Preparation method of bio-based defoaming composition
By preparing a bio-based defoaming composition containing castor oil polyoxyethylene ether-organosilicon copolymer, silica dispersion and catalyst, the problem of difficulty in balancing compatibility and defoaming properties is solved, achieving good defoaming performance and compatibility, and making it suitable for industrial applications such as water-based coatings.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NANJING RUISI CHEM TECH CO LTD
- Filing Date
- 2024-11-14
- Publication Date
- 2026-05-15
AI Technical Summary
Existing bio-based defoaming compositions struggle to balance compatibility and defoaming performance, resulting in poor performance in practical applications.
A bio-based defoaming composition was prepared by using castor oil polyoxyethylene ether-organosilicon copolymer, silica dispersion and catalyst, combined with high and low melting point waxes and mono- and tri-functional surfactants, to achieve a balance between defoaming performance and compatibility.
The prepared bio-based defoaming composition exhibits good defoaming properties and compatibility when used in small quantities, making it suitable for industrial applications such as water-based coatings.
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Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing a bio-based defoaming composition, and more precisely, to a method for preparing a green, environmentally friendly, renewable, biodegradable, compatible, and defoaming-effective bio-based defoaming composition, belonging to the field of fine chemical formulation technology. Background Technology
[0002] In industrial production and construction, many processes utilize various surfactants for dispersion, wetting, and cleaning, resulting in the generation of substantial amounts of stable foam that is difficult to defoam using mechanical methods. In the actual production and application of water-based coatings, the addition of mineral oil-based defoamers offers significant advantages over other types of defoamers (including silicone oils, polyethers, and fatty alcohols) while simultaneously meeting defoaming and compatibility requirements. Furthermore, mineral oil defoamers are significantly cheaper and are therefore widely used.
[0003] Following the introduction of the Food Safety Law, related industries have gradually imposed strict restrictions on the content of residues such as organic hydrocarbons. This has necessitated the search for oil-phase or defoamer formulations that can replace mineral oil as a carrier to meet environmental and safety requirements. There has also been some research on bio-based defoaming compositions. Patent CN102027077A describes a silicone-free defoamer of a polyalkyl vinyl ether graft copolymer, exhibiting good defoaming performance in a wide range of coating systems such as alkyd resins, transparent coatings, synthetic fatty acids, and (meth)acrylic acid. Patent CN104120624A describes an emulsion-type defoamer prepared using a biological carrier as the defoaming active ingredient. Patent CN104307215A describes a vegetable oil-modified defoamer and its preparation method, using epoxidized vegetable oil, saturated fatty monohydric alcohol, ethylene oxide, and propylene oxide as raw materials, undergoing a ring-opening polymerization reaction under the action of a catalyst to obtain a vegetable oil-modified defoamer, thereby reducing... Low dependence on petroleum products; Patent CN104606926A describes a siloxane-modified vegetable oil polymer polyether defoamer, which improves the shortcomings of vegetable oil defoamers such as poor hydrophilicity and low foam breaking rate. It has stable emulsion performance, good water dispersibility, and is non-toxic and physiologically inactive, providing a new approach for the synthesis of green and environmentally friendly defoamers; Patent CN105983252A describes a vegetable oil-based defoamer prepared using vegetable oil, defoaming substances, defoaming aids, and emulsifiers; Patent CN110327665A describes a synthesis method through copolymerization of vegetable oil raw materials, and introduces nanomaterial groups to change the polymer structure. It does not use traditional emulsifiers, formaldehyde, silicone oil, and other harmful substances, improving versatility and weather resistance.
[0004] The aforementioned patent utilizes a biomass carrier to replace mineral oil to meet the requirements of environmental protection and biodegradability. It then improves the defoaming performance of the defoamer in the application system by adding various defoaming aids. However, due to the significant structural differences between biomass carriers and mineral oil, traditional formulation processes often require the addition of large amounts of defoaming aids to achieve the desired defoaming performance. Excessive amounts of defoaming aids can negatively impact the system's compatibility, making it difficult to achieve a balance between compatibility and defoaming performance in bio-based defoaming compositions.
[0005] Through extensive experimental research, the inventors of this patent have introduced an antifoaming active ingredient, prepared from castor oil polyoxyethylene ether-organosilicon copolymer, silica dispersion, and catalyst, into a biomass carrier. By combining high and low melting point waxes and utilizing the synergistic effect of monofunctional and trifunctional surfactants, a bio-based antifoaming composition was prepared. This bio-based antifoaming composition features low dosage, good compatibility, and excellent defoaming properties. Summary of the Invention
[0006] The purpose of this invention is to provide a method for preparing a bio-based defoaming composition, which solves the problem that the compatibility and defoaming properties of defoaming compositions prepared by existing technologies cannot be simultaneously achieved in practical use.
[0007] The raw materials used to prepare the bio-based defoaming composition include: (A) a biomass carrier, (B) an antifoaming active substance, (C) a biowax, and (D) a bio-based surfactant.
[0008] A. Biomass carrier
[0009] The biomass carrier refers to vegetable oil esters, animal oil esters, and fatty acid methyl esters or ethyl esters formed by transesterification of lower alcohols such as methanol and ethanol obtained by bio-fermentation.
[0010] The plant oil esters mentioned include sunflower seed oil, peanut oil, soybean oil, flaxseed oil, castor oil, rapeseed oil, and cottonseed oil.
[0011] The animal fats mentioned include fish oil, lard, beef tallow, and mutton tallow.
[0012] The amount of the biomass carrier used is 80-90% of the total mass of the bio-based defoaming composition.
[0013] B. Defoaming active ingredients
[0014] The defoaming active ingredient in the bio-based defoaming composition plays a role in demonstrating defoaming performance. The defoaming active ingredient is prepared from castor oil polyoxyethylene ether-organosilicon copolymer B1, silica dispersion B2, and catalyst B3.
[0015] B1, Castor oil polyoxyethylene ether-organosilicon copolymer
[0016] The castor oil polyoxyethylene ether-organosilicon copolymer is formed by castor oil polyoxyethylene ether and hydrogen-containing silicone oil under the catalysis of metallic bismuth.
[0017] The required mass fractions of raw materials for preparing castor oil polyoxyethylene ether-organosilicon copolymer are:
[0018] Castor oil polyoxyethylene ether: 40-70%;
[0019] Hydrogen-containing silicone oil: 40-65%;
[0020] Bismuth metal catalyst: 0.05–0.5%;
[0021] The sum of the mass percentages of the three substances is 100%.
[0022] The degree of polymerization of ethylene oxide in the castor oil polyoxyethylene ether is 2 to 20.
[0023] The hydrogen-containing silicone oil has a dynamic viscosity of 5–40 mPa·s at 25°C and a hydrogen content of 0.05–0.3%.
[0024] The preparation method of the castor oil polyoxyethylene ether-organosilicon copolymer is as follows:
[0025] Under nitrogen protection, castor oil polyoxyethylene ether and bismuth catalyst are added to a container, stirring is started and the temperature is raised to 70-150°C. The reaction temperature is maintained, and end-hydrogen-containing silicone oil is added dropwise at a uniform rate over 30-90 minutes. After the addition is completed, the temperature is maintained for 1-3 hours and then cooled to room temperature to obtain castor oil polyoxyethylene ether-organosilicon copolymer.
[0026] The amount of castor oil polyoxyethylene ether-organosilicon copolymer used is 70-95% of the total mass of the defoaming active material.
[0027] B2, Silica Dispersion
[0028] The silica in the bio-based defoaming composition improves defoaming properties and enhances stability.
[0029] The silica mentioned is hydrophobic silica, meaning it is produced by reacting certain chemicals with the hydroxyl groups on the silica surface through a specific process, thereby eliminating or reducing the amount of silanol groups on the surface, thus changing the silica surface from hydrophilic to hydrophobic. Commonly used chemical modification methods include: active silanes (such as chlorosilanes or hexamethyldisilazane), alcohol modification, and polymer grafting. The modified silica is hydrophobic and cannot be dispersed in water.
[0030] The method for preparing the silica dispersion is as follows: 80-99 parts of treatment agent and 1-20 parts of hydrophilic silica are added to a container, and the mixture is kept at 60-150℃ for 2-5 hours under nitrogen protection using a ball mill.
[0031] The hydrophobic treatment agent is castor oil, or methyl castor oil, or ethyl castor oil, and the specific surface area of the silica is 50-200 m². 2 / g.
[0032] The amount of the silica dispersion is 4-20% of the total mass of the defoaming active material.
[0033] B3, Catalyst
[0034] The catalyst is a weak base catalyst, including one or more of potassium laurate, sodium laurate, sodium stearate, potassium stearate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, cesium carbonate, monoethanolamine, diethanolamine, triethanolamine, and ammonium bicarbonate.
[0035] The amount of catalyst used is 0.1% to 2% of the total mass of the defoaming active material.
[0036] The method for preparing the defoaming active substance is as follows: castor oil polyoxyethylene ether-organosilicon copolymer is added to a container, and silica dispersion and catalyst are added while stirring is started and the speed is maintained at 500-3000 rpm. The temperature is raised to 80-160℃ and kept at that temperature for 1-5 hours. Finally, the defoaming active substance is obtained by homogenization using a homogenizer.
[0037] The amount of the defoaming active substance used is 5-10% of the bio-based defoaming composition.
[0038] C. Biowax
[0039] The main function of the bio-wax in the bio-based defoaming composition is to improve dispersibility and stability.
[0040] The biological waxes include animal and plant waxes and ester waxes formed from higher fatty acids and higher fatty alcohols; animal waxes include beeswax, insect wax, shellac wax, whale wax, and wool wax; plant waxes include carnauba wax, candelilla wax, sugarcane wax, lacquer wax, etc.
[0041] The biowax is a mixture of materials with melting points less than 40°C and greater than 80°C, with a mass ratio of m(melting point less than 40°C):m(melting point greater than 70°C) = 1:9 to 3:7.
[0042] The amount of the bio-wax used is 2-10% of the total mass of the bio-based defoaming composition.
[0043] D. Bio-based surfactants
[0044] The bio-based surfactant refers to a surfactant obtained by incorporating ethylene oxide and / or propylene oxide with natural fatty alcohols or natural fatty acids containing hydroxyl or ester groups as initiators and with potassium hydroxide as a catalyst.
[0045] The bio-based surfactants include:
[0046] Laurate polyoxyethylene ether, laurate polyoxyethylene polyoxypropylene ether, myristic acid polyoxyethylene ether, myristic acid polyoxyethylene polyoxypropylene ether, palmitic acid polyoxyethylene ether, palmitic acid polyoxyethylene polyoxypropylene ether, stearic acid polyoxyethylene ether, stearic acid polyoxyethylene polyoxypropylene ether, oleic acid polyoxyethylene ether, oleic acid polyoxyethylene polyoxypropylene ether, arachidic acid polyoxyethylene ether, arachidic acid polyoxyethylene polyoxypropylene ether, castor oil polyoxyethylene ether, castor oil polyoxyethylene polyoxypropylene ether, methyl laurate polyoxyethylene ether, methyl laurate polyoxyethylene polyoxypropylene ether, ethyl laurate polyoxyethylene polyoxyethylene ether, methyl laurate polyoxyethylene polyoxypropylene ether, methyl laurate polyoxyethylene polyoxyethylene ether, methyl laurate polyoxyethylene polyoxypropylene ether, ethyl laurate polyoxyethylene polyoxyethylene polyoxypropylene ether Methyl palmitate polyoxyethylene ether, methyl palmitate polyoxyethylene polyoxypropylene ether, ethyl palmitate polyoxyethylene ether, ethyl palmitate polyoxyethylene polyoxypropylene ether, methyl stearate polyoxyethylene polyoxypropylene ether, methyl stearate polyoxyethylene polyoxyethylene ether, ethyl stearate polyoxyethylene polyoxyethylene ether, ethyl stearate polyoxyethylene polyoxypropylene ether, methyl oleate polyoxyethylene ether, methyl oleate polyoxyethylene polyoxypropylene ether, ethyl oleate polyoxyethylene polyoxyethylene ether, methyl oleate polyoxyethylene polyoxypropylene ether, methyl arachidate polyoxyethylene ether, methyl arachidate polyoxyethylene polyoxypropylene ether, ethyl arachidate polyoxyethylene polyoxyethylene ether, methyl castor oil polyoxyethylene ether, methyl castor oil polyoxyethylene polyoxypropylene ether, ethyl castor oil polyoxyethylene ether, ethyl castor oil polyoxyethylene polyoxypropylene ether.
[0047] The bio-based surfactant is a mixture of monofunctional and trifunctional surfactants, with a mass ratio of 10-20% to 80-90%.
[0048] The amount of the bio-based surfactant used is 2-8% of the total mass of the bio-based defoaming composition.
[0049] The preparation method of the bio-based defoaming composition is as follows:
[0050] At room temperature, add biomass carrier, defoaming active substance and biowax to a container, start stirring, control the speed at 1000-3000 rpm, raise the temperature to 100-150℃ and keep it at that temperature for 0.5-2 hours, then keep the same speed, add bio-based surfactant and cool down to room temperature within 1-3 hours, age at room temperature for 8-16 hours, and finally grind it with a ball mill to obtain the bio-based defoaming composition.
[0051] Specific implementation
[0052] Example 1
[0053] Preparation of castor oil polyoxyethylene ether-organosilicon copolymer B1-1:
[0054] Under nitrogen protection, 40 parts of castor oil polyoxyethylene ether (degree of polymerization 3) and 0.05 parts of bismuth trioxide catalyst were added to a container. Stirring was started and the temperature was raised to 75°C. The reaction temperature was maintained, and 59.95 parts of hydrogen-terminated silicone oil (hydrogen content of 0.75%, dynamic viscosity of 7 mPa·s at 25°C) were added dropwise at a uniform rate over 60 min. After the addition was completed, the temperature was maintained for another 3 h and then cooled to room temperature to obtain castor oil polyoxyethylene ether-organosilicon copolymer B1-1.
[0055] Example 2
[0056] Preparation of castor oil polyoxyethylene ether-organosilicon copolymer B1-2:
[0057] Under nitrogen protection, 31 parts of castor oil polyoxyethylene ether (degree of polymerization 18) and 0.2 parts of sodium bismuthate catalyst were added to a container. Stirring was started and the temperature was raised to 105°C. The reaction temperature was maintained, and 68.8 parts of hydrogen-terminated silicone oil (hydrogen content of 0.27%, dynamic viscosity of 38 mPa·s at 25°C) were added dropwise at a uniform rate over 90 min. After the addition was completed, the temperature was maintained for 1.5 h and then cooled to room temperature to obtain castor oil polyoxyethylene ether-organosilicon copolymer B1-2.
[0058] Example 3
[0059] Preparation of castor oil polyoxyethylene ether-organosilicon copolymer B1-3:
[0060] Under nitrogen protection, 69 parts of castor oil polyoxyethylene ether (degree of polymerization 10) and 0.5 parts of sodium bismuthate catalyst were added to a container. Stirring was started and the temperature was raised to 150°C. The reaction temperature was maintained, and 30.5 parts of hydrogen-terminated silicone oil (hydrogen content of 0.16%, dynamic viscosity of 24 mPa·s at 25°C) were added dropwise at a uniform rate over 30 min. After the addition was completed, the temperature was maintained for another 1 h and then cooled to room temperature to obtain castor oil polyoxyethylene ether-organosilicon copolymer B1-3.
[0061] Example 4
[0062] Preparation of castor oil polyoxyethylene ether-organosilicon copolymer B1-4:
[0063] Under nitrogen protection, 55 parts of castor oil polyoxyethylene ether (degree of polymerization 14) and 0.5 parts of bismuth trioxide catalyst were added to a container. Stirring was started and the temperature was raised to 116°C. The reaction temperature was maintained, and 44.5 parts of hydrogen-terminated silicone oil (hydrogen content of 0.13%, dynamic viscosity of 18 mPa·s at 25°C) were added dropwise at a uniform rate over 45 min. After the addition was completed, the temperature was maintained for another 2 h and then cooled to room temperature to obtain castor oil polyoxyethylene ether-organosilicon copolymer B1-4.
[0064] Example 5
[0065] Preparation of castor oil polyoxyethylene ether-organosilicon copolymer B1-5:
[0066] Under nitrogen protection, 43 parts of castor oil polyoxyethylene ether (degree of polymerization 16) and 0.1 parts of bismuth trioxide catalyst were added to a container. Stirring was started and the temperature was raised to 135°C. The reaction temperature was maintained, and 56.9 parts of hydrogen-terminated silicone oil (hydrogen content of 0.22%, dynamic viscosity of 36 mPa·s at 25°C) were added dropwise at a uniform rate over 65 min. After the addition was completed, the temperature was maintained for another 1.5 h and then cooled to room temperature to obtain castor oil polyoxyethylene ether-organosilicon copolymer B1-5.
[0067] Example 6
[0068] Preparation of silica dispersion B2:
[0069] The product is obtained by adding a treatment agent and hydrophilic precipitated silica to a container, and then maintaining the temperature at a certain time under nitrogen protection using a ball mill.
[0070] The process parameters selected during the preparation process are shown in Table 1 below:
[0071] Table 1. Parameter selection for preparing silica dispersion B2
[0072]
[0073] Example 7
[0074] Add 80 parts of castor oil polyoxyethylene ether-organosilicon copolymer B1-1 to a container, and add 19.9 parts of silica dispersion B2-1 and 0.1 parts of catalyst ammonium bicarbonate while stirring at 500 rpm. Raise the temperature to 80℃ and keep it at that temperature for 5 hours. Finally, homogenize the mixture to obtain the defoaming active substance BA.
[0075] Example 8
[0076] Add 95 parts of castor oil polyoxyethylene ether-organosilicon copolymer B1-4 to a container, and add 4 parts of silica dispersion B2-4 and 1 part of catalyst potassium laurate while stirring at 2500 rpm. Raise the temperature to 155℃ and keep it at that temperature for 3 hours. Finally, homogenize the mixture to obtain the defoaming active substance BB.
[0077] Example 9
[0078] Add 86 parts of castor oil polyoxyethylene ether-organosilicon copolymer B1-3 to a container, and add 12 parts of silica dispersion B2-3 and 2 parts of catalyst sodium carbonate while stirring at 3000 rpm. Raise the temperature to 105℃ and keep it at that temperature for 1 hour. Finally, homogenize the mixture using a homogenizer to obtain the defoaming active substance BC.
[0079] Example 10
[0080] Add 90 parts of castor oil polyoxyethylene ether-organosilicon copolymer B1-2 to a container, and add 9.5 parts of silica dispersion B2-2 and 0.5 parts of catalyst cesium carbonate while stirring at 1500 rpm. Raise the temperature to 120℃ and keep it at that temperature for 2.5 hours. Finally, homogenize the mixture to obtain the defoaming active substance BD.
[0081] Example 11
[0082] Add 88 parts of castor oil polyoxyethylene ether-organosilicon copolymer B1-5 to a container, and add 11.5 parts of silica dispersion B2-3 and 0.5 parts of catalyst cesium carbonate while stirring at 1800 rpm. Raise the temperature to 118℃ and keep it at that temperature for 1.5 hours. Finally, homogenize the mixture to obtain the defoaming active substance BE.
[0083] Example 12
[0084] At room temperature, add 80 parts of biomass carrier sunflower seed oil, 5 parts of defoaming active substance BB, 1 part of beeswax (melting point 30℃), and 9 parts of carnauba wax (melting point 75℃) to a container, start stirring, control the speed at 1100 rpm, raise the temperature to 132℃ and keep it warm for 1 hour, then keep the same speed, add 0.5 parts of lauric acid polyoxyethylene ether (5) and 4.5 parts of castor oil polyoxyethylene ether (10), and cool down to room temperature within 1 hour. Aging at room temperature for 8 hours, and finally grind with a ball mill to obtain the bio-based defoaming composition S1.
[0085] Example 13
[0086] Add 90 parts of biomass carrier soybean oil, 6 parts of defoaming active substance BC, 0.6 parts of lanolin wax (melting point 35℃), and 1.4 parts of stearyl octadecyl stearate (melting point 78℃) to a container at room temperature. Start stirring and control the speed at 3000 rpm. Raise the temperature to 103℃ and keep it at that temperature for 0.5 h. Then, while maintaining the same speed, add 0.4 parts of oleic acid polyoxyethylene ether (8) and 1.6 parts of castor oil polyoxyethylene ether (12). Cool the temperature to room temperature within 3 h and age it at room temperature for 16 h. Finally, grind the mixture in a ball mill to obtain the bio-based defoaming composition S2.
[0087] Example 14
[0088] At room temperature, add 80 parts of biomass carrier castor oil, 10 parts of defoaming active substance BA, 0.6 parts of lanolin wax (melting point 35℃), and 1.4 parts of docosahexadecyl stearate (melting point 85℃) to a container, start stirring, control the speed at 2500 rpm, raise the temperature to 148℃ and keep it at that temperature for 2 hours, then keep the same speed, add 1.2 parts of methyl palmitate polyoxyethylene ether (4) and 6.8 parts of castor oil polyoxyethylene ether (20), and cool down to room temperature within 1.5 hours. Aging at room temperature for 10 hours, and finally grind with a ball mill to obtain the bio-based defoaming composition S3.
[0089] Example 15
[0090] At room temperature, 85 parts of biomass carrier fatty acid methyl ester, 6 parts of defoaming active substance BD, 1 part of lacquer wax (melting point 30℃), and 4 parts of cetyl stearate (melting point 77℃) were added to a container. Stirring was started and the speed was controlled at 1800 rpm. The temperature was raised to 121℃ and kept at that temperature for 1.5 h. Then, while maintaining the same speed, 0.6 parts of castor oil methyl ester polyoxyethylene ether (6) and 3.4 parts of castor oil polyoxyethylene ether (14) were added. The temperature was then lowered to room temperature within 2 h and aged at room temperature for 12 h. Finally, the bio-based defoaming composition S4 was obtained by grinding with a ball mill.
[0091] Example 16
[0092] At room temperature, 87 parts of biomass carrier soybean oil, 7 parts of defoaming active substance BE, 0.3 parts of insect wax (melting point 33℃), and 2.7 parts of cetyl arachidate (melting point 83℃) were added to a container. Stirring was started and the speed was controlled at 1200 rpm. The temperature was raised to 116℃ and kept at that temperature for 2 hours. Then, while maintaining the same speed, 0.6 parts of methyl arachidate polyoxyethylene ether (9) and 2.4 parts of castor oil polyoxyethylene ether (40) were added. The temperature was then lowered to room temperature within 1.5 hours and aged at room temperature for 14 hours. Finally, the bio-based defoaming composition S5 was obtained by grinding with a ball mill.
[0093] Comparative Example 1:
[0094] At room temperature, 87 parts of biomass carrier soybean oil, 7 parts of defoaming active substance BE, and 3 parts of cetyl arachidonic acid ester (melting point 83℃) were added to a container. Stirring was started and the speed was controlled at 1200 rpm. The temperature was raised to 116℃ and kept at that temperature for 2 hours. Then, while maintaining the same speed, 0.6 parts of methyl arachidonic acid polyoxyethylene ether (9) and 2.4 parts of castor oil polyoxyethylene ether (40) were added. The temperature was then lowered to room temperature within 1.5 hours and aged at room temperature for 14 hours. Finally, the bio-based defoaming composition S51 was obtained by grinding with a ball mill.
[0095] Comparative Example 2:
[0096] At room temperature, 87 parts of biomass carrier soybean oil, 7 parts of defoaming active substance BE, and 3 parts of insect wax (melting point 33℃) were added to a container. Stirring was started and the speed was controlled at 1200 rpm. The temperature was raised to 116℃ and kept warm for 2 hours. Then, while maintaining the same speed, 0.6 parts of methyl arachidonic acid polyoxyethylene ether (9) and 2.4 parts of castor oil polyoxyethylene ether (40) were added. The temperature was then lowered to room temperature within 1.5 hours and aged at room temperature for 14 hours. Finally, the bio-based defoaming composition S52 was obtained by grinding with a ball mill.
[0097] Comparative Example 3:
[0098] At room temperature, 87 parts of biomass carrier soybean oil, 7 parts of defoaming active substance BE, 0.3 parts of insect wax (melting point 33℃), and 2.7 parts of cetyl arachidonic acid ester (melting point 83℃) were added to a container. Stirring was started and the speed was controlled at 1200 rpm. The temperature was raised to 116℃ and kept at that temperature for 2 hours. Then, while maintaining the same speed, 3 parts of castor oil polyoxyethylene ether (40) were added and the temperature was lowered to room temperature within 1.5 hours. The mixture was aged at room temperature for 14 hours and finally ground in a ball mill to obtain the bio-based defoaming composition S53.
[0099] Comparative Example 4:
[0100] At room temperature, 87 parts of biomass carrier soybean oil, 7 parts of defoaming active substance BE, 0.3 parts of insect wax (melting point 33℃), and 2.7 parts of cetyl arachidate (melting point 83℃) were added to a container. Stirring was started and the speed was controlled at 1200 rpm. The temperature was raised to 116℃ and kept warm for 2 hours. Then, while maintaining the same speed, 3 parts of methyl arachidate polyoxyethylene ether (9) were added and the temperature was lowered to room temperature within 1.5 hours. The mixture was aged at room temperature for 14 hours and finally ground by a ball mill to obtain the bio-based defoaming composition S54.
[0101] Comparative Example 5
[0102] At room temperature, 87 parts of biomass carrier soybean oil, 7 parts of defoaming active material (when preparing active material BE, the raw material castor oil polyether for synthesizing B1-5 was replaced with fatty alcohol polyoxyethylene ether of the same degree of polymerization, and the rest remained unchanged), 0.3 parts of insect wax (melting point 33℃), and 2.7 parts of cetyl arachidate (melting point 83℃) were added to a container. Stirring was started and the speed was controlled at 1200 rpm. The temperature was raised to 116℃ and kept at that temperature for 2 hours. Then, while maintaining the same speed, 0.6 parts of methyl arachidate polyoxyethylene ether (9) and 2.4 parts of castor oil polyoxyethylene ether (40) were added. The temperature was then lowered to room temperature within 1.5 hours and aged at room temperature for 14 hours. Finally, the bio-based defoaming composition S55 was obtained by grinding with a ball mill.
[0103] Comparative Example 6
[0104] At room temperature, 87 parts of biomass carrier soybean oil, 7 parts of defoaming active substance (using B1-5 instead of BE), 0.3 parts of insect wax (melting point 33℃), and 2.7 parts of cetyl arachidonic acid ester (melting point 83℃) were added to a container. Stirring was started and the speed was controlled at 1200 rpm. The temperature was raised to 116℃ and kept at that temperature for 2 hours. Then, while maintaining the same speed, 0.6 parts of methyl arachidonic acid polyoxyethylene ether (9) and 2.4 parts of castor oil polyoxyethylene ether (40) were added. The temperature was then lowered to room temperature within 1.5 hours and aged at room temperature for 14 hours. Finally, the mixture was ground in a ball mill to obtain the bio-based defoaming composition S56.
[0105] The performance of the bio-based defoaming composition prepared by the method of this invention is mainly evaluated from the following aspects: 1. Stability test
[0106] Add 10 ml of the bio-based defoaming composition to the sample in a centrifuge tube and centrifuge at 3000 rpm for 15 min. After centrifugation, record the volume (ml) of the clear liquid at the top of the centrifuge tube. The smaller the volume of the clear liquid at the top, the more stable the bio-based defoaming composition is. The results are shown in Table 2.
[0107] 2. Compatibility test:
[0108] Weigh 200g of commercially available water-based ink, 50g of deionized water, and 0.2g of bio-based defoaming composition into a container and disperse at 600rpm for 3min. Take an appropriate amount of the dispersion and drop it onto black and white cardstock, then use a 40μm wire rod to evenly scrape it flat. Observe the state of the dispersion on the black and white cardstock (porosity). The number of porosity with a diameter of 1mm or more per square centimeter of dry film is used as the measure. The results are shown in Table 2.
[0109] 3. Foam suppression performance test:
[0110] The defoaming performance was tested using the air blowing method. 100g of commercially available water-based ink, 30g of deionized water and 0.2g of bio-based defoaming composition were weighed and added to a 500mL graduated cylinder. Air was blown into the mixture at a certain flow rate, and the time it took for the foam to reach the 500mL mark was recorded. The longer the time, the better the defoaming performance. The results are shown in Table 2.
[0111] Table 2 Summary of Stability, Compatibility and Foam Control Performance of Defoaming Compositions
[0112] sample Stability / ml Compatibility / individual Foam control time S1 0 0 15′04″ S2 0 0 16′33″ S3 0 1 16′15″ S4 0 1 16′44″ S5 0 0 16′15″ S51 0.1 10 16′32″ S52 0.1 1 10′21″ S53 1.2 2 10′21″ S54 0.2 8 17′28″ S55 0.3 6 16′23″ S56 0.2 2 12′25″
[0113] The data above shows that:
[0114] Comparing the stability of the bio-based defoaming compositions S1-S5 of the patented invention with that of comparative examples S51-S56, the following conclusions can be drawn:
[0115] (1) Stability: Except for the high hydrophilicity of bio-based surfactants which can cause instability in defoaming compositions, other defoaming compositions have good stability.
[0116] (2) The melting point of bio-wax has a certain influence on the compatibility of the defoaming composition;
[0117] (3) The HLB value of bio-based surfactants has a certain influence on the defoaming and compatibility of defoaming compositions. By combining monofunctional and trifunctional surfactants, defoaming compositions can better balance compatibility and defoaming performance.
[0118] (4) Castor oil polyoxyethylene ether-organosilicon polymer and silica dispersion are treated with a catalyst, which makes the defoaming composition exhibit good foam suppression performance.
Claims
1. A bio-based defoaming composition, characterized in that, It is prepared using biomass carrier A, antifoaming active substance B, biowax C, and bio-based surfactant D. A. Biomass carrier The biomass carrier is selected from vegetable oil esters, animal oil esters, and fatty acid methyl esters or ethyl esters formed by transesterification of lower alcohols obtained by bio-fermentation. The amount of the biomass carrier used is 80-90% of the total mass of the bio-based defoaming composition; B. Defoaming active ingredients The defoaming active substance is prepared from castor oil polyoxyethylene ether-organosilicon copolymer B1, silica dispersion B2, and catalyst B3; The preparation method of the defoaming active substance is as follows: castor oil polyoxyethylene ether-organosilicon copolymer is added to a container, and silica dispersion and catalyst are added while stirring is started and the speed is kept at 500-3000 rpm. The temperature is raised to 80-160℃ and kept at the temperature for 1-5 hours. Finally, the defoaming active substance is obtained by homogenization in a homogenizer. The amount of the defoaming active substance used is 5-10% of the bio-based defoaming composition; C. Biowax The biowax is an animal or plant wax or an ester wax formed from higher fatty acids and higher fatty alcohols; the amount of the biowax used is 2 to 10% of the total mass of the bio-based defoaming composition; D. Bio-based surfactants The bio-based surfactant refers to a surfactant obtained by incorporating ethylene oxide and / or propylene oxide with natural fatty alcohols or natural fatty acids containing hydroxyl or ester groups as initiators and with potassium hydroxide as a catalyst. The amount of the bio-based surfactant used is 2-8% of the total mass of the bio-based defoaming composition; The preparation method of the bio-based defoaming composition is as follows: At room temperature, add biomass carrier, defoaming active substance and biowax to a container, start stirring, control the speed at 1000-3000 rpm, raise the temperature to 100-150℃ and keep it at that temperature for 0.5-2 hours, then keep the same speed, add bio-based surfactant and cool down to room temperature within 1-3 hours, age at room temperature for 8-16 hours, and finally grind it with a ball mill to obtain the bio-based defoaming composition.
2. The bio-based defoaming composition according to claim 1, characterized in that, The plant oil esters are selected from sunflower seed oil, peanut oil, soybean oil, flaxseed oil, castor oil, rapeseed oil, and cottonseed oil; the animal oil esters are selected from fish oil, lard, beef tallow, and mutton tallow.
3. The bio-based defoaming composition according to claim 1, characterized in that, The castor oil polyoxyethylene ether-organosilicon copolymer B1 is formed by castor oil polyoxyethylene ether and hydrogen-containing silicone oil under the catalysis of metallic bismuth; The required mass fractions of raw materials for preparing castor oil polyoxyethylene ether-organosilicon copolymer are: Castor oil polyoxyethylene ether: 40-70%; Hydrogen-containing silicone oil: 40-65%; Bismuth metal catalyst: 0.05–0.5%; The sum of the mass percentages of the above three substances is 100%; The degree of polymerization of ethylene oxide in the castor oil polyoxyethylene ether is 2 to 20. The hydrogen-containing silicone oil has a dynamic viscosity of 5–40 mPa·s at 25°C and a hydrogen content of 0.05–0.3% at the end of its hydrogen content; the preparation method of the castor oil polyoxyethylene ether-organosilicon copolymer is as follows: Under nitrogen protection, castor oil polyoxyethylene ether and metal bismuth catalyst are added to a container, stirring is started and the temperature is raised to 70-150℃. The reaction temperature is maintained, and end-hydrogen-containing silicone oil is added dropwise at a uniform rate over 30-90 minutes. After the addition is completed, the temperature is maintained for 1-3 hours and then cooled to room temperature to obtain castor oil polyoxyethylene ether-organosilicon copolymer. The amount of castor oil polyoxyethylene ether-organosilicon copolymer used is 70-95% of the total mass of the defoaming active material.
4. The bio-based defoaming composition according to claim 1, characterized in that, The method for preparing the silica dispersion B2 is as follows: 80-99 parts of treatment agent and 1-20 parts of hydrophilic silica are added to a container, and the mixture is kept at 60-150℃ for 2-5 hours under nitrogen protection using a ball mill. The treatment agent is castor oil, or methyl castor oil, or ethyl castor oil; The specific surface area of the silicon dioxide is 50-200 m². 2 / g; The amount of the silica dispersion is 4-20% of the total mass of the defoaming active material.
5. The bio-based defoaming composition according to claim 1, characterized in that, The catalyst B3 is selected from one or more of potassium laurate, sodium laurate, sodium stearate, potassium stearate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, cesium carbonate, monoethanolamine, diethanolamine, triethanolamine, and ammonium bicarbonate; the amount of the catalyst is 0.1-2% of the total mass of the defoaming active material.
6. The bio-based defoaming composition according to claim 1, characterized in that, The animal waxes are beeswax, insect wax, shellac wax, whale wax, and wool wax; the plant waxes are carnauba wax, candelilla wax, sugarcane wax, and lacquer wax.
7. The bio-based defoaming composition according to claim 1, characterized in that, The biowax is a mixture of materials with melting points less than 40°C and greater than 80°C, in a mass ratio of: m(melting point less than 40℃): m(melting point greater than 70℃) = 1:9 to 3:
7.
8. A bio-based defoaming composition according to claim 1, wherein the bio-based surfactant is selected from polyoxyethylene laurate ether, polyoxyethylene laurate polyoxypropylene ether, myristic acid polyoxyethylene ether, myristic acid polyoxyethylene polyoxypropylene ether, palmitic acid polyoxyethylene ether, palmitic acid polyoxyethylene polyoxypropylene ether, stearic acid polyoxyethylene ether, stearic acid polyoxyethylene polyoxypropylene ether, oleic acid polyoxyethylene ether, oleic acid polyoxyethylene polyoxypropylene ether, arachidic acid polyoxyethylene ether, arachidic acid polyoxyethylene polyoxyethylene polyoxypropylene ether, castor oil polyoxyethylene ether, castor oil polyoxyethylene polyoxypropylene ether, methyl laurate polyoxyethylene ether, methyl laurate polyoxyethylene polyoxypropylene ether, ethyl laurate polyoxyethylene ether, methyl laurate polyoxyethylene polyoxypropylene ether, methyl myristicate polyoxyethylene ether, methyl myristicate polyoxyethylene polyoxypropylene ether, ethyl myristicate polyoxyethylene polyoxypropylene ether. Ethyl myristate polyoxyethylene polyoxypropylene ether, methyl palmitate polyoxyethylene ether, methyl palmitate polyoxyethylene polyoxypropylene ether, ethyl palmitate polyoxyethylene ether, ethyl palmitate polyoxyethylene polyoxypropylene ether, methyl stearate polyoxyethylene polyoxypropylene ether, methyl stearate polyoxyethylene polyoxypropylene ether, ethyl stearate polyoxyethylene polyoxypropylene ether, methyl oleate polyoxyethylene ether, methyl oleate polyoxyethylene polyoxypropylene ether, ethyl oleate polyoxyethylene ether, ethyl oleate polyoxyethylene polyoxypropylene ether, methyl arachidate polyoxyethylene ether, methyl arachidate polyoxyethylene polyoxypropylene ether, ethyl arachidate polyoxyethylene polyoxypropylene ether, methyl castor oil polyoxyethylene ether, methyl castor oil polyoxyethylene polyoxypropylene ether, ethyl castor oil polyoxyethylene ether, ethyl castor oil polyoxyethylene polyoxypropylene ether.
9. A bio-based defoaming composition according to claim 1, wherein the bio-based surfactant is a mixture of monofunctional and trifunctional surfactants, and the mass ratio of the monofunctional surfactant to the trifunctional surfactant is 10-20%: 80-90%.