Self-dispersible powder defoaming agent and preparation method thereof

Abstract

The invention relates to the technical field of defoaming agents, in particular to a self-dispersible powder defoaming agent and a preparation method thereof, and the self-dispersible powder defoaming agent comprises the following raw materials in parts by mass: 115-140 parts of a first composition; 138 to 175 parts of a second composition; wherein the first composition with larger particle size is obtained by mixing a defoaming active matter A and a defoaming active matter B, the organic silicon composition A, a carrier, white carbon black and other auxiliaries are blended, crushed and granulated, the obtained defoaming active matter A is encapsulated by beta-cyclodextrin and sulfonated sodium alginate, and then the defoaming active matter B with slow release performance and hydrophilicity is obtained. Furthermore, the dispersity can be improved while quick defoaming is realized, the fracture of particles is delayed, and the foam inhibition effect is achieved; and the second composition with a small particle size has a high specific surface area, is easier to disperse in the system, has a fast disintegration speed, can play a rapid defoaming role, and has a wide application prospect compared with the prior art.

Description

Technical Field

[0001] The present invention relates to the technical field of defoaming agents, in particular to a self-dispersible powder defoaming agent and a preparation method thereof. Background Art

[0002] Industrial cleaning requires industrial cleaning agents to remove dirt and reduce surface tension between oil and water. Cleaning agents contain large amounts of surfactants. During agitation, these surfactants adsorb around bubbles, stabilizing them and generating significant amounts of foam. This phenomenon is particularly prominent in industrial processes such as beer bottle cleaning, various heat exchange equipment, boilers, and heat exchange pipes, steel plate cleaning, mechanical cleaning, and cement and starch gelatinization. The presence of foam can reduce production capacity, waste raw materials and products, prolong reaction cycles, affect product quality, and pollute the environment. Therefore, eliminating foam is crucial, and defoaming agents are commonly added to industrial processes to achieve this goal.

[0003] Defoamers are primarily categorized as silicone defoamers and non-silicone defoamers based on their active ingredients. Heavy-duty laundry detergents and liquid laundry detergents used in drum washing machines mostly contain silicone defoamers. Silicone defoamers are considered very effective in this application because they can be added in very small quantities and are unaffected by water hardness, whereas traditional defoamer compositions, such as soaps, have certain requirements for water hardness. The most popular silicone defoamers on the market are primarily liquid types. Because they contain a large amount of water, they cannot be added to solid products, resulting in poor compatibility with the product being defoamed and a limited range of applications. Solid defoamers offer unique advantages in the cleaning industry.

[0004] In the prior art, patent document CN113797596A discloses a solid particle defoamer and a preparation method thereof. The defoamer uses a polyacrylate active ingredient as the main defoaming substance to avoid the silicon spots and precipitation problems caused by the silicone active ingredient. A modified starch-chitosan copolymer is used as a carrier, allowing the defoamer to have slow release properties while also having good fluidity, defoaming, and anti-foaming properties. However, the dispersibility of the defoamer in the system needs to be further improved.

[0005] Therefore, according to the above-mentioned related technologies, there is an urgent need to develop a self-dispersible powder defoaming agent and a preparation method thereof. Summary of the Invention

[0006] In view of this, the purpose of the present invention is to provide a self-dispersible powder defoamer and a preparation method thereof, so as to solve the problems of poor dispersibility and poor defoaming and defoaming ability of powder defoamers in the prior art.

[0007] Based on the above objectives, the present invention provides a self-dispersible powder defoaming agent and a preparation method thereof.

[0008] A self-dispersible powder defoamer comprises the following raw materials in parts by weight: 115-140 parts of the first composition; 138-175 parts of the second composition; The particle size of the first composition is 35-45 μm; The particle size of the second composition is 1-7 μm; The first composition is obtained by mixing the defoaming active ingredient A and the defoaming active ingredient B in a mass ratio of 8-14.5:33-40; The defoaming active ingredient A is prepared from the following raw materials in parts by weight: 50-70 parts of carrier; 1.3-2 parts of dispersant; 4-7 parts of binder; 14-18 parts of organosilicon composition A; 6.8-10 parts of white carbon black; 2.2-3 parts of disintegrant; 7-11 parts of deionized water; The defoaming active ingredient B is prepared from the defoaming active ingredient A, β-cyclodextrin and sulfonated sodium alginate; The second composition is prepared from the following raw materials in parts by weight: 50-70 parts of carrier; 1.3-2 parts of dispersant; 4-7 parts of binder; 14-18 parts of organosilicon composition B; 6.8-10 parts of white carbon black; 2.2-3 parts of disintegrant; and 7-11 parts of deionized water.

[0009] Preferably, the carrier is at least one of sulfate, carbonate, phosphate, polyphosphate, starch, cellulose and aluminosilicate; The average molecular weight of the dispersant is 1000-3000; The dispersant is any one of polyethylene glycol, polyvinyl alcohol, polyethyleneimine, polymaleic anhydride, polyacrylamide, polyacrylate, polyvinyl pyrrolidone and polyquaternary ammonium salt; The adhesive is any one of maleic acid acrylic acid copolymer, polymaleic acid, polyacrylic acid, alkylbenzene sulfonic acid, tartaric acid, oxalic acid, malic acid and citric acid; The disintegrant is any one of sodium chloride, sodium sulfate, ammonium sulfate, sodium carbonate and urea.

[0010] Preferably, the preparation method of the organosilicon composition A is as follows: Dimethyl silicone oil and silicone resin are placed in a reaction kettle, heated to 100-110° C. and stirred evenly, then cooled to 45-55° C. and polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene propylene glycol ether, deionized water and sodium hydroxymethyl cellulose are added in sequence, and mixed evenly to obtain an organosilicon composition A; The mass ratio of the dimethyl silicone oil, silicone resin, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene propylene glycol ether, deionized water and sodium hydroxymethyl cellulose is 26-33:3.5-5:14-22:3-5:55-70:0.1-0.4.

[0011] Preferably, the preparation method of the organosilicon composition B is as follows: After mixing polysiloxane, MQ resin, potassium hydroxide and dimethyl silicone oil, heating and reacting, hydrophobic silica was added, and the reaction was continued for 3-5 hours, and then cooled to room temperature to obtain an organosilicon composition B; The mass ratio of the polysiloxane, MQ resin, potassium hydroxide, dimethyl silicone oil and hydrophobic silica is 22-30:15-20:0.2-0.4:1.5-2.3:1.9-2.5; The temperature during the heating reaction is 95-105°C and the time is 1-1.5h.

[0012] Preferably, the preparation method of the defoaming active ingredient A is as follows: Step A1. The carrier, dispersant, and half of the disintegrant are mixed and extruded, and the extrusion speed is controlled to 30-40 r / min and the extrusion speed is 4-6 kg / min. After molding, the silicone composition A and the binder are added thereto, mixed and crushed to obtain a mixture 1; Step A2: Add white carbon black, the remaining disintegrant and deionized water to the mixture 1, crush it again, dry it and granulate it to obtain the defoaming active ingredient A.

[0013] Preferably, the preparation method of the defoaming active ingredient B is as follows: Step B1. Add β-cyclodextrin to a 50% by mass ethanol aqueous solution, heat and stir to obtain dispersion A, add the defoaming active ingredient A to the ethanol, stir evenly, then add dispersion A, stir at room temperature for 48-50 hours, centrifuge, and lyophilize to obtain the modified defoaming active ingredient A; Step B2. Sodium nitrite and sodium bisulfate were separately added to deionized water and stirred to obtain solution A and solution B. Solution A was heated to 88-93°C, solution B was added, and the pH of the system was adjusted to 8-8.5 with sodium hydroxide. After stirring for 2-3 hours, an aqueous sodium alginate solution was added dropwise and stirred at 40-47°C for 10-12 hours. The mixture was precipitated with ethanol, washed, and freeze-dried to obtain sulfonated sodium alginate. Step B3. Add sulfonated sodium alginate to deionized water, then add modified defoaming active ingredient A, stir for 2-3 hours to obtain a mixed solution, then spray the mixed solution into a 5% by mass calcium chloride solution, and freeze-dry to obtain defoaming active ingredient B.

[0014] Preferably, the ratio of the ethanol aqueous solution to β-cyclodextrin in step B1 is 30-40 mL: 1-1.3 g; The usage ratio of the defoaming active ingredient A, ethanol and dispersion A is 1-2 g: 24-46 mL: 35-65 mL; The temperature during the heating and stirring is 55-65°C and the time is 2.5-3.5h.

[0015] Preferably, the ratio of sodium nitrite to deionized water in step B2 is 0.5-0.8 g:15-24 mL; The dosage ratio of the sodium bisulfate and deionized water is 7-8 g:30-35 mL; The volume ratio of solution A, solution B and sodium alginate aqueous solution is 32-40:37-43:200-215; The ratio of sodium alginate to deionized water in the sodium alginate aqueous solution is 2-2.6:130-165 mL; The usage ratio of the sulfonated sodium alginate, deionized water, modified defoaming active ingredient A and calcium chloride solution in step B3 is 1.5-2 g: 150-200 mL: 1.1-1.6 g: 300-400 mL.

[0016] Preferably, the preparation method of the second composition is as follows: Step C1. The carrier, dispersant, and half of the disintegrant are mixed and then extruded, and the extrusion speed is controlled at 30-40 r / min and the extrusion speed is 4-6 kg / min. After molding, the mixture is dried, and the silicone composition B and the binder are added thereto. After mixing, the mixture is crushed to obtain a mixture 2; Step C2: adding white carbon black, the remaining disintegrant and deionized water to the mixture 2, crushing again, drying and granulating to obtain a second composition.

[0017] The preparation method of a self-dispersible powder defoamer comprises the following steps: The first composition and the second composition are mixed and stirred evenly to obtain a self-dispersible powder defoaming agent.

[0018] Beneficial effects of the present invention: The present invention provides a self-dispersible powder defoamer and a preparation method thereof. The present invention obtains a powder defoamer with high dispersibility and good defoaming and antifoaming performance by compounding a first composition and a second composition with different particle sizes. The first composition with a larger particle size is obtained by mixing a defoaming active substance A and a defoaming active substance B. The organosilicon composition A, a carrier, white carbon black and other additives are blended, crushed and granulated. The obtained defoaming active substance A is further encapsulated with beta-cyclodextrin and sulfonated sodium alginate to obtain a defoaming active substance B with sustained-release performance and hydrophilicity. Furthermore, while rapidly defoaming, the powder defoamer can also improve dispersibility and delay particle rupture, thereby achieving a defoaming effect. The second composition with a smaller particle size has a higher specific surface area, is easier to disperse in the system, disintegrates faster, and can exert a rapid defoaming effect. Compared with the existing technology, the present invention has broad application prospects. DETAILED DESCRIPTION

[0019] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to specific embodiments.

[0020] The sources and properties of some of the raw materials used in the present invention are as follows: β-Cyclodextrin was purchased from Shandong Dibeck Bioengineering Co., Ltd.; sodium alginate was purchased from Qingdao Haiweisen Biotechnology Co., Ltd.; silica was purchased from Shanghai Youci New Materials Co., Ltd.; dimethyl silicone oil was purchased from Jinan Hongli Chemical Co., Ltd.; and polysiloxane was purchased from Mairui Biochemical Technology Co., Ltd.

[0021] Example 1: A method for preparing a self-dispersible powder defoamer, comprising the following steps: S1. 26g of dimethyl silicone oil and 3.5g of silicone resin were placed in a reaction vessel, heated to 100 ° C and stirred, then cooled to 45 ° C and then 14g of polyoxyethylene polyoxypropylene pentaerythritol ether, 3g of polyoxyethylene polyoxypropylene propylene glycol ether, 55g of deionized water and 0.1g of sodium hydroxymethyl cellulose were added and mixed to obtain a silicone composition A; S2. After 22g of polysiloxane, 15gMQ resin, 0.2g of potassium hydroxide and 1.5g of dimethyl silicone oil were mixed, the temperature was raised and the reaction was heated, and then 1.9g of hydrophobic silica was added, the reaction was continued for 3h, and cooled to room temperature to obtain a silicone composition B; S3 50g sulfate, 1.3g polyethylene glycol, 1.1g sodium chloride were mixed and extruded, and the extrusion speed was controlled at 30r / min, the extrusion speed was 4Kg / min, and after drying, 14g of the silicone composition A and 4g of maleic acid acrylic acid copolymer were added thereto, mixed and crushed to obtain a mixture 1; S4 was added to the mixture 1 6.8g of white carbon black, 1.1g of sodium chloride and 7g of deionized water, crushed again, dried and granulated to obtain a defoaming active substance A; S5 50g sulfate, 1.3g polyethylene glycol, 1.1g sodium chloride were mixed and extruded, and the extrusion speed was controlled to 30r / min, the extrusion speed was 4Kg / min, and after drying, 14g of the silicone composition B and 4g of maleic acid acrylic acid copolymer were added thereto, mixed and crushed to obtain a mixture 2; S6 was added to the mixture 2 6.8g of white carbon black, 1.1g of sodium chloride and 7g of deionized water, crushed again, dried and granulated to obtain a second composition; S7. 1 g of β-cyclodextrin was added to 30 mL of a 50% ethanol aqueous solution, heated and stirred at 55 ° C for 2.5 h to obtain a dispersion A. 1 g of the defoaming active substance A was added to 35 mL of ethanol and stirred uniformly. Then, 35 mL of the dispersion A was added, stirred at room temperature for 48 h, centrifuged, and lyophilized to obtain a modified defoaming active substance A; S8. 0.5 g of sodium nitrite was added to 15 mL of deionized water and stirred to obtain solution A. 7 g of sodium bisulfate was added to 30 mL of deionized water and stirred to obtain solution B. 32 mL of solution A was heated to 88 ° C, 37 mL of solution B was added, and the pH of the system was adjusted to 8 with sodium hydroxide. After stirring for 2 h, 200 mL of sodium alginate aqueous solution was added dropwise, wherein the amount ratio of sodium alginate to deionized water in the sodium alginate aqueous solution was 2 g: 130 mL. The mixture was stirred at 40 ° C for 10 h, ethanol precipitated, washed, and freeze-dried to obtain sulfonated sodium alginate. S9. 1.5 g of sulfonated sodium alginate was added to 150 mL of deionized water, followed by 1.1 g of modified defoaming active ingredient A. The mixture was stirred for 2 h to obtain a mixture, which was then sprayed into 300 mL of a 5% calcium chloride solution and lyophilized to obtain defoaming active ingredient B. S10. 8 g of defoaming active ingredient A and 33 g of defoaming active ingredient B were mixed to obtain a first composition, and then 115 g of the first composition and 138 g of the second composition were mixed and stirred to obtain a self-dispersible powder defoaming agent.

[0022] Example 2: A method for preparing a self-dispersible powder defoamer, comprising the following steps: S1. 28g of dimethyl silicone oil and 4g of silicone resin were placed in a reaction vessel, heated to 105 ° C and stirred, then cooled to 50 ° C and then 17g of polyoxyethylene polyoxypropylene pentaerythritol ether, 3.7g of polyoxyethylene polyoxypropylene propylene glycol ether, 62g of deionized water and 0.2g of sodium hydroxymethyl cellulose were added, mixed uniformly to obtain a silicone composition A; S2. After 24 g of polysiloxane, 17 g of MQ resin, 0.3 g of potassium hydroxide and 1.8 g of dimethyl silicone oil were mixed, the temperature was raised and the reaction was heated, and then 2.1 g of hydrophobic silica was added, the reaction was continued for 4 h, and cooled to room temperature to obtain a silicone composition B; S3 57g starch, 1.5g polyvinyl pyrrolidone, 1.2g ammonium sulfate were mixed and extruded, and the extrusion speed was controlled to 35r / min, the extrusion speed was 5Kg / min, and after drying, 16g of the silicone composition A and 5g of polyacrylic acid were added thereto, mixed and crushed to obtain a mixture 1; S4 was added to the mixture 1 8g of white carbon black, 1.2g of ammonium sulfate and 8g of deionized water, crushed again, dried and granulated to obtain a defoaming active substance A; S5 57g starch, 1.5g polyvinyl pyrrolidone, 1.2g ammonium sulfate were mixed and extruded, and the extrusion speed was controlled to 35r / min, the extrusion speed was 5Kg / min, and after drying, 16g of the silicone composition B and 5g of polyacrylic acid were added thereto, mixed and crushed to obtain a mixture 2; S6 was added to the mixture 2 8g of white carbon black, 1.2g of ammonium sulfate and 8g of deionized water, crushed again, dried and granulated to obtain a second composition; S7. 1.1 g of β-cyclodextrin was added to 35 mL of a 50% ethanol aqueous solution, heated and stirred at 60 ° C for 3 h to obtain a dispersion A. 1.4 g of the defoaming active substance A was added to 45 mL of ethanol and stirred uniformly. Then, 45 mL of the dispersion A was added, stirred at room temperature for 49 h, centrifuged, and freeze-dried to obtain a modified defoaming active substance A; S8. 0.6 g of sodium nitrite was added to 18 mL of deionized water and stirred to obtain solution A. 7.4 g of sodium bisulfate was added to 32 mL of deionized water and stirred to obtain solution B. 35 mL of solution A was heated to 90 ° C, 39 mL of solution B was added, and the pH of the system was adjusted to 8 with sodium hydroxide. After stirring for 2.5 h, 205 mL of sodium alginate aqueous solution was added dropwise, wherein the amount ratio of sodium alginate to deionized water in the sodium alginate aqueous solution was 2.2 g: 140 mL. The mixture was stirred at 42 ° C for 11 h, precipitated with ethanol, washed, and freeze-dried to obtain sulfonated sodium alginate. S9. 1.7 g of sulfonated sodium alginate was added to 170 mL of deionized water, followed by 1.3 g of modified defoaming active ingredient A, and stirred for 2.5 h to obtain a mixture, which was then sprayed into 340 mL of a 5% calcium chloride solution and lyophilized to obtain defoaming active ingredient B; S10. 10 g of defoaming active ingredient A and 35 g of defoaming active ingredient B were mixed to obtain a first composition, and then 127 g of the first composition and 150 g of the second composition were mixed and stirred to obtain a self-dispersible powder defoaming agent.

[0023] Example 3: A method for preparing a self-dispersible powder defoaming agent, comprising the following steps: S1. 30g of dimethyl silicone oil and 4.5g of silicone resin were placed in a reaction vessel, heated to 105 ° C and stirred, then cooled to 55 ° C and then 19g of polyoxyethylene polyoxypropylene pentaerythritol ether, 4.4g of polyoxyethylene polyoxypropylene propylene glycol ether, 65g of deionized water and 0.3g of sodium hydroxymethyl cellulose were added, mixed uniformly to obtain a silicone composition A; S2. After 27g of polysiloxane, 19gMQ resin, 0.33g of potassium hydroxide and 2g of dimethyl silicone oil were mixed, the temperature was raised and the reaction was heated, and then 2.1g of hydrophobic silica was added, the reaction was continued for 4.5h, and cooled to room temperature to obtain a silicone composition B; S3 62g cellulose, 1.7g polymaleic anhydride, 1.35g urea were mixed and extruded, and the extrusion speed was controlled to 35r / min, the extrusion speed was 5Kg / min, and after drying, 17g of the silicone composition A and 6g of citric acid were added thereto, mixed and crushed to obtain a mixture 1; S4 was added to the mixture 1 9g of white carbon black, 1.35g of urea and 10g of deionized water, crushed again, dried and granulated to obtain a defoaming active substance A; S5 62g cellulose, 1.7g polymaleic anhydride, 1.35g urea were mixed and extruded, and the extrusion speed was controlled to 35r / min, the extrusion speed was 5Kg / min, and after drying, 17g of the silicone composition B and 6g of citric acid were added thereto, mixed and crushed to obtain a mixture 2; S6 was added to the mixture 2 9g of white carbon black, 1.35g of urea and 10g of deionized water, crushed again, dried and granulated to obtain a second composition; S7. 1.2 g of β-cyclodextrin was added to 37 mL of a 50% ethanol aqueous solution, heated and stirred at 60 ° C for 3 h to obtain a dispersion A. 1.7 g of the defoaming active substance A was added to 55 mL of ethanol and stirred uniformly. Then, 55 mL of the dispersion A was added, stirred at room temperature for 49 h, centrifuged, and lyophilized to obtain a modified defoaming active substance A; S8. 0.7 g of sodium nitrite was added to 20 mL of deionized water and stirred to obtain solution A. 7.7 g of sodium bisulfate was added to 33 mL of deionized water and stirred to obtain solution B. 38 mL of solution A was heated to 90 ° C, 41 mL of solution B was added, and the pH of the system was adjusted to 8.5 with sodium hydroxide. After stirring for 3 h, 210 mL of sodium alginate aqueous solution was added dropwise, wherein the amount ratio of sodium alginate to deionized water in the sodium alginate aqueous solution was 2.4 g: 150 mL. The mixture was stirred at 45 ° C for 12 h, precipitated with ethanol, washed, and freeze-dried to obtain sulfonated sodium alginate. S9. 1.8 g of sulfonated sodium alginate was added to 180 mL of deionized water, followed by 1.5 g of modified defoaming active ingredient A, and stirred for 2-3 h to obtain a mixture, which was then sprayed into 370 mL of a 5% calcium chloride solution and lyophilized to obtain defoaming active ingredient B; S10. 12 g of defoaming active ingredient A and 38 g of defoaming active ingredient B were mixed to obtain a first composition, and then 130 g of the first composition and 162 g of the second composition were mixed and stirred to obtain a self-dispersible powder defoaming agent.

[0024] Example 4: A method for preparing a self-dispersible powder defoaming agent, comprising the following steps: S1. 33g of dimethyl silicone oil and 5g of silicone resin were placed in a reaction vessel, heated to 110 ° C and stirred, then cooled to 55 ° C and then 22g of polyoxyethylene polyoxypropylene pentaerythritol ether, 5g of polyoxyethylene polyoxypropylene propylene glycol ether, 70g of deionized water and 0.4g of sodium hydroxymethyl cellulose were added and mixed to obtain a silicone composition A; S2. After 30g of polysiloxane, 20gMQ resin, 0.4g of potassium hydroxide and 2.3g of dimethyl silicone oil were mixed, the temperature was raised and the reaction was heated, and then 2.5g of hydrophobic silica was added, the reaction was continued for 5h, and cooled to room temperature to obtain a silicone composition B; S3 70g sulfate, 2g polyethylene glycol, 1.5g sodium chloride were mixed and extruded, and the extrusion speed was controlled at 40r / min, the extrusion speed was 6Kg / min, and after drying, 18g of the silicone composition A and 7g of maleic acid acrylic acid copolymer were added thereto, mixed and crushed to obtain a mixture 1; S4 was added to the mixture 10g of white carbon black, 1.5g of sodium chloride and 11g of deionized water, crushed again, dried and granulated to obtain a defoaming active substance A; S5 70g sulfate, 2g polyethylene glycol, 1.5g sodium chloride were mixed and extruded, and the extrusion speed was controlled to 40r / min, the extrusion speed was 6Kg / min, and after drying, 18g of the silicone composition A and 7g of maleic acid acrylic acid copolymer were added thereto, mixed and crushed to obtain a mixture 2; S6 was added to the mixture 2 10g of white carbon black, 1.5g of sodium chloride and 11g of deionized water, crushed again, dried and granulated to obtain a second composition; S7. 1.3 g of β-cyclodextrin was added to 40 mL of a 50% ethanol aqueous solution, heated and stirred at 65 ° C for 3.5 h to obtain a dispersion A. 2 g of the defoaming active substance A was added to 65 mL of ethanol and stirred uniformly. Then, 65 mL of the dispersion A was added and stirred at room temperature for 50 h. The mixture was centrifuged and freeze-dried to obtain a modified defoaming active substance A. S8. 0.8 g of sodium nitrite was added to 24 mL of deionized water and stirred to obtain solution A. 8 g of sodium bisulfate was added to 35 mL of deionized water and stirred to obtain solution B. 40 mL of solution A was heated to 93 ° C, 43 mL of solution B was added, and the pH of the system was adjusted to 8.5 with sodium hydroxide. After stirring for 3 h, 215 mL of sodium alginate aqueous solution was added dropwise, wherein the amount ratio of sodium alginate to deionized water in the sodium alginate aqueous solution was 2.6 g: 165 mL. The mixture was stirred at 47 ° C for 12 h, precipitated with ethanol, washed, and freeze-dried to obtain sulfonated sodium alginate. S9. 2 g of sulfonated sodium alginate was added to 200 mL of deionized water, followed by 1.6 g of modified defoaming active ingredient A, and stirred for 3 h to obtain a mixture, which was then sprayed into 400 mL of a 5% calcium chloride solution and lyophilized to obtain defoaming active ingredient B; S10. 14.5 g of defoaming active ingredient A and 40 g of defoaming active ingredient B were mixed to obtain a first composition, and then 140 g of the first composition and 175 g of the second composition were mixed and stirred to obtain a self-dispersible powder defoaming agent.

[0025] Comparative Example 1: Compared with Example 1, the first composition was not added during the preparation of the defoaming agent in this comparative example. The remaining steps and parameters were the same and will not be repeated in this comparative example. Finally, a defoaming agent was obtained.

[0026] Comparative Example 2: Compared with Example 1, the second composition was not added during the preparation of the defoaming agent in this comparative example. The remaining steps and parameters were the same and will not be repeated in this comparative example. Finally, a defoaming agent was obtained.

[0027] Comparative Example 3: Compared with Example 1, the defoaming active ingredient A was not added during the preparation of the first composition in this comparative example. The remaining steps and parameters were the same and will not be repeated in this comparative example. Finally, a defoaming agent was obtained.

[0028] Comparative Example 4: Compared with Example 1, the defoaming active ingredient B was not added during the preparation of the first composition. The remaining steps and parameters were the same and will not be repeated in this comparative example. Finally, a defoaming agent was obtained.

[0029] Comparative Example 5: Compared with Example 1, this comparative example only replaces the "organic silicon composition A" with the "organic silicon composition B", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a defoaming agent is obtained.

[0030] Comparative Example 6: Compared with Example 1, this comparative example only replaces the "organic silicon composition B" with the "organic silicon composition A", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a defoaming agent is obtained.

[0031] Comparative Example 7: Compared with Example 1, this comparative example only replaced "8 g of defoaming active ingredient A and 33 g of defoaming active ingredient B" with "8 g of defoaming active ingredient A and 8 g of defoaming active ingredient B". The remaining steps and parameters were the same and will not be repeated in this comparative example. Finally, a defoaming agent was obtained.

[0032] Comparative Example 8: Compared with Example 1, this comparative example only replaced "8 g of defoaming active ingredient A and 33 g of defoaming active ingredient B" with "33 g of defoaming active ingredient A and 8 g of defoaming active ingredient B". The remaining steps and parameters were the same and will not be repeated in this comparative example. Finally, a defoaming agent was obtained.

[0033] Comparative Example 9: Compared with Example 1, this comparative example only replaces "115g of the first composition and 138g of the second composition" with "115g of the first composition and 115g of the second composition", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a defoaming agent is obtained.

[0034] Comparative Example 10: Compared with Example 1, this comparative example only replaces "115g of the first composition and 138g of the second composition" with "138g of the first composition and 115g of the second composition", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a defoaming agent is obtained.

[0035] Comparative Example 11: Compared with Example 1, this comparative example only replaces the "defoaming active ingredient B" with the "modified defoaming active ingredient A", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a defoaming agent is obtained.

[0036] Comparative Example 12: S1. 26g of dimethyl silicone oil and 3.5g of silicone resin were placed in a reaction vessel, heated to 100 ° C and stirred, then cooled to 45 ° C and then 14g of polyoxyethylene polyoxypropylene pentaerythritol ether, 3g of polyoxyethylene polyoxypropylene propylene glycol ether, 55g of deionized water and 0.1g of sodium hydroxymethyl cellulose were added and mixed to obtain a silicone composition A; S2 22g of polysiloxane, 15gMQ resin, 0.2g of potassium hydroxide and 1.5g of dimethyl silicone oil were mixed and heated to react, and then 1.9g of hydrophobic silica was added, and the reaction was continued for 3-5h and cooled to room temperature to obtain a silicone composition B; S3 50g sulfate, 1.3g polyethylene glycol, 1.1g sodium chloride were mixed and extruded, and the extrusion speed was controlled at 30r / min, the extrusion speed was 4Kg / min, and after drying, 14g of the silicone composition A and 4g of maleic acid acrylic acid copolymer were added thereto, mixed and crushed to obtain a mixture 1; S4 was added to the mixture 1 6.8g of white carbon black, 1.1g of sodium chloride and 7g of deionized water, crushed again, dried and granulated to obtain a defoaming active substance A; S5 50g sulfate, 1.3g polyethylene glycol, 1.1g sodium chloride were mixed and extruded, and the extrusion speed was controlled to 30r / min, the extrusion speed was 4Kg / min, and after drying, 14g of the silicone composition B and 4g of maleic acid acrylic acid copolymer were added thereto, mixed and crushed to obtain a mixture 2; S6 was added to the mixture 2 6.8g of white carbon black, 1.1g of sodium chloride and 7g of deionized water, crushed again, dried and granulated to obtain a second composition; S7. 0.5 g of sodium nitrite was added to 15 mL of deionized water and stirred to obtain solution A. 7 g of sodium bisulfate was added to 30 mL of deionized water and stirred to obtain solution B. 32 mL of solution A was heated to 88 ° C, 37 mL of solution B was added, and the pH of the system was adjusted to 8 with sodium hydroxide. After stirring for 2 h, 200 mL of sodium alginate aqueous solution was added dropwise, wherein the amount ratio of sodium alginate to deionized water in the sodium alginate aqueous solution was 2 g: 130 mL. The mixture was stirred at 40 ° C for 10 h, precipitated with ethanol, washed, and freeze-dried to obtain sulfonated sodium alginate. S8. 1.5 g of sulfonated sodium alginate was added to 150 mL of deionized water, followed by 1.1 g of defoaming active ingredient A. The mixture was stirred for 2 h to obtain a mixture, which was then sprayed into 300 mL of a 5% calcium chloride solution and lyophilized to obtain defoaming active ingredient B. S9. 8 g of defoaming active substance A and 33 g of defoaming active substance B were mixed to obtain a first composition, and then 115 g of the first composition and 138 g of the second composition were mixed and stirred to obtain a self-dispersible powder defoaming agent.

[0037] Performance testing: Anti-foaming performance test: The test was conducted using a portable defoamer performance tester, and the glass test mirror of the portable defoamer performance tester was marked with 11 scales, which were marked as 0, 10, 20...100, in sequence, where 0 is the starting point, indicating no foam; and 100 indicates full foam. 600 g of a 0.1% non-ionic aqueous solution was added to the portable defoamer performance tester, and 0.05 g of the defoamers prepared in Examples 1-4 and Comparative Examples 1-12 were added thereto, respectively. The temperature control switch was then turned on, and the foaming liquid was heated to the test temperature of 50°C. The air pump was turned on, and the foam was recorded every 2-5 minutes. The smaller the value, the less foam there was in the circulating bubbling, and the better the defoaming and anti-foaming properties. Dispersibility: 0.05 g of the defoaming agents prepared in Examples 1 to 4 and Comparative Examples 1 to 12 were poured into 100 mL of a 0.1% non-ionic aqueous solution, and the different defoaming agents were observed for 0, 10 min, 30 min, and 1 h after standing. The absence of stratification and precipitation was recorded as A, indicating excellent dispersion performance; a small amount of stratification or precipitation was recorded as B, indicating general dispersion performance; and obvious stratification or precipitation was recorded as C, indicating poor dispersibility.

[0038] Table 1

[0039] If the test time is "at that time", it means the test is done at that time; if the test time is "after aging", it means the sample is tested after being placed at a temperature of 40°C and a humidity of 70% for four weeks; Table 2

[0040] Data Analysis: As can be seen from Table 1 and Table 2, the defoaming agent prepared by the present invention has better foam elimination and suppression performance and better dispersibility. This may be because the defoaming active substance A in the first composition, after the organic silicon composition A in its molecule is blended, crushed and granulated with the carrier, white carbon black and other auxiliary agents, the organic silicon composition A can be adsorbed on the surface of the carrier, and the auxiliary agents such as white carbon black can also wrap and adsorb it, playing the effect of anti-caking and slowing release; in the defoaming active substance B, the defoaming active substance A can be effectively loaded in the hydrophobic cavity of β-cyclodextrin, effectively improving its dispersibility and stability, and then cross-linked with sulfonated sodium alginate and calcium The sulfonic acid groups contained in the first and second compositions can form a physical barrier, and the sulfonic acid groups contained in the first and second compositions can also form hydrogen bonds with the hydroxyl groups in β-cyclodextrin, thereby strengthening the intermolecular force, improving the sustained-release performance of the defoaming active substance B, and effectively exerting the anti-foaming effect; the sulfonated sodium alginate has good water solubility and the negative charge on the molecular surface causes electrostatic repulsion between the particles, effectively improving the dispersibility of the defoaming active substance B; the second composition with a smaller particle size has a higher specific surface area, is easier to disperse in the system, disintegrates faster, and can exert a rapid defoaming effect; after the first composition and the second composition are compounded, while the dispersibility of the defoaming agent is improved, the defoaming and anti-foaming performance is also improved.

[0041] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Within the scope of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

[0042] The present invention is intended to cover all such substitutions, modifications and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A self-dispersible powder defoamer, characterized in that: Including the following raw materials by weight: 115-140 parts of the first composition; 138-175 parts of the second composition; The particle size of the first composition is 35-45 μm; The particle size of the second composition is 1-7 μm; The first composition is obtained by mixing the defoaming active ingredient A and the defoaming active ingredient B in a mass ratio of 8-14.5:33-40; The defoaming active ingredient A is prepared from the following raw materials in parts by weight: 50-70 parts of carrier; 1.3-2 parts of dispersant; 4-7 parts of binder; 14-18 parts of organosilicon composition A; 6.8-10 parts of white carbon black; 2.2-3 parts of disintegrant; 7-11 parts of deionized water; The defoaming active ingredient B is prepared from the defoaming active ingredient A, β-cyclodextrin and sulfonated sodium alginate; The second composition is prepared from the following raw materials in parts by weight: 50-70 parts of carrier; 1.3-2 parts of dispersant; 4-7 parts of binder; 14-18 parts of organosilicon composition B; 6.8-10 parts of white carbon black; 2.2-3 parts of disintegrant; and 7-11 parts of deionized water.

2. The self-dispersible powder defoamer according to claim 1, characterized in that The carrier is at least one of sulfate, carbonate, phosphate, polyphosphate, starch, cellulose and aluminosilicate; The average molecular weight of the dispersant is 1000-3000; The dispersant is any one of polyethylene glycol, polyvinyl alcohol, polyethyleneimine, polymaleic anhydride, polyacrylamide, polyacrylate, polyvinyl pyrrolidone and polyquaternary ammonium salt; The adhesive is any one of maleic acid acrylic acid copolymer, polymaleic acid, polyacrylic acid, alkylbenzene sulfonic acid, tartaric acid, oxalic acid, malic acid and citric acid; The disintegrant is any one of sodium chloride, sodium sulfate, ammonium sulfate, sodium carbonate and urea.

3. The self-dispersible powder defoamer according to claim 1, characterized in that The preparation method of the organosilicon composition A is as follows: Dimethyl silicone oil and silicone resin are placed in a reaction kettle, heated to 100-110° C. and stirred evenly, then cooled to 45-55° C. and polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene propylene glycol ether, deionized water and sodium hydroxymethyl cellulose are added in sequence, and mixed evenly to obtain an organosilicon composition A; The mass ratio of the dimethyl silicone oil, silicone resin, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene propylene glycol ether, deionized water and sodium hydroxymethyl cellulose is 26-33:3.5-5:14-22:3-5:55-70:0.1-0.

4.

4. The self-dispersible powder defoamer according to claim 1, characterized in that The preparation method of the organosilicon composition B is as follows: After mixing polysiloxane, MQ resin, potassium hydroxide and dimethyl silicone oil, heating and reacting, hydrophobic silica was added, and the reaction was continued for 3-5 hours, and then cooled to room temperature to obtain an organosilicon composition B; The mass ratio of the polysiloxane, MQ resin, potassium hydroxide, dimethyl silicone oil and hydrophobic silica is 22-30:15-20:0.2-0.4:1.5-2.3:1.9-2.5; The temperature during the heating reaction is 95-105°C and the time is 1-1.5h.

5. The self-dispersible powder defoamer according to claim 1, characterized in that The preparation method of the defoaming active ingredient A is as follows: Step A1. The carrier, dispersant, and half of the disintegrant are mixed and extruded, and the extrusion speed is controlled to 30-40 r / min and the extrusion speed is 4-6 kg / min. After molding, the silicone composition A and the binder are added thereto, mixed and crushed to obtain a mixture 1; Step A2: Add white carbon black, the remaining disintegrant and deionized water to the mixture 1, crush it again, dry it and granulate it to obtain the defoaming active ingredient A.

6. The self-dispersible powder defoamer according to claim 1, characterized in that: The preparation method of the defoaming active ingredient B is as follows: Step B1. Add β-cyclodextrin to a 50% by mass ethanol aqueous solution, heat and stir to obtain dispersion A, add the defoaming active ingredient A to the ethanol, stir evenly, then add dispersion A, stir at room temperature for 48-50 hours, centrifuge, and lyophilize to obtain the modified defoaming active ingredient A; Step B2. Sodium nitrite and sodium bisulfate were separately added to deionized water and stirred to obtain solution A and solution B. Solution A was heated to 88-93°C, solution B was added, and the pH of the system was adjusted to 8-8.5 with sodium hydroxide. After stirring for 2-3 hours, an aqueous sodium alginate solution was added dropwise and stirred at 40-47°C for 10-12 hours. The mixture was precipitated with ethanol, washed, and freeze-dried to obtain sulfonated sodium alginate. Step B3. Add sulfonated sodium alginate to deionized water, then add modified defoaming active ingredient A, stir for 2-3 hours to obtain a mixed solution, then spray the mixed solution into a 5% by mass calcium chloride solution, and freeze-dry to obtain defoaming active ingredient B.

7. The self-dispersible powder defoamer according to claim 6, characterized in that: The ratio of the ethanol aqueous solution to β-cyclodextrin in step B1 is 30-40 mL: 1-1.3 g; The usage ratio of the defoaming active ingredient A, ethanol and dispersion A is 1-2 g: 24-46 mL: 35-65 mL; The temperature during the heating and stirring is 55-65°C and the time is 2.5-3.5h.

8. The self-dispersible powder defoamer according to claim 6, characterized in that: The ratio of sodium nitrite to deionized water in step B2 is 0.5-0.8 g:15-24 mL; The dosage ratio of the sodium bisulfate and deionized water is 7-8 g:30-35 mL; The volume ratio of solution A, solution B and sodium alginate aqueous solution is 32-40:37-43:200-215; The ratio of sodium alginate to deionized water in the sodium alginate aqueous solution is 2-2.6:130-165 mL; The usage ratio of the sulfonated sodium alginate, deionized water, modified defoaming active ingredient A and calcium chloride solution in step B3 is 1.5-2 g: 150-200 mL: 1.1-1.6 g: 300-400 mL.

9. The self-dispersible powder defoamer according to claim 1, characterized in that: The preparation method of the second composition is as follows: Step C1. The carrier, dispersant, and half of the disintegrant are mixed and then extruded, and the extrusion speed is controlled at 30-40 r / min and the extrusion speed is 4-6 kg / min. After molding, the mixture is dried, and the silicone composition B and the binder are added thereto. After mixing, the mixture is crushed to obtain a mixture 2; Step C2: adding white carbon black, the remaining disintegrant and deionized water to the mixture 2, crushing again, drying and granulating to obtain a second composition.

10. The method for preparing the self-dispersible powder defoaming agent according to any one of claims 1 to 9, characterized in that: The following steps are involved: The first composition and the second composition are mixed and stirred evenly to obtain a self-dispersible powder defoaming agent.

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