raised to 130℃, concentrated sulfuric acid is added dropwise, the dropwise adding time of the concentrated sulfuric acid is 40 min-50 min, when the dropwise adding is completed, the reaction temperature is controlled at 165℃, and the temperature is kept for 4 h to obtain naphthalene sulfonic acid or methyl naphthalene sulfonic acid; Step (3), after the sulfonation is completed, the temperature is lowered to 120℃, distilled water is added into the reaction system, and the hydrolysis reaction is carried out for 40 min, after the reaction is completed, the acidity of the reaction solution is analyzed, and the acidity of the reaction solution is controlled at about 30; Step (4), after the total acidity reaches the requirement, the temperature is lowered to 105℃, and formaldehyde is added dropwise under stirring, the dropwise adding time of the formaldehyde is controlled at 35-45 min, after the dropwise adding of the formaldehyde is completed, sodium lignosulfonate is added to carry out condensation reaction for 4 h; Step (5), after the reaction is completed, NaOH solution is added to adjust the pH to 7-9, and the graft copolymer A is obtained.

4. The dispersant composition solution of claim 3, wherein, In the step (2), the molar ratio of the concentrated sulfuric acid to the industrial naphthalene or methyl naphthalene is 1:1-1.5:1; in the step (3), the molar ratio of the distilled water to the naphthalene or methyl naphthalene is 1:1-1:3.2; in the step (4), the molar ratio of the formaldehyde to the naphthalene or methyl naphthalene is 1:1-1:2; and in the step (4), the mass ratio of the sodium lignosulfonate to the industrial naphthalene and methyl naphthalene is 1:0.16-1:0.

48.

5. The dispersant composition solution of claim 1, wherein, The wetting agent B is selected from at least one of wetting agent B1 styrene maleic anhydride copolymer, wetting agent B2 acrylate block copolymer solution containing amine group pigment affinity group and wetting agent B3 aqueous solution of methacrylic acid salt block copolymer.

6. The dispersant composition solution of claim 1, wherein, The defoaming agent C is selected from at least one of defoaming agent C1 polyoxypropylene polyoxyethylene glycerol ether and defoaming agent C2 polyether modified silicon.

7. Use of the dispersant composition solution according to claim 1 in the preparation of liquid disperse dyes, characterized in that, The method comprises the following steps: after the dispersant composition solution and deionized water are fully mixed, the pH of the solution is adjusted to 5-6; the dispersed dye filter cake and zirconium oxide beads are added into the prepared solution, pre-dispersed by using ultrasonic, and then put into a planetary ball mill for grinding for 6-10 h; after the grinding is completed, the zirconium oxide beads are separated by using a screen to obtain a liquid dispersed dye.

8. Use according to claim 7, characterized in that: The mass ratio of the dispersant composition to the dye filter cake is 1:10-1:2, and the solid content of the liquid dispersed dye is 30%-50%.

9. Use according to claim 7, characterized in that: The used zirconium oxide beads account for 50%-70% of the total liquid volume, and the mass ratio of the zirconium oxide beads of different specifications is 5:3:2-5:2:

1.

10. Use according to claim 9, characterized in that: The used zirconium oxide beads account for 70% of the total liquid volume, and the mass ratio of the zirconium oxide beads of different specifications is 5:3:2.

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