Preparation and application of high-molecular hyperdispersant
By designing the preparation method of polymer superdispersant, using the PUD emulsion with complex spatial structure, the problem of poor dispersion effect of traditional dispersants is solved, and better dispersion effect and stability are achieved.
Patent Information
- Application Number
- CN202411768746.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-04
- Publication Date
- 2025-02-11
AI Technical Summary
The hydrophilic groups of traditional dispersants are prone to desorption, causing particles to reflocculate, and the hydrocarbon chain structure of the oleophilic group is too short to produce sufficient steric hindrance, resulting in poor dispersion effect.
A polymer superdispersant was designed, and the preparation method includes preparing sodium 1,2-dihydroxy-3-propyl sulfonate through sulfate esterification reaction using raw materials such as sulfamic acid, glycerol, urea, etc., and with HDI trimers, polyols, etc. react to form a PUD emulsion with a complex spatial structure.
The solvation ability and steric hindrance are improved, and the attraction and agglomeration of dispersed particles is avoided, the dispersion effect is significantly improved, the particle adsorption ability is enhanced, and a stable dispersion state is maintained.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of chemical engineering, in particular to a polymer type superdispersant and a preparation method thereof. Background Art
[0002] Dispersants are substances that promote the uniform dispersion of material particles in the medium. Polymer dispersants, also known as multifunctional pigment dispersants, are the most commonly used dispersants. They are divided into polycaprolactone polyol-polyethyleneimine block copolymer dispersants, acrylate polymer dispersants, polyurethane or polyester polymer dispersants, etc. Their polymer chain segments can entangle with medium molecules and have multiple anchor groups that can firmly bind to the surface of pigment particles.
[0003] Dispersants are widely used in printing and dyeing, textile, papermaking and other industries in industrial production. As a representative of anionic dispersants, acrylic dispersants are widely used in various fields due to their environmental friendliness. Since the hydrophilic groups of traditional dispersants are generally designed only to have a certain affinity with water, the purpose in many applications is to meet the needs of forming capsules together with the lipophilic groups. The consideration of its adsorption fastness on the particle surface is often placed in a secondary position. Therefore, the hydrophilic groups in the molecular structure are easy to desorb and cause the particles to re-flocculate. The lipophilic groups of traditional dispersants are generally hydrocarbon chain structures, mainly alkane chains. Although they have good compatibility with non-polar and low-grade organic solvents and can be fully extended, because their chain length is too short, the thickness of the adsorption layer formed is also very limited, and it cannot produce enough space to resist the repulsive force to make the particles evenly dispersed, and the dispersion effect is poor. Summary of the invention
[0004] The purpose of the present invention is to solve the above problems and to design a polymer type super dispersant and a preparation method thereof.
[0005] To achieve the above-mentioned purpose, the technical scheme of the present invention is a polymer type super dispersant and a preparation method thereof, wherein the preparation raw materials include aminosulfonic acid, propylene glycol, urea, ethanol, aminoethanesulfonic acid, HDI trimer, triethylamine, polyol, acetone, and ethylenediamine.
[0006] A method for preparing a polymeric hyperdispersant comprises the following steps:
[0007] Step 1: Preparation of pure 1,2-dihydroxy-3-propyl ester sulfonate sodium;
[0008] Step 2: Preparation of intermediate products;
[0009] Step 3: Preparation of PUD emulsion.
[0010] As a further description of the technical solution, in the step 1, aminosulfonic acid and propylene glycol are added to a three-necked flask in a certain molar ratio, and then 5wt% (calculated based on the total mass of the system) of urea is added as a catalyst, a stirring device and a condensing water device are installed, and the bottle mouth is closed for sulfuric acid esterification reaction.
[0011] As a further description of the technical solution, the sulfation reaction is carried out at 120°C for 4 hours to obtain a crude product; the crude product is added to ethanol and stirred to remove unreacted propylene glycol, and then the crude product is dissolved in methanol, allowed to stand, and the aminosulfonic acid insoluble in methanol is filtered out, and the filtrate is subjected to reduced pressure distillation at 40°C to remove the solvent to obtain yellow-brown 1,2-dihydroxy-3-propyl ammonium sulfonate.
[0012] As a further description of the technical solution, 1,2-dihydroxy-3-propyl ammonium sulfonate is dissolved in water, heated to 40°C, and 1 mol / L sodium hydroxide solution is added dropwise until pH = 7 to obtain pure 1,2-dihydroxy-3-propyl sodium sulfonate, and the generated ammonia is absorbed by aqueous hydrochloric acid solution.
[0013] As a further description of the technical solution, the reaction equation of pure 1,2-dihydroxy-3-propyl sodium sulfonate is as follows:
[0014]
[0015] As a further description of the technical solution, in the step 2, aminoethanesulfonic acid and HDI trimer are premixed at 50° C. for 20 minutes, triethylamine is added using a constant pressure dropping funnel (2-3s / d), and under nitrogen protection, aminoethanesulfonic acid, HDI trimer, and triethylamine are added to a four-necked flask equipped with a condensing reflux device, a thermometer, a mechanical stirrer, and a nitrogen inlet and outlet.
[0016] As a further description of the technical solution, in step 2, the system is heated to 90°C for 4 hours, and the reaction is stopped when the NCO of the system reaches the theoretical value. After the reaction is completed, the system is kept warm and vacuumed for 15 minutes, and then the system is cooled to room temperature and discharged to obtain an intermediate product.
[0017] As a further description of the technical solution, in step three, the polyol is added to a four-necked flask, and the four interfaces of the flask are respectively equipped with a mechanical stirrer, a thermometer, a reflux condenser and a nitrogen inlet and outlet, and then the electric heating jacket is used to heat to 120°C, and the water pump is turned on to pump water for 1 hour.
[0018] As a further description of the present technical solution, in the step three, after the water is pumped out, wait for cooling to room temperature, add the intermediate product and an appropriate amount of acetone to the flask at one time, adjust to a suitable stirring speed, react and stir at room temperature for half an hour, keep the reaction temperature at 65°C, and react until the -NCO content reaches the theoretical value (determined by n-butylamine titration method) to obtain a prepolymer with NCO as the end, add a certain amount of acetone to the reaction system while hot to reduce the viscosity of the system, and quickly add 1,2-dihydroxy-3-propyl ester sulfonate sodium solution and ethylenediamine aqueous solution to the reaction system; adjust the stirring speed, add water to the reaction system, and then a phase inversion occurs to obtain a PUD emulsion; finally, remove a large amount of acetone in the reaction system by reduced pressure distillation to obtain the final PUD emulsion, that is, a polymer-type hyperdispersant.
[0019] The beneficial effect is that the polymer superdispersant of the present technical solution has improved solvation ability and steric hindrance compared with ordinary superdispersants, avoids the attraction and agglomeration of dispersed particles, and has a better dispersion effect. The superdispersant prepared by the present preparation method has improved particle adsorption capacity. At the same time, the complex spatial structure can produce greater steric hindrance, so that the particles can be effectively dispersed, not easily aggregated, and maintain a stable dispersion state. DETAILED DESCRIPTION
[0020] First of all, the original intention of the design of the present invention is explained. The lipophilic group of the traditional dispersant is generally a hydrocarbon chain structure, mainly an alkane chain. Although it has good compatibility with non-polar and low-grade organic solvents and can be fully extended, its chain length is too short, and the thickness of the adsorption layer formed is also very limited. It cannot generate enough space to resist the repulsive force so that the particles are evenly dispersed, and the dispersion effect is poor. Therefore, the present invention designs a polymer type super dispersant and a preparation method thereof.
[0021] The present invention will be described in detail below. A polymer type super dispersant is prepared from raw materials including aminosulfonic acid, propylene glycol, urea, ethanol, aminoethanesulfonic acid, HDI trimer, triethylamine, polyol, acetone and ethylenediamine.
[0022] Example 1
[0023] Step 1: Preparation of pure sodium 1,2-dihydroxy-3-propyl ester sulfonate
[0024] Add 48.5 parts of aminosulfonic acid, 46 parts of propylene glycol, and 4 parts of urea to the reactor, and heat to 120°C for 4 hours under stirring conditions; after the reaction is completed, first wash with ethanol to remove the unreacted propylene glycol, and then dry. Then dissolve with methanol to remove the unreacted aminosulfonic acid, filter and dry, dissolve with water, and adjust the pH to 7.5 with sodium hydroxide to remove ammonium ions. Finally, dry by reduced pressure distillation to obtain yellow-brown 1,2-dihydroxy-3-propyl ammonium sulfonate.
[0025] The reaction equation is as follows:
[0026]
[0027] Step 2: Preparation of intermediate products
[0028] Add 62.5 parts of aminoethanesulfonic acid and 200 parts of HDI trimer into the reactor and premix them at 50°C for 20 minutes. Then add 6 parts of triethylamine (2-3s / d) using a constant pressure dropping funnel. Under stirring and nitrogen protection, heat the system to 90°C and react for 4 hours. Stop the reaction when the NCO of the system reaches the theoretical value. After the reaction is completed, keep the reaction at 90°C and a vacuum degree of 0.06-0.1MPa for 15 minutes to obtain an intermediate product.
[0029] Step 3: Preparation of PUD emulsion
[0030] Add 50 parts of polyol and 5.8 parts of acetone to the intermediate product prepared in step 2, react at room temperature for 30 minutes under stirring conditions, the reaction temperature is 60°C to 70°C, react until the -NCO content reaches the theoretical value (determined by n-butylamine titration method), and obtain a prepolymer with NCO as the end, add a certain amount of acetone to the reaction system while hot to reduce the viscosity of the system, and quickly add the 1,2-dihydroxy-3-propyl ester sodium sulfonate solution prepared in step 1 and 9.7 parts of ethylenediamine aqueous solution to the reaction system; adjust the stirring speed, add water to the reaction system and then phase inversion occurs to obtain a PUD emulsion; finally, remove the acetone in the reaction system by reduced pressure distillation to obtain the final PUD emulsion, that is, a polymer-type hyperdispersant.
[0031] Example 2
[0032] Step 1: Preparation of pure sodium 1,2-dihydroxy-3-propyl ester sulfonate
[0033] Add 43.5 parts of aminosulfonic acid, 50 parts of propylene glycol, and 4 parts of urea to the reactor, and heat to 120°C for 4 hours under stirring conditions; after the reaction is completed, first wash with ethanol to remove the unreacted propylene glycol, and then dry. Then dissolve with methanol to remove the unreacted aminosulfonic acid, filter and dry, dissolve with water, and adjust the pH to 7.5 with sodium hydroxide to remove ammonium ions. Finally, dry by reduced pressure distillation to obtain yellow-brown 1,2-dihydroxy-3-propyl ammonium sulfonate.
[0034] Step 2: Preparation of intermediate products
[0035] Add 62.5 parts of aminoethanesulfonic acid and 250 parts of HDI trimer into the reactor and premix them at 50°C for 20 minutes. Then add 6 parts of triethylamine (2-3s / d) using a constant pressure dropping funnel. Under stirring and nitrogen protection, heat the system to 90°C and react for 4 hours. Stop the reaction when the NCO of the system reaches the theoretical value. After the reaction is completed, keep the reaction at 90°C and a vacuum degree of 0.06-0.1MPa for 15 minutes to obtain an intermediate product.
[0036] Step 3: Preparation of PUD emulsion
[0037] Add 60 parts of polyol and 5.8 parts of acetone to the intermediate product prepared in step 2, react at room temperature for 30 minutes under stirring conditions, the reaction temperature is 60°C to 70°C, react until the -NCO content reaches the theoretical value (determined by n-butylamine titration method), and obtain a prepolymer with NCO as the end, add a certain amount of acetone to the reaction system while hot to reduce the viscosity of the system, and quickly add the 1,2-dihydroxy-3-propyl ester sodium sulfonate solution prepared in step 1 and 8.7 parts of ethylenediamine aqueous solution to the reaction system; adjust the stirring speed, add water to the reaction system and then phase inversion occurs to obtain a PUD emulsion; finally, remove the acetone in the reaction system by vacuum distillation to obtain the final PUD emulsion, that is, a polymer-type hyperdispersant.
[0038] Example 3
[0039] Step 1: Preparation of pure sodium 1,2-dihydroxy-3-propyl ester sulfonate
[0040] Add 48.5 parts of aminosulfonic acid, 55 parts of propylene glycol, and 4 parts of urea to the reactor, and heat to 120°C for 4 hours under stirring conditions; after the reaction is completed, first wash with ethanol to remove the unreacted propylene glycol, and then dry. Then dissolve with methanol to remove the unreacted aminosulfonic acid, filter and dry, dissolve with water, and adjust the pH to 7.5 with sodium hydroxide to remove ammonium ions. Finally, dry by reduced pressure distillation to obtain yellow-brown 1,2-dihydroxy-3-propyl ammonium sulfonate.
[0041] Step 2: Preparation of intermediate products
[0042] Add 62.5 parts of aminoethanesulfonic acid and 220 parts of HDI trimer into the reactor and premix them at 50°C for 20 minutes. Then add 6 parts of triethylamine (2-3s / d) using a constant pressure dropping funnel. Under stirring and nitrogen protection, heat the system to 90°C and react for 4 hours. Stop the reaction when the NCO of the system reaches the theoretical value. After the reaction is completed, keep the reaction at 90°C and a vacuum degree of 0.06-0.1MPa for 15 minutes to obtain an intermediate product.
[0043] Step 3: Preparation of PUD emulsion
[0044] 70 parts of polyol and 5.8 parts of acetone are added to the intermediate product prepared in step 2, and the reaction is carried out at room temperature for 30 minutes under stirring conditions, the reaction temperature is 60°C to 70°C, and the -NCO content reaches the theoretical value (determined by n-butylamine titration method), and a prepolymer with NCO as the end is obtained. A certain amount of acetone is added to the reaction system while hot to reduce the viscosity of the system, and the 1,2-dihydroxy-3-propyl ester sodium sulfonate solution prepared in step 1 and 9.7 parts of ethylenediamine aqueous solution are quickly added dropwise to the reaction system; the stirring speed is adjusted, and water is added to the reaction system to cause a phase inversion to obtain a PUD emulsion; finally, the acetone in the reaction system is removed by reduced pressure distillation to obtain the final PUD emulsion, that is, a polymer-type hyperdispersant.
[0045] Comparative Example 1
[0046] 30.25 parts of ethyleneoxypolyoxyethylene ether 3000, 9.45 parts of n-butyl acrylate, 7.56 parts of acrylic acid, 2.0 parts of 3-mercaptopropionic acid and 116.04 parts of isopropanol were placed in a 500 mL four-necked flask, a condenser and a thermometer were installed, the stirrer was turned on (300 r / min), nitrogen was introduced, and when the temperature of the reaction liquid in the four-necked flask reached 70°C, 0.47 parts of azobisisobutyronitrile was added and the reaction was continued for 3 hours. After cooling, the dispersant was obtained.
[0047] Comparative Example 2
[0048] 28.83 parts of acrylic acid, 18.43 parts of styrene, 2.0 parts of 3-mercaptopropionic acid, and 116.03 parts of isopropanol were placed in a 500 mL four-necked flask, a condenser and a thermometer were installed, the stirrer was turned on (300 r / min), and nitrogen was introduced. When the temperature of the reaction liquid in the four-necked flask reached 70°C, 0.47 parts of azobisisobutyronitrile was added, and the reaction was continued for 3 hours. The reaction solvent was then removed by a rotary evaporator, and the dispersant was obtained after cooling.
[0049] Performance Testing
[0050] The dispersants of Examples 1 to 3, the dispersants of Comparative Examples 1 to 2, and a commercially available high-efficiency dispersant competitor (purchased from Jinan Baoda Dye Chemical Co., Ltd., brand NNO BD-10) were used.
[0051] Preparation of dye dispersion: Different dispersants were mixed with disperse blue 79 in a mass ratio of 2:8 and ball milled with agate beads at a rate of 400 r·min-1 for 4 h at a pH value of 5.0-6.0.
[0052] Dispersion stability test method: The dye dispersion obtained by ball milling is prepared into a 0.1% suspension, and its particle size is measured by scanning with a laser particle size and shape analyzer (EyeTech-Laser model produced by Ankersmid Company of the Netherlands).
[0053] Test method for fiber staining effect: prepare 100mL of 10g / L dispersant sample solution, pH 4.5-5.0, 1g of polyester fiber, heat to 130℃ at 1℃ / min and keep for 30min, rinse with tap water and dry, use blank sample as reference, and use Datacolor to test the whiteness value of polyester fiber treated with different dispersants (the larger the whiteness value, the lighter the stain).
[0054] Storage stability: The dye dispersion obtained by ball milling was stored at 55°C to observe whether it was stratified.
[0055] The specific test results are shown in Table 1
[0056] Table 1 Performance of each comparative example
[0057]
[0058]
[0059] Note: (1) The smaller the dispersion stability value, the smaller the particle size and the better the dispersion.
[0060] (2) The larger the whiteness value, the lighter the stain on the fiber.
[0061] It can be seen from the data in Table 1 that the liquid disperse dye dispersed by the dispersant of the technical solution has the advantages of small particle size and no contamination to fibers, and at the same time significantly improves the storage stability of the product.
[0062] The above technical solutions only reflect the preferred technical solutions of the technical solutions of the present invention. Some changes that may be made to certain parts thereof by technicians in this technical field all reflect the principles of the present invention and fall within the protection scope of the present invention.
Claims
1. A polymer type hyperdispersant, characterized in that: The preparation raw materials include aminosulfonic acid, propylene glycol, urea, ethanol, aminoethanesulfonic acid, HDI trimer, triethylamine, polyol, acetone and ethylenediamine.
2. A method for preparing a polymeric hyperdispersant as claimed in claim 1, characterized in that: The following steps are involved: Step 1: Preparation of pure 1,2-dihydroxy-3-propyl ester sulfonate sodium; Step 2: Preparation of intermediate products; Step 3: Preparation of PUD emulsion.
3. The method for preparing a polymeric hyperdispersant according to claim 2, characterized in that: In the step 1, aminosulfonic acid and propylene glycol are added to a three-necked flask in a certain molar ratio, and then 5wt% (calculated based on the total mass of the system) of urea is added as a catalyst, a stirring device and a condensing water device are installed, and the flask mouth is closed to carry out a sulfation reaction.
4. The method for preparing a polymeric hyperdispersant according to claim 3, characterized in that: The sulfation reaction is carried out at 120°C for 4 hours to obtain a crude product; the crude product is added to ethanol and stirred to remove unreacted propylene glycol, and then the crude product is dissolved in methanol, allowed to stand, and the aminosulfonic acid insoluble in methanol is filtered out, and the filtrate is subjected to reduced pressure distillation at 40°C to remove the solvent to obtain yellow-brown 1,2-dihydroxy-3-propyl ammonium sulfonate.
5. The method for preparing a polymeric hyperdispersant according to claim 4, characterized in that: Dissolve 1,2-dihydroxy-3-propyl ammonium sulfonate in water, heat to 40°C, and add 1 mol / L sodium hydroxide solution until pH = 7 to obtain pure 1,2-dihydroxy-3-propyl sodium sulfonate. The generated ammonia gas is absorbed by aqueous hydrochloric acid solution.
6. The method for preparing a polymeric hyperdispersant according to claim 1, characterized in that: The reaction equation of pure 1,2-dihydroxy-3-propyl ester sodium sulfonate is as follows:
7. The method for preparing a polymeric hyperdispersant according to claim 2, characterized in that: In the step 2, aminoethanesulfonic acid and HDI trimer are premixed at 50° C. for 20 minutes, triethylamine is added using a constant pressure dropping funnel (2-3 s / d), and under nitrogen protection, aminoethanesulfonic acid, HDI trimer and triethylamine are added into a four-necked flask equipped with a condensing reflux device, a thermometer, a mechanical stirrer, and a nitrogen inlet and outlet.
8. The method for preparing a polymeric hyperdispersant according to claim 7, characterized in that: In the step 2, the system is heated to 90° C. for 4 hours, and the reaction is stopped when the NCO of the system reaches the theoretical value. After the reaction is completed, the system is kept warm and vacuumed for 15 minutes, and then cooled to room temperature before discharging to obtain an intermediate product.
9. The method for preparing a polymeric hyperdispersant according to claim 8, characterized in that: In the step 3, the polyol is added into a four-necked flask, and the four interfaces of the flask are respectively equipped with a mechanical stirrer, a thermometer, a reflux condenser and a nitrogen inlet and outlet, and then the electric heating mantle is used to heat to 120° C., and the water pump is turned on to pump water for 1 hour.
10. The method for preparing a polymeric hyperdispersant according to claim 9, characterized in that: In the step 3, after the water is pumped out, the mixture is cooled to room temperature, and the intermediate product and an appropriate amount of acetone are added to the flask at one time. The stirring speed is adjusted to an appropriate speed, and the reaction is stirred at room temperature for half an hour. The reaction temperature is maintained at 65°C, and the reaction is carried out until the -NCO content reaches the theoretical value (determined by n-butylamine titration method), and a prepolymer with NCO as the end is obtained. A certain amount of acetone is added to the reaction system while it is hot to reduce the viscosity of the system, and a sodium 1,2-dihydroxy-3-propyl ester sulfonate solution and an ethylenediamine aqueous solution are quickly added dropwise to the reaction system; the stirring speed is adjusted, and a phase inversion occurs after water is added to the reaction system to obtain a PUD emulsion; finally, a large amount of acetone in the reaction system is removed by reduced pressure distillation to obtain the final PUD emulsion, i.e., a polymer-type hyperdispersant.