Electrolyte-resistant printing thickening agent for improving coloring effect and preparation method of electrolyte-resistant printing thickening agent

Abstract

The invention relates to the technical field of textile chemicals, in particular to an electrolyte-resistant printing thickening agent for improving the coloring effect and a preparation method thereof.The electrolyte-resistant printing thickening agent is prepared from, by weight, 10-20 parts of methacrylic acid, 15-30 parts of triethanolamine, 0.1-0.5 part of N, N '-methylene bisacrylamide, 4-8 parts of functional monomers and 2-5 parts of organic modified nano bentonite. 3-6 parts of an emulsifier, 0.1-0.6 part of sodium hydrogen sulfite, 0.1-0.6 part of sodium persulfate, 8-15 parts of an oil-phase solvent, 2-5 parts of a reverse-phase emulsifier and 30-50 parts of water; the functional monomer is prepared from p-styrene propanesulfonic acid, 2-acrylamide-2-methyl propanesulfonic acid and triphenylethyl phenol polyoxyethylene ether methacrylate according to the weight ratio of (3 to 5) to (1 to 2) to 1. According to the electrolyte-resistant printing thickening agent capable of improving the coloring effect, through matching and combination of the raw materials, the electrolyte resistance of the thickening agent can be improved, and the coloring effect in textile printing is improved.

Description

Technical Field

[0001] The present application relates to the technical field of textile chemicals, and in particular to an electrolyte-resistant printing thickener for improving coloring effect and a preparation method thereof. Background Art

[0002] Printing thickener is a chemical widely used in the textile printing industry. It is mainly used to increase the viscosity and consistency of printing paste to ensure the clarity, color vividness and durability of the printed pattern.

[0003] Currently, the most common printing thickeners are mainly anionic polyacrylic acid thickeners. Anionic thickeners are polymer electrolyte compounds containing a large number of ionizable carboxyl groups in their molecules. They are lightly cross-linked copolymers characterized by low viscosity, strong thickening ability, good stability, resistance to mildew, and low thixotropy. Their viscosity is minimally affected by shear rate, and they have excellent leveling and splash resistance, with minimal effect on gloss. They can be used to thicken glossy products, eliminating the use of hydrocarbons in printing pastes. However, anionic thickeners are sensitive to electrolytes and have poor adaptability.

[0004] Therefore, providing an electrolyte-resistant and more stable printing thickener is an urgent problem to be solved. Summary of the Invention

[0005] The present application aims to overcome at least one of the defects of the prior art and provide an electrolyte-resistant printing thickener with improved coloring effect and a preparation method thereof. The printing thickener can improve the electrolyte resistance of the thickener and improve the coloring effect in textile printing through the combination of raw materials.

[0006] In the first aspect, the embodiments of the present application provide an electrolyte-resistant printing thickener for improving the coloring effect, which is achieved by the following technical solutions:

[0007] An electrolyte-resistant printing thickener for improving coloring effect, comprising the following raw materials in parts by weight:

[0008] Methacrylic acid 10-20 parts, triethanolamine 15-30 parts, N,N'-methylenebisacrylamide 0.1-0.5 parts, functional monomer 4-8 parts, organic modified nano bentonite 2-5 parts, emulsifier 3-6 parts, sodium bisulfite 0.1-0.6 parts, sodium persulfate 0.1-0.6 parts, oil phase solvent 8-15 parts, reverse emulsifier 2-5 parts, water 30-50 parts;

[0009] The functional monomer is composed of p-styrenepropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid and triphenylethylphenol polyoxyethylene ether methacrylate in a weight ratio of (3-5): (1-2): 1.

[0010] The electrolyte-resistant printing thickener for improving the coloring effect according to the embodiment of the present application has at least the following beneficial effects:

[0011] The functional monomers of the present application are composed of 4-styrenepropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid and triphenylphenol polyoxyethylene ether methacrylate. Due to the hydrophobicity of the styrene group in 4-styrenepropanesulfonic acid, the loss of charge shielding is compensated by hydrophobic association, the amount of emulsifier used is reduced, and the sensitivity to pH and electrolytes is reduced. At the same time, the introduced sulfonic acid group improves salt tolerance, making it more suitable for high-electrolyte systems; the sulfonic acid group in 2-acrylamide-2-methylpropanesulfonic acid is more electronegative and less sensitive to electrolytes; triphenylphenol polyoxyethylene ether methacrylate, as a macromolecular hydrophobic monomer, further reduces the sensitivity to electrolytes.

[0012] This application introduces organically modified nano-bentonite into a printing thickener. The layered silicate structure of bentonite has a strong cation exchange capacity and has the function of adsorbing heavy objects and thickening. After being organically modified, the hydrophobicity and dispersibility can be further improved.

[0013] The triethanolamine of the present application has both neutralization and emulsification auxiliary functions, and can improve the stability of the emulsion.

[0014] According to some embodiments of the present application, the oil phase solvent is 2,6,10-trimethyldodecane. 2,6,10-trimethyldodecane is a bio-based solvent with low toxicity, environmental protection and health. Its use in the preparation of the printing thickener of the present application can significantly improve the emulsion stability.

[0015] According to some embodiments of the present application, the emulsifier is selected from one of sorbitan monooleate and sodium dodecyl diphenyl ether disulfonate.

[0016] According to some embodiments of the present application, the inverse emulsifier is selected from one of polyoxyethylene sorbitan monooleate and nonylphenol polyoxyethylene ether.

[0017] According to some embodiments of the present application, the preparation of the organically modified nano bentonite includes the following steps: dissolving the nano bentonite in deionized water, adding Na2CO3 solution dropwise while stirring until the pH value stabilizes at 10, and simultaneously adding propylene glycol alginate and letting it stand to obtain a stable suspension, heating to 120-150°C, adding hexadecyltrimethylammonium bromide solution and isopropanol, reacting for 5-8 hours to obtain a modified nano bentonite suspension slurry, centrifuging to obtain a nano bentonite precipitate, washing away excess Br ions with an ethanol solution, using AgNO3 to test whether no yellow precipitate is produced, drying and grinding to obtain an organically modified nano bentonite.

[0018] Furthermore, the weight ratio of the nano-bentonite, cetyltrimethylammonium bromide solution and isopropyl alcohol is 1:(1-2):(0.5-0.8).

[0019] Furthermore, the amount of propylene glycol alginate is 1% by weight of the nano bentonite.

[0020] Furthermore, the mass percentage concentration of the Na2CO3 solution is 20-30%.

[0021] Furthermore, the stirring speed is 2000-3000 r / min.

[0022] In a second aspect, the present invention provides a method for preparing the electrolyte-resistant printing thickener for improving the coloring effect, which is achieved by the following technical solutions:

[0023] A method for preparing an electrolyte-resistant printing thickener for improving coloring effect comprises the following steps:

[0024] (1) Mix methacrylic acid and water according to parts by weight, add triethanolamine under stirring at 20-25 Hz, and control the temperature at 20-35° C.;

[0025] (2) adding N,N'-methylenebisacrylamide, functional monomer, and sodium persulfate and stirring evenly to obtain an aqueous phase liquid;

[0026] (3) mixing the oil phase solvent and the emulsifier, adding the organic modified nano bentonite and stirring, adding the aqueous phase liquid of step (2) under rapid stirring, and emulsifying at a temperature of 20-35° C. for 20-40 minutes to obtain an emulsion;

[0027] (4) Sodium bisulfite is prepared into a sodium bisulfite aqueous solution with a mass fraction of 3%, the emulsion described in step (3) is added to a reactor, and a sodium bisulfite aqueous solution with a mass fraction of 3% is slowly added under stirring conditions of 10-15 Hz until no obvious heat is released, the reaction temperature is controlled to 40-50° C., the reaction is carried out for 2-3 hours, the temperature is raised to 80° C., the reaction is carried out for 1-2 hours, the reaction is completed, the temperature is lowered to 60° C.-65° C., an inverse emulsifier is added, stirring is continued for 10-20 minutes, and filtering is performed to obtain an electrolyte-resistant printing thickener with improved coloring effect.

[0028] The method for preparing an electrolyte-resistant printing thickener for improving coloring effect according to an embodiment of the present application has at least the following beneficial effects:

[0029] The preparation method of the present application has simple steps, does not require the use of complex production equipment, has low cost, is pollution-free during the manufacturing process, does not emit toxic substances, does not harm the health of operators, and is suitable for industrial production. DETAILED DESCRIPTION

[0030] To make the purpose, technical solutions and advantages of this application more clear, the following will be further described in detail with reference to specific embodiments. The embodiments described here are only part of the embodiments of this application and should not be understood as limiting the scope of protection of this application.

[0031] Example 1

[0032] Preparation of electrolyte-resistant printing thickener to improve coloring effect:

[0033] (1) 15 parts of methacrylic acid and 40 parts of water were mixed according to weight, and 22 parts of triethanolamine was added under stirring at 23 Hz. The temperature was controlled at 28°C.

[0034] (2) adding 0.3 parts of N,N'-methylenebisacrylamide, 6 parts of functional monomer, and 0.4 parts of sodium persulfate and stirring evenly to obtain an aqueous phase liquid;

[0035] (3) 12 parts of 2,6,10-trimethyldodecane and 5 parts of sorbitan monooleate were mixed, 4 parts of organic modified nano bentonite were added and stirred, and the aqueous phase liquid of step (2) was added under rapid stirring, and emulsified at a temperature of 28° C. for 30 minutes to obtain an emulsion;

[0036] (4) 0.3 parts of sodium bisulfite are prepared into a 3% sodium bisulfite aqueous solution by mass, the emulsion described in step (3) is added to the reactor, and the 3% sodium bisulfite aqueous solution by mass is slowly added under stirring conditions of 12 Hz until no obvious heat is released, the reaction temperature is controlled to 45° C., the reaction is carried out for 2.5 hours, the temperature is raised to 80° C., the reaction is carried out for 1.5 hours, the reaction is completed, the temperature is lowered to 63° C., 3 parts of polyoxyethylene sorbitan monooleate are added, stirring is continued for 15 minutes, and filtering is performed to obtain an electrolyte-resistant printing thickener with improved coloring effect;

[0037] The functional monomer is composed of p-styrenepropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid and triphenyl phenol polyoxyethylene ether methacrylate in a weight ratio of 4:1.5:1;

[0038] Preparation of organically modified nano-bentonite: Nano-bentonite was dissolved in deionized water, and a 25% by mass concentration of Na2CO3 solution was added dropwise while stirring at a speed of 2500 r / min until the pH value stabilized at 10. Propylene glycol alginate was added dropwise and allowed to stand to obtain a stable suspension. The temperature was raised to 135°C, and a cetyltrimethylammonium bromide solution and isopropanol were added. The reaction was carried out for 6.5 hours to obtain a modified nano-bentonite suspension slurry. The suspension was centrifuged to obtain a nano-bentonite precipitate. Excess Br ions were washed off with an ethanol solution. No yellow precipitate was produced by AgNO3 testing. The suspension was dried and ground to obtain the organically modified nano-bentonite.

[0039] The weight ratio of nano bentonite, cetyltrimethylammonium bromide solution and isopropyl alcohol is 1:1.5:0.7; the amount of propylene glycol alginate is 1% of the weight of the nano bentonite.

[0040] Example 2

[0041] Preparation of electrolyte-resistant printing thickener to improve coloring effect:

[0042] (1) 20 parts of methacrylic acid and 30 parts of water were mixed according to weight, and 15 parts of triethanolamine was added under stirring at 25 Hz. The temperature was controlled at 35°C.

[0043] (2) adding 0.1 parts of N,N'-methylenebisacrylamide, 8 parts of functional monomer, and 0.1 parts of sodium persulfate and stirring evenly to obtain an aqueous phase liquid;

[0044] (3) 15 parts of 2,6,10-trimethyldodecane and 3 parts of sodium dodecyl diphenyl ether disulfonate were mixed, 5 parts of organic modified nano bentonite were added and stirred, and the aqueous phase liquid of step (2) was added under rapid stirring, and emulsified at a temperature of 20° C. for 40 minutes to obtain an emulsion;

[0045] (4) 0.1 parts of sodium bisulfite are prepared into a 3% sodium bisulfite aqueous solution by mass, the emulsion described in step (3) is added to the reactor, and the 3% sodium bisulfite aqueous solution by mass is slowly added under stirring conditions of 15 Hz until no obvious heat is released, the reaction temperature is controlled to 40° C., the reaction is carried out for 3 hours, the temperature is raised to 80° C., the reaction is carried out for 1 hour, the reaction is completed, the temperature is lowered to 65° C., 2 parts of nonylphenol polyoxyethylene ether are added, stirring is continued for 20 minutes, and filtering is performed to obtain an electrolyte-resistant printing thickener with improved coloring effect;

[0046] The functional monomer is composed of p-styrenepropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid and triphenyl phenol polyoxyethylene ether methacrylate in a weight ratio of 3:2:1;

[0047] Preparation of organically modified nano-bentonite: Nano-bentonite was dissolved in deionized water, and a 30% by mass concentration of Na2CO3 solution was added dropwise while stirring at a speed of 2000 r / min until the pH value stabilized at 10. Propylene glycol alginate was added dropwise and allowed to stand to obtain a stable suspension. The temperature was raised to 120°C, and a cetyltrimethylammonium bromide solution and isopropanol were added. The reaction was carried out for 8 hours to obtain a modified nano-bentonite suspension slurry. The suspension was centrifuged to obtain a nano-bentonite precipitate. Excess Br ions were washed off with an ethanol solution. No yellow precipitate was produced by AgNO3 testing. The suspension was dried and ground to obtain the organically modified nano-bentonite.

[0048] The weight ratio of nano bentonite, cetyltrimethylammonium bromide solution and isopropyl alcohol is 1:1:0.8; the amount of propylene glycol alginate is 1% of the weight of the nano bentonite.

[0049] Example 3

[0050] Preparation of electrolyte-resistant printing thickener to improve coloring effect:

[0051] (1) 10 parts of methacrylic acid and 50 parts of water were mixed according to weight, and 30 parts of triethanolamine was added under stirring at 20 Hz. The temperature was controlled at 20°C.

[0052] (2) adding 0.5 parts of N,N'-methylenebisacrylamide, 4 parts of functional monomer, and 0.6 parts of sodium persulfate and stirring evenly to obtain an aqueous phase liquid;

[0053] (3) 8 parts of 2,6,10-trimethyldodecane and 6 parts of sorbitan monooleate were mixed, 2 parts of organic modified nano bentonite were added and stirred, and the aqueous phase liquid of step (2) was added under rapid stirring, and emulsified at a temperature of 35° C. for 20 minutes to obtain an emulsion;

[0054] (4) 0.6 parts of sodium bisulfite are prepared into a 3% sodium bisulfite aqueous solution by mass, the emulsion described in step (3) is added to the reactor, and the 3% sodium bisulfite aqueous solution by mass is slowly added under stirring conditions of 10 Hz until no obvious heat is released, the reaction temperature is controlled to 50° C., the reaction is carried out for 2 hours, the temperature is raised to 80° C., the reaction is carried out for 2 hours, the reaction is completed, the temperature is lowered to 60° C., 5 parts of polyoxyethylene sorbitan monooleate are added, stirring is continued for 10 minutes, and filtering is performed to obtain an electrolyte-resistant printing thickener with improved coloring effect;

[0055] The functional monomer is composed of p-styrenepropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid and triphenyl phenol polyoxyethylene ether methacrylate in a weight ratio of 5:1:1;

[0056] Preparation of organically modified nano-bentonite: Nano-bentonite was dissolved in deionized water, and a 20% by mass concentration of Na2CO3 solution was added dropwise while stirring at a speed of 3000 r / min until the pH value stabilized at 10. Propylene glycol alginate was added dropwise and allowed to stand to obtain a stable suspension. The temperature was raised to 150°C, and a cetyltrimethylammonium bromide solution and isopropanol were added. The reaction was carried out for 5 hours to obtain a modified nano-bentonite suspension slurry. The suspension was centrifuged to obtain a nano-bentonite precipitate. Excess Br ions were washed off with an ethanol solution. No yellow precipitate was produced by AgNO3 testing. The suspension was dried and ground to obtain the organically modified nano-bentonite.

[0057] The weight ratio of nano bentonite, cetyltrimethylammonium bromide solution and isopropyl alcohol is 1:2:0.5; the amount of propylene glycol alginate is 1% of the weight of the nano bentonite.

[0058] Example 4

[0059] Preparation of electrolyte-resistant printing thickener to improve coloring effect:

[0060] (1) 15 parts of methacrylic acid and 40 parts of water were mixed according to weight, and 20 parts of triethanolamine was added under stirring at 22 Hz. The temperature was controlled at 25°C.

[0061] (2) adding 0.3 parts of N,N'-methylenebisacrylamide, 6 parts of functional monomer, and 0.4 parts of sodium persulfate and stirring evenly to obtain an aqueous phase liquid;

[0062] (3) 10 parts of 2,6,10-trimethyldodecane and 4 parts of sodium dodecyl diphenyl ether disulfonate were mixed, 3 parts of organic modified nano bentonite were added and stirred, and the aqueous phase liquid of step (2) was added under rapid stirring, and emulsified at a temperature of 30° C. for 30 minutes to obtain an emulsion;

[0063] (4) 0.3 parts of sodium bisulfite are prepared into a 3% sodium bisulfite aqueous solution by mass, the emulsion described in step (3) is added to the reactor, and the 3% sodium bisulfite aqueous solution by mass is slowly added under stirring conditions of 12 Hz until no obvious heat is released, the reaction temperature is controlled to 45° C., the reaction is carried out for 2 hours, the temperature is raised to 80° C., the reaction is carried out for 2 hours, the reaction is completed, the temperature is lowered to 64° C., 3 parts of nonylphenol polyoxyethylene ether are added, stirring is continued for 10-20 minutes, and filtering is performed to obtain an electrolyte-resistant printing thickener with improved coloring effect;

[0064] The functional monomer is composed of p-styrenepropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid and triphenyl phenol polyoxyethylene ether methacrylate in a weight ratio of 4:2:1;

[0065] Preparation of organically modified nano-bentonite: Nano-bentonite was dissolved in deionized water, and a 25% by mass concentration of Na2CO3 solution was added dropwise while stirring at a speed of 2500 r / min until the pH value stabilized at 10. Propylene glycol alginate was added dropwise and allowed to stand to obtain a stable suspension. The temperature was raised to 140°C, and a cetyltrimethylammonium bromide solution and isopropanol were added. The reaction was carried out for 7 hours to obtain a modified nano-bentonite suspension slurry. The suspension was centrifuged to obtain a nano-bentonite precipitate. Excess Br ions were washed off with an ethanol solution. No yellow precipitate was produced by AgNO3 testing. The suspension was dried and ground to obtain the organically modified nano-bentonite.

[0066] The weight ratio of nano bentonite, cetyltrimethylammonium bromide solution and isopropyl alcohol is 1:2:0.6; the amount of propylene glycol alginate is 1% of the weight of the nano bentonite.

[0067] Comparative Example 1

[0068] Preparation of electrolyte-resistant printing thickener to improve coloring effect:

[0069] (1) 15 parts of methacrylic acid and 40 parts of water were mixed according to weight, and 22 parts of triethanolamine was added under stirring at 23 Hz. The temperature was controlled at 28°C.

[0070] (2) adding 0.3 parts of N,N'-methylenebisacrylamide, 6 parts of functional monomer, and 0.4 parts of sodium persulfate and stirring evenly to obtain an aqueous phase liquid;

[0071] (3) 12 parts of 2,6,10-trimethyldodecane and 5 parts of sorbitan monooleate were mixed, 4 parts of organic modified nano bentonite were added and stirred, and the aqueous phase liquid of step (2) was added under rapid stirring, and emulsified at a temperature of 28° C. for 30 minutes to obtain an emulsion;

[0072] (4) 0.3 parts of sodium bisulfite are prepared into a 3% sodium bisulfite aqueous solution by mass, the emulsion described in step (3) is added to the reactor, and the 3% sodium bisulfite aqueous solution by mass is slowly added under stirring conditions of 12 Hz until no obvious heat is released, the reaction temperature is controlled to 45° C., the reaction is carried out for 2.5 hours, the temperature is raised to 80° C., the reaction is carried out for 1.5 hours, the reaction is completed, the temperature is lowered to 63° C., 3 parts of polyoxyethylene sorbitan monooleate are added, stirring is continued for 15 minutes, and filtering is performed to obtain an electrolyte-resistant printing thickener with improved coloring effect;

[0073] The functional monomer is composed of 2-acrylamide-2-methylpropanesulfonic acid and triphenyl phenol polyoxyethylene ether methacrylate in a weight ratio of 1.5:1;

[0074] Preparation of organically modified nano-bentonite: Nano-bentonite was dissolved in deionized water, and a 25% by mass concentration of Na2CO3 solution was added dropwise while stirring at a speed of 2500 r / min until the pH value stabilized at 10. Propylene glycol alginate was added dropwise and allowed to stand to obtain a stable suspension. The temperature was raised to 135°C, and a cetyltrimethylammonium bromide solution and isopropanol were added. The reaction was carried out for 6.5 hours to obtain a modified nano-bentonite suspension slurry. The suspension was centrifuged to obtain a nano-bentonite precipitate. Excess Br ions were washed off with an ethanol solution. No yellow precipitate was produced by AgNO3 testing. The suspension was dried and ground to obtain the organically modified nano-bentonite.

[0075] The weight ratio of nano bentonite, cetyltrimethylammonium bromide solution and isopropyl alcohol is 1:1.5:0.7; the amount of propylene glycol alginate is 1% of the weight of the nano bentonite.

[0076] Comparative Example 2

[0077] Preparation of electrolyte-resistant printing thickener to improve coloring effect:

[0078] (1) 15 parts of methacrylic acid and 40 parts of water were mixed according to weight, and 22 parts of triethanolamine was added under stirring at 23 Hz. The temperature was controlled at 28°C.

[0079] (2) adding 0.3 parts of N,N'-methylenebisacrylamide, 6 parts of functional monomer, and 0.4 parts of sodium persulfate and stirring evenly to obtain an aqueous phase liquid;

[0080] (3) 12 parts of 2,6,10-trimethyldodecane and 5 parts of sorbitan monooleate were mixed and stirred, and the aqueous phase liquid of step (2) was added under rapid stirring, and emulsified at a temperature of 28° C. for 30 minutes to obtain an emulsion;

[0081] (4) 0.3 parts of sodium bisulfite are prepared into a 3% sodium bisulfite aqueous solution by mass, the emulsion described in step (3) is added to the reactor, and the 3% sodium bisulfite aqueous solution by mass is slowly added under stirring conditions of 12 Hz until no obvious heat is released, the reaction temperature is controlled to 45° C., the reaction is carried out for 2.5 hours, the temperature is raised to 80° C., the reaction is carried out for 1.5 hours, the reaction is completed, the temperature is lowered to 63° C., 3 parts of polyoxyethylene sorbitan monooleate are added, stirring is continued for 15 minutes, and filtering is performed to obtain an electrolyte-resistant printing thickener with improved coloring effect;

[0082] The functional monomer is composed of p-styrenepropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid and triphenylphenol polyoxyethylene ether methacrylate in a weight ratio of 4:1.5:1.

[0083] Comparative Example 3

[0084] Preparation of electrolyte-resistant printing thickener to improve coloring effect:

[0085] (1) 15 parts of methacrylic acid and 40 parts of water were mixed according to weight, and 22 parts of triethanolamine was added under stirring at 23 Hz. The temperature was controlled at 28°C.

[0086] (2) adding 0.3 parts of N,N'-methylenebisacrylamide, 6 parts of functional monomer, and 0.4 parts of sodium persulfate and stirring evenly to obtain an aqueous phase liquid;

[0087] (3) 12 parts of 2,6,10-trimethyldodecane and 5 parts of sorbitan monooleate were mixed, 4 parts of organic modified nano bentonite were added and stirred, and the aqueous phase liquid of step (2) was added under rapid stirring, and emulsified at a temperature of 28° C. for 30 minutes to obtain an emulsion;

[0088] (4) 0.3 parts of sodium bisulfite are prepared into a 3% sodium bisulfite aqueous solution by mass, the emulsion described in step (3) is added to the reactor, and the 3% sodium bisulfite aqueous solution by mass is slowly added under stirring conditions of 12 Hz until no obvious heat is released, the reaction temperature is controlled to 45° C., the reaction is carried out for 2.5 hours, the temperature is raised to 80° C., the reaction is carried out for 1.5 hours, the reaction is completed, the temperature is lowered to 63° C., 3 parts of polyoxyethylene sorbitan monooleate are added, stirring is continued for 15 minutes, and filtering is performed to obtain an electrolyte-resistant printing thickener with improved coloring effect;

[0089] The functional monomer is composed of p-styrenepropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid and triphenyl phenol polyoxyethylene ether methacrylate in a weight ratio of 4:1.5:1;

[0090] Preparation of organically modified nano-bentonite: Nano-bentonite was dissolved in deionized water, and a 25% by mass concentration of Na2CO3 solution was added dropwise while stirring at a speed of 2500 r / min until the pH value stabilized at 10. Propylene glycol alginate was added dropwise and allowed to stand to obtain a stable suspension. The temperature was raised to 135°C, and a cetyltrimethylammonium bromide solution and isopropanol were added. The reaction was carried out for 6.5 hours to obtain a modified nano-bentonite suspension slurry. The suspension was centrifuged to obtain a nano-bentonite precipitate. Excess Br ions were washed off with an ethanol solution. No yellow precipitate was produced by AgNO3 testing. The suspension was dried and ground to obtain the organically modified nano-bentonite.

[0091] The weight ratio of nano bentonite, cetyltrimethylammonium bromide solution and isopropyl alcohol is 1:1.5:0.7; the amount of propylene glycol alginate is 1% of the weight of the nano bentonite.

[0092] Experimental example

[0093] The electrolyte-resistant printing thickeners for improving coloring effect prepared in Examples 1-4 and Comparative Examples 1-3 were tested for relevant properties. The testing method is as follows:

[0094] Viscosity of white paste: Accurately weigh 2g of thickener, add 98g of distilled water, stir, and add 3-4 drops of aqueous ammonia. Stir thoroughly to make a 2% by weight white paste. Measure the viscosity of the white paste using a Brookfield DV-II+ Pro viscometer at a constant speed of 10 rpm (spindle 6) at room temperature.

[0095] Viscosity retention rate: Electrolyte resistance is expressed by viscosity retention rate. The viscosity of the thickener slurry with 0.05% NaCl (solid) added is measured. The higher the viscosity retention rate, the better the electrolyte resistance.

[0096] Performance test data is shown in Table 1 below:

[0097] Table 1

[0098] Test items Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 White slurry viscosity (mPa·s) 13760 13750 13750 13760 11670 12130 12630 Viscosity retention rate (%) 84 83 83 84 51 58 56

[0099] As can be seen from Table 1, the electrolyte-resistant printing thickeners for improving the coloring effect of Examples 1-4 of the present application have good performance, and the thickening effect and electrolyte resistance can reach a high level when the specific raw material ratios are matched with each other.

[0100] The raw materials of Comparative Example 1 do not contain styrenepropanesulfonic acid, and the rest are the same as Example 1. The white paste viscosity and viscosity retention rate of the electrolyte-resistant printing thickener for improving the coloring effect prepared in Comparative Example 1 are significantly reduced, indicating that due to the hydrophobicity of the styrene group part in the styrenepropanesulfonic acid of the present application, the loss of charge shielding is compensated by hydrophobic association, the amount of emulsifier used is reduced, and the sensitivity to pH and electrolyte is reduced. At the same time, the introduced sulfonic acid group improves salt resistance, making it more suitable for high electrolyte systems.

[0101] The raw materials of Comparative Example 2 do not contain organically modified nano-bentonite, and the rest are the same as Example 1. The white slurry viscosity and viscosity retention rate of the electrolyte-resistant printing thickener with improved coloring effect prepared in Comparative Example 2 are significantly reduced, indicating that the present application introduces organically modified nano-bentonite into the printing thickener. The layered silicate structure of bentonite has a strong cation exchange capacity and has the effect of adsorbing weight and thickening. After organic modification, the hydrophobicity and dispersibility can be further improved.

[0102] The raw materials of Comparative Example 3 do not contain 2-acrylamide-2-methylpropanesulfonic acid, and the rest are the same as Example 1. The white paste viscosity and viscosity retention rate of the electrolyte-resistant printing thickener for improving the coloring effect prepared in Comparative Example 3 are significantly reduced, indicating that the electronegativity of the sulfonic acid group in the 2-acrylamide-2-methylpropanesulfonic acid of the present application is stronger and less sensitive to electrolytes.

[0103] Although the embodiments of the present application have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions or variations may be made to these embodiments without departing from the principles and purpose of the present application, and that the technical solutions after these changes, modifications, substitutions or variations will fall within the scope of protection of the present application.

Claims

1. An electrolyte-resistant printing thickener for improving coloring effect, characterized in that: The preparation comprises the following raw materials in parts by weight: Methacrylic acid 10-20 parts, triethanolamine 15-30 parts, N,N'-methylenebisacrylamide 0.1-0.5 parts, functional monomer 4-8 parts, organic modified nano bentonite 2-5 parts, emulsifier 3-6 parts, sodium bisulfite 0.1-0.6 parts, sodium persulfate 0.1-0.6 parts, oil phase solvent 8-15 parts, reverse emulsifier 2-5 parts, water 30-50 parts; The functional monomer is composed of p-styrenepropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid and triphenylethylphenol polyoxyethylene ether methacrylate in a weight ratio of (3-5): (1-2):

1.

2. The electrolyte-resistant printing thickener for improving coloring effect according to claim 1, characterized in that: The oil phase solvent is 2,6,10-trimethyldodecane.

3. The electrolyte-resistant printing thickener for improving coloring effect according to claim 1, characterized in that: The emulsifier is selected from one of sorbitan monooleate and sodium dodecyl diphenyl ether disulfonate.

4. The electrolyte-resistant printing thickener for improving coloring effect according to claim 1, characterized in that: The reverse emulsifier is selected from one of polyoxyethylene sorbitan monooleate and nonylphenol polyoxyethylene ether.

5. The electrolyte-resistant printing thickener for improving coloring effect according to claim 1, characterized in that: The preparation of the organically modified nano bentonite comprises the following steps: The nano-bentonite was dissolved in deionized water, and Na2CO3 solution was added dropwise while stirring until the pH value stabilized at 10. At the same time, propylene glycol alginate was added dropwise and allowed to stand to obtain a stable suspension. The temperature was raised to 120-150°C, and hexadecyltrimethylammonium bromide solution and isopropanol were added. The reaction was carried out for 5-8 hours to obtain a modified nano-bentonite suspension slurry. The nano-bentonite was centrifuged to obtain a nano-bentonite precipitate. The excess Br ions were washed off with an ethanol solution. No yellow precipitate was produced by AgNO3 test. The organically modified nano-bentonite was dried and ground.

6. The electrolyte-resistant printing thickener for improving coloring effect according to claim 5, characterized in that: The weight ratio of the nano-bentonite, the cetyltrimethylammonium bromide solution and the isopropyl alcohol is 1:(1-2):(0.5-0.8).

7. The electrolyte-resistant printing thickener for improving coloring effect according to claim 5, characterized in that: The amount of propylene glycol alginate used is 1% by weight of the nano bentonite.

8. The electrolyte-resistant printing thickener for improving coloring effect according to claim 5, characterized in that: The mass percentage concentration of the Na2CO3 solution is 20-30%.

9. The electrolyte-resistant printing thickener for improving coloring effect according to claim 5, characterized in that: The stirring speed is 2000-3000r / min.

10. A method for preparing an electrolyte-resistant printing thickener for improving coloring effect according to any one of claims 1 to 9, characterized in that: The following steps are involved: (1) Mix methacrylic acid and water according to parts by weight, add triethanolamine under stirring at 20-25 Hz, and control the temperature at 20-35° C.; (2) adding N,N'-methylenebisacrylamide, functional monomer, and sodium persulfate and stirring evenly to obtain an aqueous phase liquid; (3) mixing the oil phase solvent and the emulsifier, adding the organic modified nano bentonite and stirring, adding the aqueous phase liquid of step (2) under rapid stirring, and emulsifying at a temperature of 20-35° C. for 20-40 minutes to obtain an emulsion; (4) Sodium bisulfite is prepared into a sodium bisulfite aqueous solution with a mass fraction of 3%, the emulsion described in step (3) is added to a reactor, and a sodium bisulfite aqueous solution with a mass fraction of 3% is slowly added under stirring conditions of 10-15 Hz until no obvious heat is released, the reaction temperature is controlled to 40-50° C., the reaction is carried out for 2-3 hours, the temperature is raised to 80° C., the reaction is carried out for 1-2 hours, the reaction is completed, the temperature is lowered to 60° C.-65° C., an inverse emulsifier is added, stirring is continued for 10-20 minutes, and filtering is performed to obtain an electrolyte-resistant printing thickener with improved coloring effect.