CN112742073A - Modified tung linoleic acid polyether ester coating defoaming agent and preparation method thereof - Google Patents
Modified tung linoleic acid polyether ester coating defoaming agent and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of defoaming agents, and particularly relates to a modified tung linoleic acid polyether ester coating defoaming agent which is characterized by comprising the following components in percentage by mass: 6-10% of fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, 5-9% of mineral oil, 4-6% of propylene glycol block polyether, 2-4% of emulsifier, 1-2% of thickener, 1-3% of modified white carbon black, 3-5% of diglyceride oleate, and the balance of water. The invention also provides a preparation method of the modified tung linoleic acid polyether ester coating defoamer. The modified tung linoleic acid polyether ester coating defoamer disclosed by the invention is rapid in defoaming, strong in foam inhibition capability, excellent in foam breaking capability and good in coating compatibility, rarely causes silicon spots and shrinkage cavities on a coating, and is added with a small amount of mineral oil.
Description
Technical Field
The invention belongs to the technical field of defoaming agents, and particularly relates to a modified tung linoleic acid polyether ester coating defoaming agent and a preparation method thereof.
Background
The defoaming agent is a surfactant for inhibiting and eliminating various harmful foams, is the most effective method for controlling foams, is widely applied to the fields of chemical industry, medicine, spinning, printing and dyeing, mineral separation, coating, sewage treatment and the like, and the foams in industrial production bring harm such as reduction of productivity, waste of raw materials, reduction of quality and the like, thereby causing adverse effects on production, and the control and elimination of the harmful foams have great technical and economic significance.
During the production of the coating, agitation can cause the coating to generate a large amount of foam which can result in reduced production capacity, wasted raw materials, extended reaction cycles, reduced product quality, etc., and the most cost effective way to eliminate foam is by means of defoamers. The paint defoamer can be classified into an organic silicon defoamer, a polyether defoamer, a mineral oil defoamer and the like. The mineral oil defoaming agent has good compatibility with the coating, rarely causes the shrinkage cavity phenomenon to the coating, but has better defoaming and foam inhibiting capability than the organic silicon defoaming agent; the organic silicon defoaming agent has good defoaming and long foam inhibition time, but the organic silicon defoaming agent is easy to break emulsion, so that the organic silicon defoaming agent has precipitates and is poor in compatibility with a system, and silicon spots and shrinkage cavities are caused on a coating; the defoaming ability of the polyether defoamer is weak, so that the application of the polyether defoamer is limited.
The existing coating defoamer is mainly a mineral oil defoamer and mainly comprises mineral oil, fatty acid metal soap, fatty acid amide, fatty alcohol and polyether, wherein the mineral oil has a certain defoaming effect, but mainly serves as a carrier, the content of the carrier is 75-80%, and the carrier is a non-renewable resource, so that the carrier becomes a development trend by utilizing the renewable resource, but the mineral oil is not successfully replaced at present, and partial products replaced in a small amount cannot meet the performance requirement, so that the problem to be solved urgently is solved. The invention discloses a mineral oil defoamer for general purpose in water and oil, which is prepared by sequentially carrying out epoxidation reaction and amino silicone oil grafting on castor oil to obtain amino silicone oil modified epoxy castor oil, and compounding the amino silicone oil modified epoxy castor oil with mineral oil, a defoaming substance, a defoaming auxiliary agent, hydrophobic white carbon black and an emulsifier. Although the hydrophilicity and defoaming capability of the castor oil are improved by modifying the epoxy castor oil with the amino silicone oil, the castor oil still has the disadvantages of high mineral oil content, insufficient defoaming capability and large using amount, and the existing hydrophobic white carbon black has insufficient defoaming capability and cannot form a competitive product.
Based on the above situation, it is important to develop a coating defoamer which has the advantages of rapid defoaming, strong foam inhibition capability, excellent foam breaking capability, good coating compatibility, little generation of silicon spots and shrinkage cavity of the coating, and addition of a small amount of mineral oil.
Disclosure of Invention
Aiming at solving the problems that the existing mineral oil defoaming agent applied to the coating industry has better defoaming and foam inhibiting capability than an organic silicon defoaming agent, and mineral oil is a non-renewable resource; the organic silicon defoamer is easy to demulsify, and causes silicon spots and shrinkage cavities on the coating; the defoaming capability of the polyether defoaming agent is weak; the invention provides a coating defoamer which has the advantages of rapid defoaming, strong foam inhibition capability, good coating compatibility, little generation of silicon spots and shrinkage cavity of a coating, and addition of a small amount of mineral oil, and is particularly important. In order to achieve the purpose, the invention adopts the following technical scheme:
the modified tung linoleic acid polyether ester coating antifoaming agent is characterized by comprising the following components in percentage by mass: 6-10% of fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, 5-9% of mineral oil, 4-6% of propylene glycol block polyether, 2-4% of emulsifier, 1-2% of thickener, 1-3% of modified white carbon black, 3-5% of diglyceride oleate, and the balance of water.
Furthermore, the preparation method of the fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester comprises the following steps:
step I, fluorine-containing alkyl grafted amino silicone oil: adding 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane, amino hydrogen-containing silicone oil and a catalyst into a reaction kettle, reacting for 7-9h at the temperature of 60-80 ℃ under the protection of nitrogen to obtain fluoroalkyl hydrogen-containing silicone oil;
step II, preparing the fluoroalkyl-amino silicone oil modified tung linoleic acid polyether ester: adding tung linoleic acid, hydroxyl-terminated polyether and p-toluenesulfonic acid into a reaction kettle, reacting for 6-10h at the temperature of 120-140 ℃, cooling to room temperature, adding the fluoroalkyl hydrogen-containing silicone oil obtained in the step I, uniformly mixing at the temperature of 40-60 ℃, vacuumizing for 30-40min at the temperature of 80-100 ℃ and the pressure of-0.095-0.001 MPa, dehydrating, removing low boiling point, adding an isopropanol solution of chloroplatinic acid under the protection of nitrogen, and reacting for 6-8h at the temperature of 100-120 ℃ to obtain the fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester.
Furthermore, in the step I, the catalyst is one or more of a strong-acid cation exchange resin, acid clay and trifluoromethanesulfonic acid, and the molar ratio of 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane to amino hydrogen-containing silicone oil is as follows: 1: (1.2-1.5).
Further, the ratio of EO and PO of the tung linoleic acid polyether ester in the step II is (3-7): 7; the tung linoleic acid is prepared by mixing tung oil acid and linoleic acid according to the molar ratio of 6 (4-6); the mol ratio of Si-H of the tung linoleic acid, the hydroxyl-terminated polyether and the fluoroalkyl hydrogen-containing silicone oil is (1.1-1.2): 1: (2.8-3.2).
Furthermore, the emulsifier is fatty alcohol-polyoxyethylene ether, lecithin and sodium dodecyl benzene sulfonate according to the mass ratio of (4-6): 1: (0.6-0.8).
Furthermore, the mineral oil is industrial white oil prepared by taking light lubricating oil fraction at 250-400 ℃ in crude oil, and performing acid-base refining, water washing, drying, clay adsorption, antioxidant addition and other processes.
Further, the propylene glycol block polyether is PO-EO-PO propylene glycol block polyether with the molecular weight of 1000-3000, and the thickening agent is one or more of carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose.
Furthermore, the preparation method of the modified white carbon black comprises the following steps: adding white carbon black and 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane into a hydrocarbon organic solvent, performing ultrasonic treatment for 10-30min, performing reflux reaction for 4-8h, adding epoxy polyoxyethylene polyoxypropylene ether, performing reflux reaction for 3-7h, cooling to room temperature, concentrating, washing with absolute ethyl alcohol, drying, and grinding into powder to obtain the modified white carbon black.
Further, the hydrocarbon organic solvent is one of cyclohexane, n-hexane or petroleum ether; the molecular weight of the epoxy-terminated polyoxyethylene polyoxypropylene ether is 1500-2500, and the ratio of EO to PO is (3-7): 7; the mass ratio of the white carbon black, the 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane and the epoxy-terminated polyoxyethylene polyoxypropylene ether is 1: (0.3-0.5): (2-4).
Furthermore, the preparation method of the modified tung linoleic acid polyether ester defoaming agent comprises the following steps: heating fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, mineral oil, propylene glycol block polyether, modified white carbon black and diglyceride oleate to 40-60 ℃, uniformly mixing, adding an emulsifier, a thickening agent and water, stirring at 6000r/min for 12-15min at the temperature of 30-60 ℃, and cooling to room temperature to obtain the modified tung linoleic acid polyether ester defoaming agent.
Furthermore, the modified tung linoleic acid polyether ester coating antifoaming agent can also be used in the fields of spinning, printing and dyeing, mineral separation, printing ink, sewage treatment and papermaking.
The beneficial effects of the invention are shown in the following aspects:
1. according to the preparation method, an epoxy group on 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane and an amino group on amino hydrogen-containing silicone oil are subjected to an open loop reaction, fluorine-containing alkane is connected to the hydrogen-containing silicone oil, fluoroalkyl hydrogen-containing silicone oil is obtained, tung oil linoleic acid is formed by mixing tung oil acid containing three double bonds and one carboxyl group and linoleic acid containing two double bonds and one carboxyl group, the carboxyl group of tung oil linoleic acid and the hydroxyl group of hydroxyl-terminated polyether are subjected to an esterification reaction, tung oil linoleic acid polyether ester is obtained, the contained double bonds are subjected to an addition reaction with Si-H of the fluoroalkyl hydrogen-containing silicone oil, the fluoroalkyl hydrogen-containing silicone oil modified tung oil linoleic acid polyether ester is obtained, and organic silicon. The tung oil linoleic acid introduces a long carbon chain, the long carbon chain and fluoroalkyl hydrogen-containing silicone oil both increase hydrophobicity, and hydroxyl polyether increases hydrophilicity, so that the fluoroalkyl hydrogen-containing silicone oil modified tung oil linoleic acid polyether ester not only has excellent defoaming and foam inhibition performance and water dispersibility, but also is not easy to break emulsion in emulsion preparation, has no precipitate, and rarely causes silicon spots and shrinkage cavity phenomena on a coating.
2. The surface of the white carbon black contains a large amount of silicon hydroxyl groups and has hydrophilicity, and two ends of 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyl disiloxane respectively contain one end amino group, the invention firstly makes the amino group at one end of the 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyl disiloxane and the silicon hydroxyl group on the surface of the white carbon black undergo a hydroxyl amination reaction, and makes the amino group at the other end and the end epoxy group on the end epoxy group polyoxyethylene polyoxypropylene ether undergo a ring-opening reaction to obtain the modified white carbon black, and the 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyl disiloxane and the end epoxy group polyoxyethylene polyoxypropylene ether are grafted on the surface of the white carbon black, so that the surface of the white carbon black is connected with siloxane and polyoxyethylene polyoxypropylene ether, the siloxane increases the hydrophobicity of the white carbon black, so that the white carbon black has excellent defoaming and foam inhibition properties; the epoxy-terminated polyoxyethylene polyoxypropylene ether ensures that the white carbon black grafted with siloxane groups has good water dispersibility and foam inhibition; the 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane is grafted on the surface of the white carbon black, so that the nitrogen content of the surface of the white carbon black is increased, the permeation of the white carbon black to a foam wall is improved, and the foam breaking rate is improved.
3. According to the invention, fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, mineral oil, propylene glycol block polyether, modified white carbon black and diglyceride oleate are used as raw materials, and the emulsion type coating defoamer is prepared under the action of water, an emulsifier and a thickener, so that the defoamer is rapid in defoaming, strong in foam inhibition capability, excellent in foam breaking capability and good in coating compatibility, and rarely causes silicon spots and shrinkage cavity phenomena of a coating, and only a small amount of mineral oil which is a non-renewable resource is added.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The raw materials used in the following examples of the present invention were all purchased commercially.
Example 1
The modified tung linoleic acid polyether ester coating antifoaming agent is characterized by comprising the following components in percentage by mass: 6% of fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, 5% of mineral oil, 4% of propylene glycol block polyether, 2% of emulsifier, 1% of thickener, 1% of modified white carbon black, 3% of diglyceride oleate and the balance of water.
Furthermore, the preparation method of the fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester comprises the following steps:
step I, fluorine-containing alkyl grafted amino silicone oil: adding 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane, amino hydrogen-containing silicone oil and a catalyst into a reaction kettle, and reacting for 7 hours at the temperature of 60 ℃ under the protection of nitrogen to obtain fluoroalkyl hydrogen-containing silicone oil;
step II, preparing the fluoroalkyl-amino silicone oil modified tung linoleic acid polyether ester: adding tung linoleic acid, hydroxyl-terminated polyether and p-toluenesulfonic acid into a reaction kettle, reacting for 6h at 120 ℃, cooling to room temperature, adding the fluoroalkyl hydrogen-containing silicone oil obtained in the step I, uniformly mixing at 40 ℃, vacuumizing for 30min at 80 ℃ and under the pressure of-0.095 MPa, dehydrating, removing low boiling point, adding an isopropanol solution of chloroplatinic acid under nitrogen protection, and reacting for 6h at 100 ℃ to obtain the fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester.
Furthermore, in the step I, the catalyst is one or more of a strong-acid cation exchange resin, acid clay and trifluoromethanesulfonic acid, and the molar ratio of 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane to amino hydrogen-containing silicone oil is as follows: 1: 1.2.
further, the ratio of EO to PO of the tung oil linoleic polyether ester in the step II is 3: 7; the tung oil linoleic acid is prepared from tung oil acid and linoleic acid according to the mol ratio of 6: 4, mixing; the mol ratio of Si-H of the tung linoleic acid, the hydroxyl-terminated polyether and the fluoroalkyl hydrogen-containing silicone oil is 1.1: 1: 2.8.
furthermore, the emulsifier is fatty alcohol-polyoxyethylene ether, lecithin and sodium dodecyl benzene sulfonate according to a mass ratio of 4: 1: 0.6 of the mixture.
Further, the propylene glycol block polyether is PO-EO-PO propylene glycol block polyether with the molecular weight of 1000, and the thickening agent is carboxymethyl cellulose.
Furthermore, the preparation method of the modified white carbon black comprises the following steps: adding white carbon black and 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane into a hydrocarbon organic solvent, carrying out ultrasonic treatment for 10min, carrying out reflux reaction for 4h, then adding epoxy-terminated polyoxyethylene polyoxypropylene ether, carrying out reflux reaction for 3h, cooling to room temperature, concentrating, washing with absolute ethyl alcohol, drying, and grinding into powder to obtain the modified white carbon black.
Further, the hydrocarbon organic solvent is one of cyclohexane, n-hexane or petroleum ether, the molecular weight of the epoxy polyoxyethylene polyoxypropylene ether is 1500, and the ratio of EO to PO is 3: 7, the mass ratio of white carbon black, 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane to epoxy-terminated polyoxyethylene polyoxypropylene ether is 1: 0.3: 2.
furthermore, the preparation method of the modified tung linoleic acid polyether ester defoaming agent comprises the following steps: heating fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, mineral oil, propylene glycol block polyether, modified white carbon black and diglyceride oleate to 40 ℃, uniformly mixing, adding an emulsifier, a thickening agent and water, stirring at 6000r/min at 30 ℃ for 12min, and cooling to room temperature to obtain the modified tung linoleic acid polyether ester defoaming agent.
Example 2
The modified tung linoleic acid polyether ester coating antifoaming agent is characterized by comprising the following components in percentage by mass: 7% of fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, 6% of mineral oil, 4.5% of propylene glycol block polyether, 2.5% of emulsifier, 1.2% of thickener, 1.5% of modified white carbon black, 3.5% of diglyceride oleate, and the balance of water.
Furthermore, the preparation method of the fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester comprises the following steps:
step I, fluorine-containing alkyl grafted amino silicone oil: adding 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane, amino hydrogen-containing silicone oil and a catalyst into a reaction kettle, reacting for 7.5 hours at 65 ℃ under the protection of nitrogen to obtain fluoroalkyl hydrogen-containing silicone oil;
step II, preparing the fluoroalkyl-amino silicone oil modified tung linoleic acid polyether ester: adding tung linoleic acid, hydroxyl-terminated polyether and p-toluenesulfonic acid into a reaction kettle, reacting for 7h at 125 ℃, cooling to room temperature, adding the fluoroalkyl hydrogen-containing silicone oil obtained in the step I, uniformly mixing at 45 ℃, vacuumizing for 32min at 85 ℃ and under the pressure of-0.096 MPa, dehydrating, removing low boiling point, adding an isopropanol solution of chloroplatinic acid under nitrogen protection, and reacting for 6.5h at 105 ℃ to obtain the fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester.
Further, in the step I, the catalyst is one or more of a strong-acid cation exchange resin, acid clay and trifluoromethanesulfonic acid, and the molar ratio of 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane to amino hydrogen-containing silicone oil is 1: 1.27.
further, the ratio of EO to PO of the tung oil linoleic polyether ester in the step II is 4: 7; the tung oil linoleic acid is prepared from tung oil acid and linoleic acid according to the mol ratio of 6: 4.5 mixing; the mol ratio of Si-H of the tung linoleic acid, the hydroxyl-terminated polyether and the fluoroalkyl hydrogen-containing silicone oil is 1.12: 1: 2.9.
furthermore, the emulsifier is fatty alcohol-polyoxyethylene ether, lecithin and sodium dodecyl benzene sulfonate according to a mass ratio of 4.5: 1: 0.65 of the mixture.
Further, the propylene glycol block polyether is PO-EO-PO propylene glycol block polyether with the molecular weight of 1500, and the thickening agent is hydroxyethyl cellulose.
Furthermore, the preparation method of the modified white carbon black comprises the following steps: adding white carbon black and 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane into a hydrocarbon organic solvent, carrying out ultrasonic treatment for 15min, carrying out reflux reaction for 5h, then adding epoxy-terminated polyoxyethylene polyoxypropylene ether, carrying out reflux reaction for 4h, cooling to room temperature, concentrating, washing with absolute ethyl alcohol, drying, and grinding into powder to obtain the modified white carbon black.
Further, the hydrocarbon organic solvent is one of cyclohexane, n-hexane or petroleum ether, the molecular weight of the epoxy polyoxyethylene polyoxypropylene ether is 1800, and the ratio of EO to PO is 4: 7, the mass ratio of white carbon black, 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane to epoxy-terminated polyoxyethylene polyoxypropylene ether is 1: 0.35: 2.5.
furthermore, the preparation method of the modified tung linoleic acid polyether ester defoaming agent comprises the following steps: heating fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, mineral oil, propylene glycol block polyether, modified white carbon black and diglyceride oleate to 45 ℃, uniformly mixing, adding an emulsifier, a thickening agent and water, stirring at 6000r/min at 37 ℃ for 13min, and cooling to room temperature to obtain the modified tung linoleic acid polyether ester defoaming agent.
Example 3
The modified tung linoleic acid polyether ester coating antifoaming agent is characterized by comprising the following components in percentage by mass: 8% of fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, 7% of mineral oil, 5% of propylene glycol block polyether, 3% of emulsifier, 1.5% of thickener, 2% of modified white carbon black, 4% of diglyceride oleate and the balance of water.
Furthermore, the preparation method of the fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester comprises the following steps:
step I, fluorine-containing alkyl grafted amino silicone oil: adding 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane, amino hydrogen-containing silicone oil and a catalyst into a reaction kettle, and reacting for 8 hours at 70 ℃ under the protection of nitrogen to obtain fluoroalkyl hydrogen-containing silicone oil;
step II, preparing the fluoroalkyl-amino silicone oil modified tung linoleic acid polyether ester: adding tung linoleic acid, hydroxyl-terminated polyether and p-toluenesulfonic acid into a reaction kettle, reacting for 8h at 130 ℃, cooling to room temperature, adding the fluoroalkyl hydrogen-containing silicone oil obtained in the step I, uniformly mixing at 50 ℃, vacuumizing for 35min at 90 ℃ and under the pressure of-0.097 MPa, dehydrating, removing low boiling point, adding an isopropanol solution of chloroplatinic acid, and reacting for 7h at 110 ℃ to obtain the fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester.
Furthermore, in the step I, the catalyst is one or more of a strong-acid cation exchange resin, acid clay and trifluoromethanesulfonic acid, and the molar ratio of 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane to amino hydrogen-containing silicone oil is as follows: 1: 1.35.
further, the ratio of EO to PO of the tung oil linoleic polyether ester in the step II is 5: 7; the tung oil linoleic acid is prepared from tung oil acid and linoleic acid according to the mol ratio of 6: 5, mixing the components; the mol ratio of Si-H of the tung linoleic acid, the hydroxyl-terminated polyether and the fluoroalkyl hydrogen-containing silicone oil is 1.15: 1: 3.
furthermore, the emulsifier is fatty alcohol-polyoxyethylene ether, lecithin and sodium dodecyl benzene sulfonate according to a mass ratio of 5: 1: 0.7 of a mixture.
Further, the propylene glycol block polyether is PO-EO-PO propylene glycol block polyether with molecular weight of 2000, and the thickening agent is hydroxypropyl methyl cellulose.
Furthermore, the preparation method of the modified white carbon black comprises the following steps: adding white carbon black and 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane into a hydrocarbon organic solvent, carrying out ultrasonic treatment for 20min, carrying out reflux reaction for 6h, then adding epoxy-terminated polyoxyethylene polyoxypropylene ether, carrying out reflux reaction for 5h, cooling to room temperature, concentrating, washing with absolute ethyl alcohol, drying, and grinding into powder to obtain the modified white carbon black.
Further, the hydrocarbon organic solvent is one of cyclohexane, n-hexane or petroleum ether, the molecular weight of the epoxy polyoxyethylene polyoxypropylene ether is 2000, and the ratio of EO to PO is 5: 7, the mass ratio of white carbon black, 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane to epoxy-terminated polyoxyethylene polyoxypropylene ether is 1: 0.4: 3.
furthermore, the preparation method of the modified tung linoleic acid polyether ester defoaming agent comprises the following steps: heating fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, mineral oil, propylene glycol block polyether, modified white carbon black and diglyceride oleate to 50 ℃, uniformly mixing, adding an emulsifier, a thickening agent and water, stirring at 6000r/min at 45 ℃ for 13min, and cooling to room temperature to obtain the modified tung linoleic acid polyether ester defoaming agent.
Example 4
The modified tung linoleic acid polyether ester coating antifoaming agent is characterized by comprising the following components in percentage by mass: 9% of fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, 8% of mineral oil, 5.5% of propylene glycol block polyether, 3.5% of emulsifier, 1.7% of thickener, 2.5% of modified white carbon black, 4.5% of diglyceride oleate, and the balance of water.
Furthermore, the preparation method of the fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester comprises the following steps:
step I, fluorine-containing alkyl grafted amino silicone oil: adding 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane, amino hydrogen-containing silicone oil and a catalyst into a reaction kettle, reacting for 8.5 hours at 75 ℃ under the protection of nitrogen to obtain fluoroalkyl hydrogen-containing silicone oil;
step II, preparing the fluoroalkyl-amino silicone oil modified tung linoleic acid polyether ester: adding tung linoleic acid, hydroxyl-terminated polyether and p-toluenesulfonic acid into a reaction kettle, reacting for 9h at 135 ℃, cooling to room temperature, adding fluoroalkyl hydrogen-containing silicone oil obtained in the step I, uniformly mixing at 55 ℃, vacuumizing for 38min at 95 ℃ and under the pressure of-0.099 MPa, dehydrating, removing low boiling point, adding an isopropanol solution of chloroplatinic acid under the protection of nitrogen, and reacting for 7.5h at 115 ℃ to obtain the fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester.
Furthermore, in the step I, the catalyst is one or more of a strong-acid cation exchange resin, acid clay and trifluoromethanesulfonic acid, and the molar ratio of 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane to amino hydrogen-containing silicone oil is as follows: 1: 1.42.
further, the ratio of EO to PO of the tung oil linoleic acid polyether ester in the step II is 6: 7; the tung oil linoleic acid is prepared from tung oil acid and linoleic acid according to the mol ratio of 6: 5.5 mixing; the mol ratio of Si-H of the tung linoleic acid, the hydroxyl-terminated polyether and the fluoroalkyl hydrogen-containing silicone oil is 1.18: 1: 3.1.
furthermore, the emulsifier is fatty alcohol-polyoxyethylene ether, lecithin and sodium dodecyl benzene sulfonate according to a mass ratio of 5.5: 1: 0.75 of the mixture.
Furthermore, the propylene glycol block polyether is PO-EO-PO propylene glycol block polyether with the molecular weight of 2500, and the thickening agent is carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose according to the mass ratio of 1: 2: 3 in a mixture of two or more.
Furthermore, the preparation method of the modified white carbon black comprises the following steps: adding white carbon black and 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane into a hydrocarbon organic solvent, carrying out ultrasonic treatment for 25min, carrying out reflux reaction for 7h, then adding epoxy-terminated polyoxyethylene polyoxypropylene ether, carrying out reflux reaction for 6h, cooling to room temperature, concentrating, washing with absolute ethyl alcohol, drying, and grinding into powder to obtain the modified white carbon black.
Further, the hydrocarbon organic solvent is one of cyclohexane, n-hexane or petroleum ether, the molecular weight of the epoxy polyoxyethylene polyoxypropylene ether is 2200, and the ratio of EO to PO is 6: 7, the mass ratio of white carbon black, 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane to epoxy-terminated polyoxyethylene polyoxypropylene ether is 1: 0.45: 3.5.
furthermore, the preparation method of the modified tung linoleic acid polyether ester defoaming agent comprises the following steps: heating fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, mineral oil, propylene glycol block polyether, modified white carbon black and diglyceride oleate to 55 ℃, uniformly mixing, adding an emulsifier, a thickening agent and water, stirring at 6000r/min at 52 ℃ for 14min, and cooling to room temperature to obtain the modified tung linoleic acid polyether ester defoaming agent.
Example 5
The modified tung linoleic acid polyether ester coating antifoaming agent is characterized by comprising the following components in percentage by mass: 10% of fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, 9% of mineral oil, 6% of propylene glycol block polyether, 4% of emulsifier, 2% of thickener, 3% of modified white carbon black, 5% of diglyceride oleate, and the balance of water.
Furthermore, the preparation method of the fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester comprises the following steps:
step I, fluorine-containing alkyl grafted amino silicone oil: adding 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane, amino hydrogen-containing silicone oil and a catalyst into a reaction kettle, and reacting for 9 hours at 80 ℃ under the protection of nitrogen to obtain fluoroalkyl hydrogen-containing silicone oil;
step II, preparing the fluoroalkyl-amino silicone oil modified tung linoleic acid polyether ester: adding tung linoleic acid, hydroxyl-terminated polyether and p-toluenesulfonic acid into a reaction kettle, reacting for 10h at 140 ℃, cooling to room temperature, adding the fluoroalkyl hydrogen-containing silicone oil obtained in the step I, uniformly mixing at 60 ℃, vacuumizing for 40min at 100 ℃ and under the pressure of-0.001 MPa, dehydrating, removing low boiling point, adding an isopropanol solution of chloroplatinic acid under nitrogen protection, and reacting for 8h at 120 ℃ to obtain the fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester.
Furthermore, in the step I, the catalyst is one or more of a strong-acid cation exchange resin, acid clay and trifluoromethanesulfonic acid, and the molar ratio of 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane to amino hydrogen-containing silicone oil is as follows: 1: 1.5.
further, the ratio of EO and PO of the tung linoleic acid polyether ester in the step II is (3-7): 7; the tung oil linoleic acid is prepared from tung oil acid and linoleic acid according to the mol ratio of 6: 6, mixing; the mol ratio of Si-H of the tung linoleic acid, the hydroxyl-terminated polyether and the fluoroalkyl hydrogen-containing silicone oil is 1.2: 1: 3.2.
furthermore, the emulsifier is fatty alcohol-polyoxyethylene ether, lecithin and sodium dodecyl benzene sulfonate according to a mass ratio of 6: 1: 0.8 of the mixture.
Furthermore, the propylene glycol block polyether is PO-EO-PO propylene glycol block polyether with the molecular weight of 3000, and the thickening agent is a mixture of carboxymethyl cellulose and hydroxypropyl methyl cellulose in a mass ratio of 1: 1.
Furthermore, the preparation method of the modified white carbon black comprises the following steps: adding white carbon black and 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane into a hydrocarbon organic solvent, carrying out ultrasonic treatment for 30min, carrying out reflux reaction for 8h, then adding epoxy-terminated polyoxyethylene polyoxypropylene ether, carrying out reflux reaction for 7h, cooling to room temperature, concentrating, washing with absolute ethyl alcohol, drying, and grinding into powder to obtain the modified white carbon black.
Further, the hydrocarbon organic solvent is one of cyclohexane, n-hexane or petroleum ether, the molecular weight of the epoxy-terminated polyoxyethylene polyoxypropylene ether is 2500, and the ratio of EO to PO is 7: 7, the mass ratio of white carbon black, 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane to epoxy-terminated polyoxyethylene polyoxypropylene ether is 1: 0.5: 4.
furthermore, the preparation method of the modified tung linoleic acid polyether ester defoaming agent comprises the following steps: heating fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, mineral oil, propylene glycol block polyether, modified white carbon black and diglyceride oleate to 60 ℃, uniformly mixing, adding an emulsifier, a thickening agent and water, stirring at 6000r/min at the temperature of 60 ℃ for 15min, and cooling to room temperature to obtain the modified tung linoleic acid polyether ester defoaming agent.
Comparative example 1
A modified tung linoleic acid polyether ester coating defoamer, the preparation method and the formula of which are basically the same as those in the example 1, except that: no fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester is added.
Comparative example 2
A modified tung linoleic acid polyether ester coating defoamer, the preparation method and the formula of which are basically the same as those in the example 1, except that: modified white carbon black is not added.
Comparative example 3
German BYK-023 silicone antifoam agent is commercially available.
Comparative example 4
The water-oil universal mineral oil defoamer prepared in example 1 of Chinese invention patent CN 112057907A. The experimental results are as follows:
the defoaming property of the coating defoaming agents of examples 1 to 5 and comparative examples 1 to 3 was tested by the following method: adding 200g of emulsion (pure acrylic emulsion: styrene-acrylic emulsion 1: 1) into a 1000ml enamel cup, then adding 0.2g of defoaming agent, dispersing for 15min at a high speed of 2000rpm by using a laboratory high-speed dispersion machine, immediately pouring into a 100ml measuring cylinder after stopping, wherein the liquid level is 100ml of graduation line of the measuring cylinder, weighing the total weight of the measuring cylinder and the emulsion, and marking the total weight as M, wherein the measuring cylinder needs to be weighed in advance, the weight is M, and calculating the dispersion density (g/ml) of the emulsion to be (M-M)/100 ml. The larger the dispersion density is, the smaller the gas content is, which indicates that the defoaming agent has good foam inhibition performance, and the test results are shown in Table 1.
The storage stability test method of the coating defoamer comprises the following steps: after the emulsion containing the defoaming agent (acrylic emulsion: styrene-acrylic emulsion ═ 1: 1) was allowed to stand for 4 hours, the number of precipitates on the surface of the emulsion was observed, and the larger the number of precipitates, the poorer the storage stability of the defoaming agent, and on the contrary, the better the storage stability of the defoaming agent was confirmed.
The compatibility test method of the coating defoamer comprises the following steps: and (3) preparing the emulsion into a coating, placing for 15min, taking out a small amount of the emulsion, allowing the emulsion to stand, dripping the emulsion on a clean glass plate, uniformly scraping the coating by using a wet film preparation device, observing and recording the number of shrinkage holes and the gloss of a coating film on the glass plate, wherein the flatter the coating film is, the smaller the number of the shrinkage holes is, the better the compatibility of the defoaming agent is, and otherwise, the poorer the compatibility of the defoaming agent is, and the test result is shown in table 1.
TABLE 1 Dispersion Density, number of precipitates and compatibility of coating defoamers for different examples
| Test items | Dispersion density (g/mL) | Number of precipitates | Compatibility of antifoam |
| Example 1 | 0.91 | Is rarely used | Smooth coating film, 1 pinhole |
| Example 2 | 0.92 | Is rarely used | Smooth coating film, 1 pinhole |
| Example 3 | 0.93 | Is rarely used | Smooth coating film, 2 pinholes |
| Example 4 | 0.94 | Is rarely used | Smooth coating film, 2 pinholes |
| Example 5 | 0.95 | Is rarely used | Smooth coating film, 3 pinholes |
| Comparative example 1 | 0.61 | Is rarely used | Smooth coating film, 2 pinholes |
| Comparative example 2 | 0.76 | Is rarely used | Smooth coating film, 2 pinholes |
| Comparative example 3 | 0.62 | A little bit more | The coating film is slightly uneven, 4 pinholes |
| Comparative example 4 | 0.81 | Is rarely used | Smooth coating film, 2 pinholes |
As can be seen from Table 1, the modified tung linoleic acid polyether ester coating antifoaming agent and the coating antifoaming agent prepared by the preparation method have excellent defoaming and foam inhibition properties, storage stability and compatibility.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The modified tung linoleic acid polyether ester coating antifoaming agent is characterized by comprising the following components in percentage by mass: 6-10% of fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, 5-9% of mineral oil, 4-6% of propylene glycol block polyether, 2-4% of emulsifier, 1-2% of thickener, 1-3% of modified white carbon black, 3-5% of diglyceride oleate, and the balance of water.
2. The modified tung linoleic acid polyether ester coating antifoaming agent in accordance with claim 1, wherein the preparation method of fluoroalkyl hydrogen silicone oil modified tung linoleic acid polyether ester comprises the following steps:
step I, fluorine-containing alkyl grafted amino silicone oil: adding 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane, amino hydrogen-containing silicone oil and a catalyst into a reaction kettle, reacting for 7-9h at the temperature of 60-80 ℃ under the protection of nitrogen to obtain fluoroalkyl hydrogen-containing silicone oil;
step II, preparing the fluoroalkyl-amino silicone oil modified tung linoleic acid polyether ester: adding tung linoleic acid, hydroxyl-terminated polyether and p-toluenesulfonic acid into a reaction kettle, reacting for 6-10h at the temperature of 120-140 ℃, cooling to room temperature, adding the fluoroalkyl hydrogen-containing silicone oil obtained in the step I, uniformly mixing at the temperature of 40-60 ℃, vacuumizing for 30-40min at the temperature of 80-100 ℃ and the pressure of-0.095-0.001 MPa, dehydrating, removing low boiling point, adding an isopropanol solution of chloroplatinic acid under the protection of nitrogen, and reacting for 6-8h at the temperature of 100-120 ℃ to obtain the fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester.
3. The modified tung linoleic acid polyether ester coating antifoaming agent in claim 2, wherein in step I, the catalyst is one or more of strong acid cation exchange resin, acid clay and trifluoromethanesulfonic acid, and the molar ratio of 2, 2-difluoro-3, 3-bis (trifluoromethyl) ethylene oxide to amino hydrogen-containing silicone oil is as follows: 1: (1.2-1.5).
4. The modified tung linoleic acid polyether ester coating defoamer as claimed in claim 2, wherein said hydroxyl terminated polyether in step II has EO and PO ratio of (3-7): 7; the tung linoleic acid is prepared by mixing tung oil acid and linoleic acid according to the molar ratio of 6 (4-6); the mol ratio of Si-H of the tung linoleic acid, the hydroxyl-terminated polyether and the fluoroalkyl hydrogen-containing silicone oil is (1.1-1.2): 1: (2.8-3.2).
5. The modified tung linoleic acid polyether ester coating antifoaming agent according to claim 1, characterized in that the emulsifier is fatty alcohol-polyoxyethylene ether, lecithin and sodium dodecyl benzene sulfonate in a mass ratio of (4-6): 1: (0.6-0.8).
6. The modified tung linoleic acid polyether ester coating antifoaming agent in claim 1, wherein the propylene glycol block polyether is PO-EO-PO propylene glycol block polyether with molecular weight of 1000-3000, and the thickener is one or more of carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose.
7. The modified tung linoleic acid polyether ester coating antifoaming agent according to claim 1, characterized in that the preparation method of the modified white carbon black comprises the following steps: adding white carbon black and 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane into a hydrocarbon organic solvent, performing ultrasonic treatment for 10-30min, performing reflux reaction for 4-8h, adding epoxy polyoxyethylene polyoxypropylene ether, performing reflux reaction for 3-7h, cooling to room temperature, concentrating, washing with absolute ethyl alcohol, drying, and grinding into powder to obtain the modified white carbon black.
8. The modified tung linoleic acid polyether ester coating antifoaming agent in accordance with claim 7, wherein the hydrocarbon organic solvent is one of cyclohexane, n-hexane or petroleum ether; the molecular weight of the epoxy-terminated polyoxyethylene polyoxypropylene ether is 1500-2500, and the ratio of EO to PO is (3-7): 7; the mass ratio of the white carbon black, the 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane and the epoxy-terminated polyoxyethylene polyoxypropylene ether is 1: (0.3-0.5): (2-4).
9. The modified tung linoleic polyether ester coating defoamer as claimed in any one of claims 1 to 8, wherein the preparation method of the modified tung linoleic polyether ester defoamer comprises the following steps: heating fluoroalkyl hydrogen-containing silicone oil modified tung linoleic acid polyether ester, mineral oil, propylene glycol block polyether, modified white carbon black and diglyceride oleate to 40-60 ℃, uniformly mixing, adding an emulsifier, a thickening agent and water, stirring at 6000r/min for 12-15min at the temperature of 30-60 ℃, and cooling to room temperature to obtain the modified tung linoleic acid polyether ester defoaming agent.
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