CN112175415B - Water-insoluble pigment dispersion stabilizer and preparation method thereof - Google Patents
Water-insoluble pigment dispersion stabilizer and preparation method thereof Download PDFInfo
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- CN112175415B CN112175415B CN202011015912.8A CN202011015912A CN112175415B CN 112175415 B CN112175415 B CN 112175415B CN 202011015912 A CN202011015912 A CN 202011015912A CN 112175415 B CN112175415 B CN 112175415B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
- C09B67/009—Non common dispersing agents polymeric dispersing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/326—Polymers modified by chemical after-treatment with inorganic compounds containing sulfur
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Abstract
The application relates to the technical field of dispersion stabilizers, and particularly discloses a water-insoluble pigment dispersion stabilizer and a preparation method thereof, wherein the water-insoluble pigment dispersion stabilizer comprises the following components in percentage by weight: wetting agent: 10 to 50 percent; polyoxyethylene-modified polystyrene alcohol: 5 to 80 percent; leveling lubricant: 0.01-10%; defoaming agent: 0.01-1%; and (3) bactericide: 0.01-1%; water: and (4) the balance. The water-insoluble pigment dispersion stabilizer has high wettability and high dispersibility on dispersed pigment particles, effectively accelerates the formation of a stable dynamic core-shell type dispersion system of the dispersed pigment particles in a grinding process, greatly improves the stability and the dispersibility of a mixed system and the dyeing fixation rate and the color fastness, and has the characteristics of low dosage, high stability, high cost performance and the like.
Description
Technical Field
The application relates to the technical field of dispersing agents, in particular to a water-insoluble pigment dispersion stabilizer and a preparation method thereof.
Background
The water insoluble coloring material includes liquid disperse dye, slurry disperse dye, paint, textile pigment, etc. and has small molecular structure and no water soluble group, so that it needs to be dispersed in water solution or other solvent to form coloring material-dispersant system.
When the water-insoluble pigment is stored for a long time, a pigment-dispersant system is easily damaged, so that pigment particles are subjected to secondary agglomeration, the particle size of the pigment is increased, precipitates are generated, even the liquid pigment is layered up and down, the storage stability is poor, the performance of the liquid pigment is influenced, and the phenomenon of color change or uneven distribution is easily generated in the using process.
Content of application
In order to solve the problem of poor dispersibility and stability of the water-insoluble coloring material in the related art, the present application provides a water-insoluble coloring material dispersion stabilizer and a preparation method thereof.
In a first aspect, the present application provides a water-insoluble colorant dispersion stabilizer, which adopts the following technical scheme:
a water-insoluble pigment dispersion stabilizer comprises the following components in percentage by weight:
wetting agent: 10 to 50 percent;
polyoxyethylene-modified polystyrene alcohol: 5 to 80 percent;
leveling lubricant: 0.01-10%;
defoaming agent: 0.01-1%;
and (3) bactericide: 0.01-1%;
water: the balance;
the structural formula of the polyoxyethylene modified polystyrene alcohol is shown as the formula (I):
r in the formula (I)1-R4Is a polyoxyethylene chain
Or derivatives thereof
At least one of (1).
By adopting the scheme, the polyethylene oxide modified polystyrene alcohol is obtained by grafting and modifying polyether PEO (polyethylene oxide) and polystyrene alcohol. Wherein, the polystyrene alcohol has excellent film forming property and a large number of groups of pigment-philic molecules; while polyether PEO has excellent water solubility and dispersibility. Therefore, the polyoxyethylene modified polystyrene alcohol obtained by polymerizing the two can be stably adsorbed on the surface of the nano pigment particles to form a core-shell structure, so that the stability of a pigment dispersion system is enhanced; and because of polar groups such as-OH and the like contained in the polyoxyethylene chain, the polyoxyethylene modified polystyrene has excellent water solubility, so that the diffusion speed of the nano coloring material particles in the aqueous solution is remarkably increased, and the dispersibility of the water-insoluble coloring material in the aqueous solution is improved.
In addition, a polyoxyethylene chain extends outwards to generate charge and steric hindrance effects, so that the aggregation tendency of a nano pigment dispersion system is difficult, secondary agglomeration of nano pigment particles is prevented, and the water-insoluble pigment has excellent dispersion stability.
The leveling lubricant is used for assisting, on one hand, the leveling lubricant can reduce the friction resistance of movement among pigment particles, increase the fluidity and reduce the phenomenon of color bloom or uneven dyeing caused by the reduction of the dispersion performance of the liquid pigment in the dip dyeing process; on the other hand, the leveling lubricant has excellent leveling property, promotes the pigment to form a flat, smooth and uniform coating film in the drying film forming process, and improves the color fixing rate and the color fastness of the pigment on the colored surface.
The present application may be further configured in a preferred example to: n in the formula (I) is within the range of 1-100; m in the formulas (II) and (III) is more than or equal to 1 and less than or equal to 30.
By adopting the technical scheme, the higher the polymerization degree of the polyoxyethylene modified polystyrene is, the better the dispersing performance is, the viscosity of the nano pigment dispersion system is increased, the color fastness after dyeing is increased, but the overhigh molecular mass can cause the overhigh viscosity, so that the nano pigment particles are easy to agglomerate and are not beneficial to diffusion. In addition, under the conditions that n is more than or equal to 1 and less than or equal to 100 and m is more than or equal to 1 and less than or equal to 30, the polyethylene oxide modified polystyrene alcohol has good compatibility with the leveling lubricant, and the fluidity and the dispersibility of the nano pigment dispersion system are improved.
The present application may be further configured in a preferred example to: the polyoxyethylene modified polystyrene alcohol is prepared by the following steps:
step A1, placing the polystyrene alcohol for vacuum dehydration to obtain a first reactant with the water content not higher than 1%;
and step A2, cooling the first reactant to 40-80 ℃, adding a catalyst, heating to 80-120 ℃ under the protection of nitrogen, metering ethylene oxide, completely reacting at 80-120 ℃ under the pressure of 0.01-0.04MPa, cooling and discharging to obtain the polyoxyethylene modified polystyrene alcohol containing the formula (II).
Wherein the dosage of the catalyst is 0.1-1% of the total weight of the polystyrene alcohol and the ethylene oxide.
By adopting the technical scheme, the water content of the polystyrene alcohol reaches the requirement of less than 1% by adopting a vacuum dehydration mode after temperature rise.
The present application may be further configured in a preferred example to: heating the polyoxyethylene modified polystyrene alcohol prepared in the step A2 to 60-90 ℃, adding urea and sulfamic acid, stirring uniformly, heating to 120 ℃, and carrying out heat preservation reaction; and (3) after the pH value is measured to be 5-6, cooling to 80-100 ℃, adding deionized water, fully stirring, standing and cooling to obtain the polyoxyethylene modified polystyrene containing the formula (III).
By adopting the technical scheme, the step is a sulfonation reaction, the sulfamic acid is reacted with the polyoxyethylene modified polystyrene alcohol by using urea as a catalyst, and a sulfonic group is introduced into a polyoxyethylene chain so as to improve the dispersibility of the polyoxyethylene modified polystyrene alcohol in an aqueous solution. In addition, the anionic sulfonic acid group can improve the cloud point of the polyoxyethylene modified polystyrene alcohol and ensure the solubility and the dispersion of the polyoxyethylene modified polystyrene alcohol at high temperature.
The present application may be further configured in a preferred example to: the leveling lubricant comprises nonionic polyacrylamide and at least one of thiodiglycol, diethylene glycol, isopropanol and ethylene glycol.
By adopting the technical scheme, the molecular chain of the nonionic polyacrylamide contains amide groups, has excellent hydrophilicity, can directly generate an electrostatic bridge effect with fibers and organic polymers, and enhances the bonding strength of nano pigment particles and cloth in the dyeing process, thereby improving the color fixing rate and the color fastness. The thiodiglycol, the diglycol, the isopropanol and the ethylene glycol have good lubricity and emulsification, and are beneficial to the dispersion of pigment particles.
The present application may be further configured in a preferred example to: the wetting agent comprises at least one of acetylene glycol polyoxyethylene ether, silanol nonionic surfactant, alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
By adopting the technical scheme, the alkynediol polyoxyethylene ether, the silanol nonionic surfactant, the alkylphenol polyoxyethylene ether, the fatty alcohol polyoxyethylene ether and the like are all nonionic surfactants, and have the functions of wetting, leveling, defoaming and the like. The main function is to improve the dispersibility of the nano pigment particles together with the polyoxyethylene modified polystyrene alcohol; meanwhile, the adhesiveness and the deposition amount of the nano pigment particles on the colored surface are improved, so that the color fixing rate is improved.
The present application may be further configured in a preferred example to: the defoaming agent comprises at least one of an organic silicon defoaming agent, a polyether defoaming agent and a high-carbon alcohol defoaming agent.
By adopting the technical scheme, foam is easily generated in the preparation process of the dispersion stabilizer, and the diffusion of nano pigment particles is influenced; meanwhile, the foam may affect the penetration of the colorant during dyeing or coating, resulting in a colored or uneven color. The defoaming agent can eliminate foam, improve the dispersibility of pigment particles and improve the uniformity of coloring.
The present application may be further configured in a preferred example to: the bactericide comprises at least one of isothiazolinone bactericides, quaternary ammonium salt bactericides and peroxide bactericides.
By adopting the technical scheme, the pigment is polluted by microorganisms, and phenomena of viscosity reduction, pigment precipitation, odor generation, pH value drift and the like caused by the damage of a dispersion system occur. The isothiazolinone germicide destroys DNA molecule in bacterial cell by active part on heterocycle to inactivate bacteria, and the isothiazolinone germicide has the advantages of good compatibility, high compatibility, wide pH application range, natural biodegradation, low toxicity, etc.
In a second aspect, the present application provides a method for preparing a dispersion stabilizer for a water-insoluble coloring material, which adopts the following technical scheme: a preparation method of a water-insoluble pigment dispersion stabilizer is prepared by the following steps:
s1, heating 0.01-3% of water to 40-50 ℃, stirring at the rotating speed of 100-500rpm, adding a leveling lubricant into the water while stirring, and fully mixing to obtain a first mixture;
s2, sequentially adding the wetting agent, the defoaming agent and the polyoxyethylene modified polystyrene alcohol into the first mixture, and fully mixing to form a second mixture;
s3, adding the bactericide and the rest of water into the second mixture, and fully mixing to obtain the liquid colorant dispersion stabilizer.
By adopting the technical scheme, high molecular organic matters such as nonionic polyacrylamide and the like are not easy to dissolve in water, and the dissolving rate can be improved under the conditions of heating and stirring. The dissolution rate is influenced by too low rotating speed; the molecular structure in the nonionic polyacrylamide is damaged when the rotating speed is too high, the use effect is influenced by the reduction of the molecular weight, and the stirring speed is preferably controlled at 100-500 rpm.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the dispersion stabilizer is prepared from polyoxyethylene modified polystyrene alcohol and a leveling lubricant and is used for preparing a water-insoluble pigment, wherein the average particle size of the prepared liquid disperse red dye is within an interval of 80-200 nm; d (90) is less than or equal to 400 nm; PDI is less than 0.2, and the distribution is relatively uniform, which shows that the liquid disperse red dye obtained in the application has smaller particle size and high dispersity; the average grain diameter of the water-insoluble coloring material prepared by the commercial dispersant is 375 nm; d (90) is less than or equal to 700 nm; the distribution uniformity PDI is less than 0.36; in addition, the water-insoluble colorant dispersion stabilizer of the present application produces a liquid dispersion red dye having a small change in particle size after long-term storage. The dispersion stabilizer prepared by the polyoxyethylene modified polystyrene alcohol and the leveling lubricant is obviously improved in the dispersibility and stability of the water-insoluble pigment.
2. According to the method, the nonionic polyacrylamide is used as a leveling lubricant, the alkynediol polyoxyethylene ether is used as a wetting agent, and the polyoxyethylene modified polystyrene with appropriate molecular weight is selected, so that the dyeing fastness of the prepared liquid disperse red dye is improved, and the color fixing rate is increased by 4.85%. The dispersion stabilizer prepared by adopting the nonionic polyacrylamide as the leveling lubricant and the alkynediol polyoxyethylene ether as the wetting agent can improve the color fastness and the color fixing rate of the water-insoluble pigment.
3. According to the application, the polyethylene oxide modified polystyrene vinyl alcohol is subjected to sulfonation treatment, and a sulfonic group is introduced into a polyethylene oxide chain, so that the dispersibility and stability of the polyethylene oxide modified polystyrene vinyl alcohol to the water-insoluble pigment are further improved.
Detailed Description
The present application is described in further detail below.
Preparation example 1: the polyoxyethylene modified polystyrene alcohol is prepared by the following steps:
step A1, placing the polystyrene alcohol into a reaction container filled with nitrogen, heating to 110 ℃, and dehydrating in vacuum for 0.5 hour to obtain a first reactant;
step A2, cooling the first reactant to 50 ℃, adding tin tetrachloride (catalyst), then placing the mixture under the protection of nitrogen, heating to 100 ℃, metering ethylene oxide, and completely reacting at the temperature of 100 ℃ and under the pressure of 0.03 Mpa; cooling to 25 ℃, and discharging to obtain polyether modified polystyrene alcohol;
wherein the dosage of the catalyst is 1 percent of the total weight of the polystyrene alcohol and the ethylene oxide.
The structural formula (I) of the prepared polyoxyethylene modified polystyrene alcohol is as follows:
wherein R in the formula (I)1-R4Is a polyoxyethylene chain
And n is 20 and m is 8.
Preparation example 2: the polyoxyethylene modified polystyrene alcohol is prepared by the following preparation process:
step A1, placing the polystyrene alcohol into a reaction container filled with nitrogen, heating to 100 ℃, and dehydrating for 1 hour in vacuum;
step A2, cooling the first reactant to 80 ℃, adding tin tetrachloride (catalyst), wherein the dosage of the catalyst is 0.6 percent of the total weight of the polystyrene alcohol and the ethylene oxide, then placing the mixture under the protection of nitrogen, heating to 120 ℃, metering and adding the ethylene oxide, and completely reacting at the temperature of 120 ℃ and the pressure of 0.04 Mpa; cooling to 25 ℃, and discharging to obtain polyether modified polystyrene alcohol; step A3, adding the polyoxyethylene modified polystyrene alcohol prepared in the step A2 into a container, heating to 90 ℃, slowly dropwise adding urea and sulfamic acid, and obtaining a reaction solution after dropwise adding is finished within 2 hours; stirring for 30min, heating to 120 ℃, keeping the temperature and reacting for 3h, when the pH of the reaction solution is 5, cooling to 85 ℃, adding deionized water to adjust the viscosity, wherein the deionized water accounts for 8 percent of the total weight of the materials, stirring and reacting for 1h, standing and cooling, and collecting to obtain the polyoxyethylene modified polystyrene alcohol.
Wherein the structural formula (I) of the polyoxyethylene modified polystyrene alcohol prepared in the step A3 is as follows:
r in the formula (I)1-R4Being derivatives of polyoxyethylene chains
n＝20，m＝8。
Preparation example 3: a polyoxyethylene-modified polystyrene alcohol, which is different from preparation example 2 in the content of each component, and n-1 and m-1 in step a 3.
Preparation example 4: a polyoxyethylene-modified polystyrene alcohol, which is different from preparation example 2 in the content of each component, and n is 10 and m is 10 in step a 3.
Preparation example 5: a polyoxyethylene-modified polystyrene alcohol, which is different from preparation example 2 in the content of each component, and n is 100 and m is 30 in step a 3.
TABLE 1 summary of the components and molar mass ratios of preparation examples 1 to 5
Example 1: a water-insoluble pigment dispersion stabilizer is prepared by the following preparation process:
s1, adding 2kg of water into a container, heating to 42 ℃, stirring at a stirring speed of 300rpm, slowly adding 0.2 kg of nonionic polyacrylamide while stirring, adding after 1min, and uniformly stirring;
s2, sequentially adding 20 kg of the acetylene glycol polyoxyethylene ether, 0.2 kg of the organosilicon polyether antifoaming agent and 50 kg of the polyoxyethylene modified polystyrene alcohol prepared in the preparation example 1, and uniformly stirring;
s3, 0.1 kg of isothiazolinone biocide was added with 27.5 kg of the remaining water and stirred well to obtain the water-insoluble colorant dispersion stabilizer.
Examples 2 to 5: a water-insoluble colorant dispersion stabilizer differing from example 1 in the content of each component.
Table 2 compositions and recipes for examples 1-5 and examples 10-11 (kg)
Example 6: a water-insoluble coloring material dispersion stabilizer differs from example 1 in that the polyoxyethylene-modified polystyrene alcohol obtained in production example 1 and added in step S2 is replaced with the polyoxyethylene-modified polystyrene alcohol obtained in production example 2.
Example 7: a water-insoluble coloring material dispersion stabilizer differs from example 1 in that the polyoxyethylene-modified polystyrene alcohol obtained in production example 1 and added in step S2 is replaced with the polyoxyethylene-modified polystyrene alcohol obtained in production example 3.
Example 8: a water-insoluble coloring material dispersion stabilizer differs from example 1 in that the polyoxyethylene-modified polystyrene alcohol obtained in production example 1 and added in step S2 is replaced with the polyoxyethylene-modified polystyrene alcohol obtained in production example 4.
Example 9: a water-insoluble coloring material dispersion stabilizer differs from example 1 in that the polyoxyethylene-modified polystyrene alcohol obtained in production example 1 and added in step S2 is replaced with the polyoxyethylene-modified polystyrene alcohol obtained in production example 5.
Example 10: a water-insoluble colorant dispersion stabilizer differs from example 1 in that thiodiglycol is used instead of the nonionic polyacrylamide.
Example 11: a water-insoluble colorant dispersion stabilizer differs from that in example 1 in that acetylene glycol polyoxyethylene ether is replaced with a combination of fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether at a weight ratio of 1: 1.5.
Example 12: a water-insoluble coloring material dispersion stabilizer differs from example 1 in that a polyether defoaming agent is used instead of a silicone defoaming agent.
Example 13: a water-insoluble coloring material dispersion stabilizer differing from that in example 1 in that the stirring speed in step S1 was 1000rpm.
Comparative example 1: the difference from example 1 is that the nonionic polyacrylamide and the polyethylene oxide-modified polystyrene alcohol are not added.
Comparative example 2: the difference from example 1 is that an equal amount of water was used instead of the polyoxyethylene-modified polystyrene alcohol.
Comparative example 3: the difference from example 1 is that the polyethylene oxide-modified polystyrene vinyl alcohol was replaced with the same amount of AEO 07.
Comparative example 4: the difference from example 1 is that the wetting agent acetylenediol polyoxyethylene ether is replaced by an equal amount of water.
Sample preparation: the c.i. disperse red 167 pigment cake was uniformly mixed with water, 17 groups of the same samples were taken, and the water-insoluble pigment dispersion stabilizers prepared in examples 1 to 14 and comparative examples 1 to 4 were added, respectively, and uniformly stirred to prepare a premix, wherein the weight ratio of the dispersion stabilizer to the c.i. disperse red 167 pigment cake to the water was 8: 30: 62, a first step of mixing;
grinding each group of premix for 5h at normal temperature by a grinder, filtering by a double-layer 100-mesh screen to obtain a finished product of the liquid disperse red dye, and storing for later use.
Test 1: particle size distribution test of liquid disperse red dye: the liquid disperse red dyes prepared in the respective examples and comparative examples were tested by a JL9200 laser particle size analyzer, and the test results are shown in table 3.
Test 2: storage stability testing of liquid disperse red dyes: a sample of 100ml of the liquid disperse red dye prepared above was stored at room temperature (25 to 35 ℃) for 3 months, and the particle size distribution of the liquid disperse red dye was measured again, and the test results are shown in Table 3.
TABLE 3 particle size distribution of liquid disperse Red dyes obtained from examples 1 to 13 and comparative examples 1 to 3
And (3) analyzing test results:
as can be seen from table 3, in examples 1 to 13 of the liquid disperse red dyes prepared by using the dispersion stabilizer in the present application, the average particle size of the liquid disperse red dyes is smaller than that of the liquid disperse red dyes prepared without using the dispersion stabilizer in the present application, and the distribution is more uniform, which indicates that the dispersion stabilizer in the present application has more excellent dispersibility for the liquid disperse dyes; in addition, the average particle size of the former was less than that of the latter after three months of storage, indicating that the dispersion stabilizer in the present application has more excellent stability to liquid dispersion dyes.
Comparative examples 1-5, comparative example 1 and comparative example 3: the liquid coloring material dispersion stabilizers of examples 1 to 5 were each added with a polyoxyethylene-modified polystyrene alcohol and a leveling lubricant, comparative example 1 was not added with a polyoxyethylene-modified polystyrene alcohol and a leveling lubricant, and comparative example 3 was carried out using only a common commercially available dispersant. The liquid disperse red dyes obtained from the water-insoluble colorant dispersion stabilizers of examples 1 to 5 all had a particle size distribution of 360nm or less, an average particle size of 90 to 200nm and a particle size uniformity of 0.12 to 0.18, and the average particle size after three months as measured in examples 1 to 5 was found to have a very small change in the particle size and high stability. In comparative examples 1 and 3, the particle size distribution ranges were 1000nm or less and 700nm or less, the average particle sizes were 550nm and 375nm, and the particle size uniformity was 0.5 and 0.36, respectively, which are higher than those of examples 1 to 5, respectively, indicating that the dispersion stabilizers for the water-insoluble coloring materials in comparative examples 1 and 3 had poor dispersibility. In addition, the average particle diameters after 3 months were 750nm and 490nm, respectively, and the change was large, indicating that the stability was poor. From this, it is understood that the dispersibility and stability of the water-insoluble coloring material dispersion stabilizer prepared using the polyoxyethylene-modified polystyrene alcohol and the leveling lubricant are remarkably improved with respect to the liquid disperse dye.
Comparing example 1 with example 6, example 1, R1-R4 in formula (I) are polyethylene oxide chains
Example 6 formula (I) wherein R1-R4 are polyoxyethylene chains
And derivatives thereof
The liquid disperse red dye prepared from the water-insoluble colorant dispersion stabilizer of example 1 has a particle size distribution range of 180nm or less, an average particle size of 90nm, and a particle size uniformity of 0.12; the liquid disperse red dyes obtained from the water-insoluble colorant dispersion stabilizer of example 6 each had a particle size distribution of 140nm or less, an average particle size of 65nm, and a particle size uniformity of 0.09. It is thus understood that a sulfonic acid group having excellent water solubility is introduced into a polyoxyethylene chain so as to be separatedThe dispersibility of the dispersion stabilizer to the liquid disperse dye is improved.
Comparing example 7 with example 8, where n is 20 and m is 8 in example 7; in example 8, n is 1 and m is 1, that is, the polymerization degree of the polyoxyethylene-modified polystyrene alcohol in example 7 is higher than that in example 8. As is clear from Table 3, the liquid disperse red dyes obtained from the water-insoluble coloring material dispersion stabilizer of example 7 had particle size distribution ranges of 140nm or less, an average particle size of 65nm and particle size uniformity of 0.09; the liquid disperse red dyes obtained from the water-insoluble coloring material dispersion stabilizer of example 8 each had a particle size distribution of 400nm or less, an average particle size of 195nm and a particle size uniformity of 0.19, indicating that the dispersibility of example 7 was higher than that of example 8. From this result, it was found that as the polymerization degree of the polyoxyethylene-modified polystyrene alcohol increases, the molecular weight increases, and the dispersibility of the polyoxyethylene-modified polystyrene alcohol in the liquid disperse dye increases.
Comparing example 7 with examples 8-10, when n > 20 and m > 8, the dispersion dispersity of the liquid disperse dye is increased with the molecular weight of the polyoxyethylene modified polystyrene alcohol, but the viscosity of the polyoxyethylene modified polystyrene alcohol is increased rapidly, so that the dispersion dispersity of the nano dye dispersion system is reduced. As can be seen from table 3, when n is 20 and m is 8, the dispersibility of the water-insoluble colorant dispersion stabilizer in the liquid disperse dye is high.
Test 3: and (3) testing the fixation rate of the liquid disperse dye: the liquid disperse red pigments prepared by the dispersion stabilizers of examples 1-13 and comparative examples 1-2 were used to dye terylene cloth by conventional high temperature disperse dye process, and the fixation rate and color fastness of the dyed cloth were tested by the method specified in GB/T2396-.
TABLE 4 results of color fastness and fixation testing of examples 1-8 and comparative examples 3-4
And (3) analyzing test results:
comparing example 1 with example 3, the liquid disperse red dye prepared in example 3 has better color fastness and color fastness than example 1, and compared with example 1, the leveling lubricant (nonionic polyacrylamide) is added in a larger amount in example 3, so that a flat, smooth and uniform coating film is formed in the dried film forming process of the dye, and the color fastness of the dye are improved.
Comparing example 6 with example 8, the color fastness and the fixation rate of example 6 are better than those of example 7, and compared with example 6, n of the polyoxyethylene modified polystyrene alcohol in example 7 is reduced from 20 to 1, m is reduced from 8 to 1, the molecular weight is obviously reduced, the viscosity is reduced, and the fixation rate and the color fastness of the liquid disperse red dye after dyeing are also obviously reduced.
Compared with the comparative example 4, the color fastness and the color fixing rate of the example 1 are obviously reduced, and compared with the comparative example 4, the wetting agent acetylene glycol polyoxyethylene ether is used in the dispersion stabilizer of the example 1, so that the adhesion and the deposition amount of the nano dye particles on the surface of the fabric can be improved in the dyeing process, and the color fixing rate is improved.
The embodiments of the present invention are preferred embodiments of the present application, and the scope of protection of the present application is not limited by the embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (9)
1. A water-insoluble colorant dispersion stabilizer, characterized by comprising the following components in percentage by weight:
wetting agent: 10 to 50 percent;
polyoxyethylene-modified polystyrene alcohol: 5 to 80 percent;
leveling lubricant: 0.01-10%;
defoaming agent: 0.01-1%;
and (3) bactericide: 0.01-1%;
water: the balance;
the structural formula of the polyoxyethylene modified polystyrene alcohol is shown as the formula (I):
r in the formula (I)1-R4Is a polyoxyethylene chain
(II) or derivatives of polyoxyethylene chains
At least one of (III);
n in the formula (I) is within the range of 1-100; m in the formulas (II) and (III) is more than or equal to 1 and less than or equal to 30.
2. The water-insoluble colorant dispersion stabilizer according to claim 1, wherein said polyoxyethylene-modified polystyrene alcohol is produced by the following steps:
step A1, placing the polystyrene alcohol for vacuum dehydration to obtain a first reactant with the water content not higher than 1%;
step A2, cooling the first reactant to 40-80 ℃, adding a catalyst, heating to 80-120 ℃ under the protection of nitrogen, metering ethylene oxide, completely reacting at 80-120 ℃ under the pressure of 0.01-0.04MPa, cooling and discharging to obtain polyoxyethylene modified polystyrene containing the formula (II);
wherein the dosage of the catalyst is 0.1-1% of the total weight of the polystyrene alcohol and the ethylene oxide.
3. The dispersion stabilizer for a water-insoluble coloring material as claimed in claim 2, wherein in the step A1, the polystyrene alcohol is heated to 110 ℃ under the protection of nitrogen, and then vacuum dehydration is carried out for 0.5-1 h.
4. The water-insoluble colorant dispersion stabilizer according to claim 3, wherein the polyoxyethylene modified polystyrene alcohol obtained in step A2 is heated to 60-90 ℃, urea and sulfamic acid are added dropwise, after the dropwise addition is completed within 1-2 hours, the mixture is stirred uniformly, the temperature is raised to 120 ℃, the heat preservation reaction is carried out, when the pH value is 5-6, the temperature is lowered to 80-100 ℃, deionized water is added, the mixture is stirred fully, and the mixture is cooled and discharged, thus obtaining the polyoxyethylene modified polystyrene alcohol containing formula (III).
5. The dispersion stabilizer for a water-insoluble coloring material according to claim 1, wherein said leveling lubricant comprises at least one of nonionic polyacrylamide, thiodiglycol, diethylene glycol, isopropyl alcohol and ethylene glycol.
6. The water-insoluble colorant dispersion stabilizer according to claim 1, wherein the wetting agent comprises at least one of acetylene glycol polyoxyethylene ether, silanol-based nonionic surfactant, alkylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether.
7. The water-insoluble coloring material dispersion stabilizer according to claim 1, wherein said defoaming agent comprises at least one of a silicone defoaming agent, a polyether defoaming agent, and a higher alcohol defoaming agent.
8. The water-insoluble colorant dispersion stabilizer according to claim 1, wherein the bactericide comprises at least one of an isothiazolinone bactericide, a quaternary ammonium salt bactericide, and a peroxide bactericide.
9. A method for producing the water-insoluble colorant dispersion stabilizer according to any one of claims 1 to 8, characterized in that: is prepared by the following steps:
s1, heating 0.01-3% of water to 40-50 ℃, stirring at the rotating speed of 100-500rpm, adding a leveling lubricant into the water while stirring, and fully mixing to obtain a first mixture;
s2, sequentially adding the wetting agent, the defoaming agent and the polyoxyethylene modified polystyrene alcohol into the first mixture, and fully mixing to form a second mixture;
s3, adding the bactericide and the rest of water into the second mixture, and fully mixing to obtain the liquid colorant dispersion stabilizer.
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