CN112057907A - Water-oil universal mineral oil defoaming agent and preparation method thereof - Google Patents
Water-oil universal mineral oil defoaming agent and preparation method thereof Download PDFInfo
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- CN112057907A CN112057907A CN202010881752.9A CN202010881752A CN112057907A CN 112057907 A CN112057907 A CN 112057907A CN 202010881752 A CN202010881752 A CN 202010881752A CN 112057907 A CN112057907 A CN 112057907A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0413—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing N-atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0495—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance containing hetero rings
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Abstract
The invention belongs to the technical field of defoaming agents, and particularly discloses a water-oil universal mineral oil defoaming agent and a preparation method thereof. The defoaming agent comprises the following components in parts by weight: 40-60 parts of mineral oil, 40-60 parts of amino silicone oil modified epoxy castor oil, 2-10 parts of defoaming substances, 0.5-5 parts of defoaming auxiliaries, 1-10 parts of hydrophobic white carbon black and 0.1-10 parts of emulsifier, wherein the preparation method of the amino silicone oil modified epoxy castor oil comprises the following steps: adding epoxy castor oil and amino silicone oil into an organic solvent, adding an alkaline catalyst, stirring and reacting for 8-12 hours at the temperature of 60-80 ℃, centrifuging to obtain a supernatant, and performing rotary evaporation to remove the organic solvent to obtain the amino silicone oil modified epoxy castor oil. The invention uses amino silicone oil to carry out graft modification on epoxidized castor oil, changes the proportion of oleophylic and hydrophilic groups of the castor oil, thereby reducing the surface tension of the castor oil and improving the hydrophilicity and defoaming capability of the castor oil.
Description
Technical Field
The invention relates to the technical field of defoaming agents, in particular to a water-oil universal mineral oil defoaming agent and a preparation method thereof.
Background
Defoamers, also known as defoamers, are aids that suppress foam generation or eliminate foam already generated by reducing surface tension. The defoaming agent is mainly divided into three types: mineral oils, organic silicon and polyethers are applied to the fields of life, industrial production and the like, for example, low-foam washing powder, laundry detergent and the like in the current market, industries such as sewage treatment, seawater desalination, industrial fermentation and the like have different requirements on defoaming agents, and the combination of the defoaming agents can also have different effects.
The mineral oil defoamer at present is mainly applied to the fields of coatings and the like, mainly comprises mineral oil, fatty acid metal soap, fatty acid amide, fatty alcohol and polyether, the mineral oil has a certain defoaming effect, but mainly serves as a carrier, and as the mineral oil is a non-renewable resource, the carrier becomes a development trend by utilizing the renewable resource, but no successful case is found for completely replacing the mineral oil at present, and partial products replaced in a small amount cannot meet the performance requirements, so that the mineral oil defoamer becomes a problem to be solved urgently.
Castor, a plant of the genus ricinus of the family euphorbiaceae, mainly produced in india, brazil and china, is a herbaceous plant growing for one or more years, with oval seeds and an oil content of 40-48%, and is used for preparing biodegradable lubricating oils, coal dyes, drugs, etc. Castor oil derived from castor is a natural triglyceride of fatty acids, 90% of which are ricinoleic acid (9-alkenyl-12-hydroxyoctadecanoic acid) and 10% of which are oleic acid and linoleic acid without hydroxyl groups, and is the only vegetable oil containing hydroxyl groups in nature. The vegetable oil has certain defoaming performance, castor oil is no exception, and the vegetable oil such as castor oil is used as a raw material as a component of the defoaming agent, so that the consumption of mineral oil can be reduced, the cost is saved, the dependence on petrochemical products is reduced, the energy is saved, the pollution to the environment is reduced, and the requirements of a conservation-minded society and a sustainable development society are met. At present, vegetable oil such as castor oil and soybean oil is used as a defoaming component in many defoaming agents, but the vegetable oil such as castor oil has poor hydrophilicity due to the long carbon chain structure, is difficult to be rapidly and effectively dispersed in a water phase, and has poor defoaming performance, so that the defoaming agent is not suitable for being used as a defoaming agent for a water phase system.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a water-oil universal mineral oil defoamer and a preparation method thereof, which are used for solving the problems of poor hydrophilicity, poor dispersibility in water phase, poor defoaming performance and the like of the mineral oil defoamer containing castor oil in the prior art.
In order to achieve the above purpose and other related purposes, the invention provides a water-oil universal mineral oil defoamer, which comprises the following components in parts by weight: 40-60 parts of mineral oil, 40-60 parts of amino silicone oil modified epoxy castor oil, 2-10 parts of defoaming substances, 0.5-5 parts of defoaming auxiliaries, 1-10 parts of hydrophobic white carbon black and 0.1-10 parts of emulsifier, wherein the preparation method of the amino silicone oil modified epoxy castor oil comprises the following steps:
adding epoxy castor oil and amino silicone oil into an organic solvent, adding an alkaline catalyst into the organic solvent, stirring the mixture to react for 8 to 12 hours at the temperature of between 60 and 80 ℃, centrifuging the mixture to obtain supernatant, and performing rotary evaporation to remove the organic solvent to obtain the amino silicone oil modified epoxy castor oil.
Optionally, the molar ratio of the epoxy castor oil to the amino silicone oil is 1: 3-5.
Alternatively, the amount of the basic catalyst required for adding 1mol of the epoxidized castor oil to react with the aminosilicone oil is 0.5-1.0 mL.
Optionally, the alkaline catalyst is selected from at least one of sodium hydroxide and potassium hydroxide.
Optionally, the organic solvent is selected from one of absolute ethyl alcohol, N dimethylformamide, tetrahydrofuran, benzene and toluene.
Further, the preparation method of the epoxy castor oil comprises the following steps: under the action of an acid catalyst, heating formic acid or acetic acid, hydrogen peroxide and castor oil for reaction, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with water, removing a water phase, and then carrying out alkali washing, water washing and reduced pressure distillation to obtain the epoxy castor oil.
Optionally, the molar ratio of formic acid or acetic acid to hydrogen peroxide to castor oil is 3: 8-10: 6-8.
Optionally, the heating reaction temperature is 60-70 ℃, and the heating reaction time is 3-6 hours.
Alternatively, the acid catalyst is concentrated sulfuric acid, and the amount of concentrated sulfuric acid required for adding 1mol of formic acid or acetic acid is 0.3-0.5 mL.
Optionally, the mass fraction of the concentrated sulfuric acid is 95-98%.
Optionally, the mineral oil is at least one selected from white oil, liquid paraffin and alkylbenzene.
Optionally, the antifoaming substance is at least one of a fatty acid metal soap, a fatty acid amide.
Optionally, the fatty acid metal soap is selected from at least one of aluminum monofatty acid selected from at least one of aluminum butyrate, aluminum caprylate, aluminum tetradecanoate, aluminum pentadecanoate, aluminum hexadecanoate, aluminum heptadecanoate, aluminum octadecanoate, aluminum nonadecane, aluminum eicosanoate, aluminum docosanoate, aluminum triacontanoate, aluminum tetradecanoate, aluminum docosaconate, and aluminum difatty acid selected from at least one of aluminum dibutyrate, aluminum dioctanoate, aluminum dimyristate, aluminum dipentanoate, aluminum dihexadecanoate, aluminum diheptadecanoate, aluminum dioctadecanoate, aluminum ditodecanoate, aluminum docosahexanoate, aluminum didodecanoate, aluminum ditriacontanoate, aluminum dihexadecenoate, and aluminum dioctadecanoate.
Alternatively, the fatty acid amide is selected from at least one of ethylene bis stearamide, ethylene bis palmitamide, ethylene bis myristamide, ethylene bis laurate amide, ethylene bis oleamide, propylene bis stearamide, propylene bis palmitamide, propylene bis myristamide amide, propylene bis laurate amide, propylene bis oleamide, butylene bis stearamide, butylene bis palmitamide, butylene bis myristamide amide, butylene bis laurate amide, and butylene bis oleamide.
Optionally, the defoaming auxiliary agent is selected from at least one of polyether, triethanolamine, n-octanol and isooctanol.
Optionally, the emulsifier is selected from at least one of span 20, tween 20, span 60, tween 60, span 80, tween 80 or polyoxyethylene 40 stearate.
The invention also provides a preparation method of the water-oil universal mineral oil defoaming agent, which comprises the following steps:
(1) adding epoxy castor oil and amino silicone oil into an organic solvent, adding an alkaline catalyst into the organic solvent, stirring the mixture to react for 8 to 12 hours at the temperature of between 60 and 80 ℃, centrifuging the mixture to obtain supernatant, and performing rotary evaporation to remove the organic solvent to obtain amino silicone oil modified epoxy castor oil;
(2) adding mineral oil, amino silicone oil modified epoxy castor oil, a defoaming substance, a defoaming auxiliary agent, hydrophobic white carbon black and an emulsifier into a reaction kettle in sequence according to a ratio, stirring and dispersing the system uniformly, heating to 70-80 ℃, stirring for 1-2 hours, then preserving heat for 1-2 hours, cooling to 40-50 ℃, stirring for 1-2 hours, and finally cooling to room temperature to obtain the mineral oil defoaming agent.
Optionally, in the step (1), the molar ratio of the epoxy castor oil to the amino silicone oil is 1: 3-5.
Alternatively, in the step (1), the amount of the basic catalyst required for adding 1mol of the epoxidized castor oil to react with the aminosilicone is 0.5-1.0 mL.
Optionally, in the step (1), the alkaline catalyst is at least one selected from sodium hydroxide and potassium hydroxide.
Optionally, in the step (1), the organic solvent is selected from one of absolute ethyl alcohol, N dimethylformamide, tetrahydrofuran, benzene and toluene.
Further, in the step (1), the preparation method of the epoxidized castor oil comprises the following steps: under the action of an acid catalyst, heating formic acid or acetic acid, hydrogen peroxide and castor oil for reaction, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with water, removing a water phase, and then carrying out alkali washing, water washing and reduced pressure distillation to obtain the epoxy castor oil.
Optionally, the molar ratio of formic acid or acetic acid to hydrogen peroxide to castor oil is 3: 8-10: 6-8.
Optionally, the heating reaction temperature is 60-70 ℃, and the heating reaction time is 3-6 hours.
Alternatively, the acid catalyst is concentrated sulfuric acid, and the amount of concentrated sulfuric acid required for adding 1mol of formic acid or acetic acid is 0.3-0.5 mL.
Optionally, the mass fraction of the concentrated sulfuric acid is 95-98%.
As described above, the water-oil universal mineral oil defoamer and the preparation method thereof of the present invention have the following beneficial effects:
according to the invention, the double bonds of the castor oil are epoxidized, the surface activity of the castor oil can be greatly increased by hydrophilic epoxy bonds, so that the dispersing power of the castor oil at the interface of water bubbles is improved, the defoaming performance of the castor oil is improved, and the epoxy castor oil is further subjected to graft modification by amino silicone oil to obtain amino silicone oil modified epoxy castor oil, so that the ratio of lipophilic groups to hydrophilic groups in the castor oil is changed, the surface tension of the castor oil is further reduced, and the hydrophilicity and defoaming capability of the castor oil are improved. The amino silicone oil modified epoxy castor oil is applied to the preparation of the defoaming agent, and is compounded with the mineral oil, the defoaming substance, the defoaming auxiliary agent, the hydrophobic white carbon black and the emulsifier to obtain the novel water-oil universal mineral oil defoaming agent.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The invention provides a water-oil universal mineral oil defoaming agent which comprises the following components in parts by weight: 40-60 parts of mineral oil, 40-60 parts of amino silicone oil modified epoxy castor oil, 2-10 parts of defoaming substance, 0.5-5 parts of defoaming auxiliary agent, 1-10 parts of hydrophobic white carbon black and 0.1-10 parts of emulsifier.
Wherein the mineral oil is at least one selected from white oil, liquid paraffin and alkylbenzene.
Wherein the defoaming substance is at least one of fatty acid metal soap and fatty acid amide. Specifically, the fatty acid metal soap is selected from at least one of aluminum monofatty acid and aluminum bisfatty acid, the aluminum monofatty acid is selected from at least one of aluminum butyrate, aluminum caprylate, aluminum tetradecanoate, aluminum pentadecanoate, aluminum hexadecanoate, aluminum heptadecanoate, aluminum octadecanoate, aluminum nonadecane, aluminum eicosanoate, aluminum docosane, aluminum triacontanoate, aluminum tetradecanoate, and aluminum docosacenate, and the aluminum bisfatty acid is selected from at least one of aluminum dibutyrate, aluminum dioctanoate, aluminum dimyristate, aluminum dipentanoate, aluminum dihexadecylate, aluminum diheptadecanoate, aluminum dioctadecylate, aluminum didodecanoate, aluminum dicetylenoate, and aluminum dioctadecenoate; the fatty acid amide is at least one selected from the group consisting of ethylene bis-stearamide, ethylene bis-palmitamide, ethylene bis-myristamide, ethylene bis-laurate amide, ethylene bis-oleamide, propylene bis-stearamide, propylene bis-palmitamide, propylene bis-myristamide, propylene bis-laurate amide, propylene bis-oleamide, butylene bis-stearamide, butylene bis-palmitamide, butylene bis-myristate amide, butylene bis-laurate amide and butylene bis-oleamide.
Wherein the defoaming auxiliary agent is at least one selected from polyether, triethanolamine, n-octanol and isooctanol.
Wherein the emulsifier is at least one selected from span 20, Tween 20, span 60, Tween 60, span 80, Tween 80 or polyoxyethylene 40 stearate.
The preparation method of the water-oil universal mineral oil defoaming agent comprises the following steps:
(1) under the action of an acid catalyst, heating formic acid or acetic acid, hydrogen peroxide and castor oil for reaction, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with water, removing a water phase, and then carrying out alkali washing, water washing and reduced pressure distillation to obtain epoxy castor oil; and then adding the epoxy castor oil and the amino silicone oil into an organic solvent, adding an alkaline catalyst into the organic solvent, stirring the mixture to react for 8 to 12 hours at the temperature of between 60 and 80 ℃, centrifuging the mixture to obtain a supernatant, and performing rotary evaporation to remove the organic solvent to obtain the amino silicone oil modified epoxy castor oil.
(2) Adding mineral oil, amino silicone oil modified epoxy castor oil, a defoaming substance, a defoaming auxiliary agent, hydrophobic white carbon black and an emulsifier into a reaction kettle in sequence according to a ratio, stirring and dispersing the system uniformly, heating to 70-80 ℃, stirring for 1-2 hours, then preserving heat for 1-2 hours, cooling to 40-50 ℃, stirring for 1-2 hours, and finally cooling to room temperature to obtain the mineral oil defoaming agent.
Wherein in the step (1), the molar use ratio of the formic acid or the acetic acid to the hydrogen peroxide to the castor oil is 3: 8-10: 6-8.
Wherein in the step (1), the heating reaction temperature is 60-70 ℃, and the heating reaction time is 3-6 hours.
Wherein, in the step (1), the acid catalyst is concentrated sulfuric acid, and the amount of the concentrated sulfuric acid required by adding 1mol of formic acid or acetic acid is 0.3-0.5 mL. Concentrated sulfuric acid is used as a catalyst to facilitate the formation of peroxy acid, but the use amount of the concentrated sulfuric acid is too small, the catalytic effect is not strong, the required reaction time is long, the epoxy bonds of the obtained epoxy castor oil are few, and the improvement of the defoaming performance is not facilitated; however, if the amount is too large, the castor oil may be carbonized.
Wherein in the step (1), the mass fraction of the concentrated sulfuric acid is 95-98%.
In the step (1), the molar use ratio of the epoxy castor oil to the amino silicone oil is 1: 3-5.
Wherein, in the step (1), the amount of the basic catalyst required by adding 1mol of epoxy castor oil to react with the amino silicone oil is 0.5-1.0 mL.
Wherein, in the step (1), the alkaline catalyst is at least one of sodium hydroxide and potassium hydroxide.
Wherein, in the step (1), the organic solvent is selected from one of absolute ethyl alcohol, N dimethylformamide, tetrahydrofuran, benzene and toluene.
Ricinoleic acid in castor oil has a hydrophilic group and a hydrophobic group, but the long carbon chain structure of the ricinoleic acid causes poor hydrophilicity, poor dispersibility in a water phase and poor defoaming capability. The amino silicone oil modified epoxy castor oil is applied to the preparation of the defoaming agent, and is compounded with the mineral oil, the defoaming substance, the defoaming auxiliary agent, the hydrophobic white carbon black and the emulsifier to obtain the novel water-oil universal mineral oil defoaming agent.
Specific examples are given below to further illustrate the preparation of the present invention. The reagents used in the following examples are all commercially available.
Example 1
The preparation method of the water-oil universal mineral oil defoaming agent in the embodiment comprises the following steps:
(1) mixing the components in a molar ratio of 3: 8: placing 6 formic acid, hydrogen peroxide and castor oil into a reaction kettle, adding concentrated sulfuric acid (0.3 mL of concentrated sulfuric acid needs to be added correspondingly to 1mol of formic acid), heating to 60 ℃, reacting for 6 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain epoxy castor oil; then adding the epoxy castor oil and the amino silicone oil (the molar ratio is 1:3) into N, N dimethyl formamide, adding sodium hydroxide (0.5 mL of sodium hydroxide needs to be correspondingly added to 1mol of epoxy castor oil), stirring and reacting for 12 hours at 60 ℃, centrifuging to obtain a supernatant, and performing rotary evaporation to remove the N, N dimethyl formamide to obtain the amino silicone oil modified epoxy castor oil.
(2) Adding 40 parts of white oil, 40 parts of amino silicone oil modified epoxy castor oil, 2 parts of aluminum butyrate, 0.5 part of polyether, 5 parts of hydrophobic white carbon black and 801 parts of span into a reaction kettle in sequence, stirring and dispersing the system uniformly, heating to 70 ℃, stirring for 2 hours, then preserving heat for 2 hours, cooling to 40 ℃, stirring for 2 hours, and finally cooling to room temperature to obtain the mineral oil defoamer.
Example 2
The preparation method of the water-oil universal mineral oil defoaming agent in the embodiment comprises the following steps:
(1) mixing the components in a molar ratio of 3: 10: placing 8 formic acid, hydrogen peroxide and castor oil in a reaction kettle, adding concentrated sulfuric acid (0.5 mL of concentrated sulfuric acid needs to be correspondingly added to 1mol of formic acid), heating to 70 ℃, reacting for 3 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain epoxy castor oil; then adding the epoxy castor oil and the amino silicone oil (the molar ratio is 1:5) into N, N dimethyl formamide, adding sodium hydroxide (1mol of epoxy castor oil needs to be added with 1.0mL of sodium hydroxide correspondingly), stirring and reacting for 8-12 hours at 60-80 ℃, centrifuging to obtain supernatant, and removing the N, N dimethyl formamide through rotary evaporation to obtain the amino silicone oil modified epoxy castor oil.
(2) Adding 60 parts of liquid paraffin, 60 parts of amino silicone oil modified epoxy castor oil, 5 parts of aluminum octoate, 5 parts of ethylene bis-stearamide, 5 parts of triethanolamine, 1 part of hydrophobic white carbon black and 8010 parts of span into a reaction kettle in sequence, stirring and dispersing the system uniformly, heating to 80 ℃, stirring for 1 hour, then preserving heat for 1 hour, cooling to 50 ℃, stirring for 1 hour, and finally cooling to room temperature to obtain the mineral oil defoamer.
Example 3
The preparation method of the water-oil universal mineral oil defoaming agent in the embodiment comprises the following steps:
(1) mixing the components in a molar ratio of 3: 8: placing 8 formic acid, hydrogen peroxide and castor oil in a reaction kettle, adding concentrated sulfuric acid (0.4 mL of concentrated sulfuric acid needs to be correspondingly added for 1mol of formic acid), heating to 70 ℃, reacting for 5 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain epoxy castor oil; then adding the epoxy castor oil and the amino silicone oil (the molar ratio is 1:4) into N, N dimethyl formamide, adding sodium hydroxide (0.6 mL of sodium hydroxide needs to be correspondingly added to 1mol of epoxy castor oil), stirring and reacting for 10 hours at 70 ℃, centrifuging to obtain a supernatant, and performing rotary evaporation to remove the N, N dimethyl formamide to obtain the amino silicone oil modified epoxy castor oil.
(2) And sequentially adding 50 parts of alkylbenzene, 60 parts of amino silicone oil modified epoxy castor oil, 3 parts of ethylene bis-stearamide, 3 parts of triethanolamine, 3 parts of hydrophobic white carbon black and 603 parts of tween into a reaction kettle, stirring and dispersing the system uniformly, heating to 80 ℃, stirring for 2 hours, then preserving heat for 1 hour, cooling to 40 ℃, stirring for 1 hour, and finally cooling to room temperature to obtain the mineral oil defoamer.
Example 4
The preparation method of the water-oil universal mineral oil defoaming agent in the embodiment comprises the following steps:
(1) mixing the components in a molar ratio of 3: 9: placing 7 formic acid, hydrogen peroxide and castor oil in a reaction kettle, adding concentrated sulfuric acid (0.4 mL of concentrated sulfuric acid needs to be added correspondingly to 1mol of formic acid), heating to 60 ℃, reacting for 4 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain epoxy castor oil; then adding the epoxy castor oil and the amino silicone oil (the molar ratio is 1:3) into N, N dimethyl formamide, adding sodium hydroxide (0.8 mL of sodium hydroxide needs to be correspondingly added to 1mol of epoxy castor oil), stirring and reacting for 8 hours at 80 ℃, centrifuging to obtain a supernatant, and performing rotary evaporation to remove the N, N dimethyl formamide to obtain the amino silicone oil modified epoxy castor oil.
(2) Adding 40 parts of white oil, 60 parts of amino silicone oil modified epoxy castor oil, 5 parts of aluminum octoate, 5 parts of polyether, 5 parts of hydrophobic white carbon black and 805 parts of span into a reaction kettle in sequence, stirring and dispersing the system uniformly, heating to 70 ℃, stirring for 2 hours, then preserving heat for 1 hour, cooling to 50 ℃, stirring for 1 hour, and finally cooling to room temperature to obtain the mineral oil defoamer.
Example 5
The preparation method of the water-oil universal mineral oil defoaming agent in the embodiment comprises the following steps:
(1) mixing the components in a molar ratio of 3: 8: placing 8 formic acid, hydrogen peroxide and castor oil in a reaction kettle, adding concentrated sulfuric acid (0.5 mL of concentrated sulfuric acid needs to be correspondingly added to 1mol of formic acid), heating to 60 ℃, reacting for 6 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain epoxy castor oil; then adding the epoxy castor oil and the amino silicone oil (the molar ratio is 1:5) into N, N dimethyl formamide, adding sodium hydroxide (1mol of epoxy castor oil needs to be added with 1.0mL of sodium hydroxide correspondingly), stirring and reacting for 10 hours at 70 ℃, centrifuging to obtain a supernatant, and performing rotary evaporation to remove the N, N dimethyl formamide to obtain the amino silicone oil modified epoxy castor oil.
(2) Adding 50 parts of white oil, 40 parts of amino silicone oil modified epoxy castor oil, 4 parts of aluminum butyrate, 4 parts of ethylene bis-stearamide, 4 parts of polyether, 8 parts of hydrophobic white carbon black and 808 parts of span into a reaction kettle in sequence, stirring and dispersing the system uniformly, heating to 80 ℃, stirring for 1 hour, then preserving heat for 1 hour, cooling to 50 ℃, stirring for 2 hours, and finally cooling to room temperature to obtain the mineral oil defoamer.
Example 6
The preparation method of the water-oil universal mineral oil defoaming agent in the embodiment comprises the following steps:
(1) mixing the components in a molar ratio of 3: 8: placing 8 acetic acid, hydrogen peroxide and castor oil in a reaction kettle, adding concentrated sulfuric acid (0.5 mL of concentrated sulfuric acid needs to be correspondingly added to 1mol of formic acid), heating to 60 ℃, reacting for 6 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain epoxy castor oil; then adding the epoxy castor oil and the amino silicone oil (the molar ratio is 1:5) into N, N dimethyl formamide, adding sodium hydroxide (1mol of epoxy castor oil needs to be added with 1.0mL of sodium hydroxide correspondingly), stirring and reacting for 10 hours at 70 ℃, centrifuging to obtain a supernatant, and performing rotary evaporation to remove the N, N dimethyl formamide to obtain the amino silicone oil modified epoxy castor oil.
(2) Adding 50 parts of liquid paraffin, 40 parts of amino silicone oil modified epoxy castor oil, 4 parts of aluminum butyrate, 4 parts of ethylene bis-stearamide, 4 parts of triethanolamine, 8 parts of hydrophobic white carbon black and 208 parts of span into a reaction kettle in sequence, stirring and dispersing the system uniformly, heating to 80 ℃, stirring for 1 hour, then preserving heat for 1 hour, cooling to 50 ℃, stirring for 2 hours, and finally cooling to room temperature to obtain the mineral oil defoamer.
Comparative example 1
The preparation method of the mineral oil defoamer in the comparative example is as follows:
(1) mixing the components in a molar ratio of 3: 8: placing 8 acetic acid, hydrogen peroxide and castor oil in a reaction kettle, adding concentrated sulfuric acid (0.5 mL of concentrated sulfuric acid needs to be correspondingly added to 1mol of formic acid), heating to 60 ℃, reacting for 6 hours, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with hot distilled water (50-60 ℃), discarding a water phase, neutralizing with sodium hydroxide, washing with distilled water, and carrying out reduced pressure distillation to obtain the epoxy castor oil.
(2) Adding 50 parts of liquid paraffin, 40 parts of epoxy castor oil, 4 parts of aluminum butyrate, 4 parts of ethylene bis-stearamide, 4 parts of triethanolamine, 8 parts of hydrophobic white carbon black and 208 parts of span into a reaction kettle in sequence, stirring and dispersing the system uniformly, heating to 80 ℃, stirring for 1 hour, then preserving heat for 1 hour, cooling to 50 ℃, stirring for 2 hours, and finally cooling to room temperature to obtain the mineral oil defoamer.
Comparative example 2
The preparation method of the mineral oil defoamer in the comparative example is as follows:
adding 50 parts of liquid paraffin, 40 parts of castor oil, 4 parts of aluminum butyrate, 4 parts of ethylene bis-stearamide, 4 parts of triethanolamine, 8 parts of hydrophobic white carbon black and 208 parts of span into a reaction kettle in sequence, stirring and dispersing the system uniformly, heating to 80 ℃, stirring for 1 hour, then preserving heat for 1 hour, cooling to 50 ℃, stirring for 2 hours, and finally cooling to room temperature to obtain the mineral oil defoamer.
The defoaming performance of the mineral oil DEFOAMERs of examples 1 to 6 and comparative examples 1 to 2 was tested and compared with that of commercially available DEFOAMERs (silicone DEFOAMER, BYK-023, Germany, and SN-DEFAOAMER NXZ DEFOAMER for water-borne coatings, Germany). The specific test method is as follows:
200g of emulsion (pure acrylic emulsion: styrene-acrylic emulsion ═ 1:1) and 0.3g of defoamer were added to a 1000mL plastic cup, dispersed at a high speed of 1500rpm for 15min, then immediately the emulsion in the beaker was introduced into a 500mL measuring cylinder (cylinder weighed beforehand, indicated as M), the volume of the emulsion was read, indicated as V, and the total weight of the cylinder and the emulsion was weighed, indicated as M, and the dispersion density (g/mL) of the emulsion was equal to (M-M)/V. The larger the dispersion density, the better the defoaming effect of the defoaming agent. The test results were as follows:
TABLE 1 Dispersion Density of mineral oil defoamers in examples 1 to 6
As can be seen from the test results in Table 1, the defoaming performance of the mineral oil defoaming agents prepared in examples 1 to 6 of the present invention is superior to that of the mineral oil defoaming agents in comparative examples 1 to 2 and two defoaming agents purchased from the market, which indicates that the defoaming performance of the mineral oil defoaming agent of the present invention is excellent and the modification of castor oil effectively improves the defoaming capability of the mineral oil defoaming agent.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. The water-oil universal mineral oil defoaming agent is characterized by comprising the following components in parts by weight: 40-60 parts of mineral oil, 40-60 parts of amino silicone oil modified epoxy castor oil, 2-10 parts of defoaming substances, 0.5-5 parts of defoaming auxiliaries, 1-10 parts of hydrophobic white carbon black and 0.1-10 parts of emulsifier, wherein the preparation method of the amino silicone oil modified epoxy castor oil comprises the following steps:
adding epoxy castor oil and amino silicone oil into an organic solvent, adding an alkaline catalyst into the organic solvent, stirring the mixture to react for 8 to 12 hours at the temperature of between 60 and 80 ℃, centrifuging the mixture to obtain supernatant, and performing rotary evaporation to remove the organic solvent to obtain the amino silicone oil modified epoxy castor oil.
2. The water and oil universal mineral oil defoamer as set forth in claim 1, wherein: the molar ratio of the epoxy castor oil to the amino silicone oil is 1: 3-5;
and/or adding 0.5-1.0mL of alkaline catalyst required by the reaction of 1mol of epoxy castor oil and amino silicone oil;
and/or, the alkaline catalyst is selected from at least one of sodium hydroxide and potassium hydroxide;
and/or the organic solvent is selected from one of absolute ethyl alcohol, N dimethylformamide, tetrahydrofuran, benzene and toluene.
3. The water and oil universal mineral oil defoamer as set forth in claim 1, wherein: the preparation method of the epoxy castor oil comprises the following steps: under the action of an acid catalyst, heating formic acid or acetic acid, hydrogen peroxide and castor oil for reaction, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with water, removing a water phase, and then carrying out alkali washing, water washing and reduced pressure distillation to obtain the epoxy castor oil.
4. The water and oil universal mineral oil defoamer as set forth in claim 3, wherein: the molar ratio of the formic acid or the acetic acid to the hydrogen peroxide to the castor oil is 3: 8-10: 6-8;
and/or the heating reaction temperature is 60-70 ℃, and the heating reaction time is 3-6 hours;
and/or the acid catalyst is concentrated sulfuric acid, and the amount of the concentrated sulfuric acid required by adding 1mol of formic acid or acetic acid is 0.3-0.5 mL;
and/or the mass fraction of the concentrated sulfuric acid is 95-98%.
5. The water and oil universal mineral oil defoamer as set forth in claim 1, wherein: the mineral oil is at least one of white oil, liquid paraffin and alkylbenzene;
and/or the defoaming substance is at least one of fatty acid metal soap and fatty acid amide;
and/or the defoaming auxiliary agent is selected from at least one of polyether, triethanolamine, n-octanol and isooctanol;
and/or the emulsifier is at least one selected from span 20, tween 20, span 60, tween 60, span 80, tween 80 and polyoxyethylene 40 stearate.
6. The water and oil universal mineral oil defoamer as set forth in claim 5, wherein: the fatty acid metal soap is selected from at least one of aluminum monofatty acid and aluminum bisfatty acid, the aluminum monofatty acid is selected from at least one of aluminum butyrate, aluminum caprylate, aluminum tetradecanoate, aluminum pentadecanoate, aluminum hexadecanoate, aluminum heptadecane, aluminum octadecanoate, aluminum nonadecane, aluminum eicosanoate, aluminum docosane, aluminum triacontanoate, aluminum tetradecanoate, aluminum docosenoate, and the aluminum bisfatty acid is selected from at least one of aluminum dibutyrate, aluminum dioctanoate, aluminum dimyristate, aluminum dipentanoate, aluminum dihexadecanoate, aluminum diheptadecanoate, aluminum dioctadecylate, aluminum didodecanoate, aluminum dicetylenoate, and aluminum dioctadecenoate;
and/or the fatty acid amide is selected from at least one of ethylene bis stearamide, ethylene bis palmitamide, ethylene bis myristamide, ethylene bis laurate amide, ethylene bis oleamide, propylene bis stearamide, propylene bis palmitamide, propylene bis myristamide, propylene bis laurate amide, propylene bis oleamide, butylene bis stearamide, butylene bis palmitamide, butylene bis myristamide, butylene bis laurate amide and butylene bis oleamide.
7. The method for producing the mineral oil antifoaming agent for water and oil use according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
(1) adding epoxy castor oil and amino silicone oil into an organic solvent, adding an alkaline catalyst into the organic solvent, stirring the mixture to react for 8 to 12 hours at the temperature of between 60 and 80 ℃, centrifuging the mixture to obtain supernatant, and performing rotary evaporation to remove the organic solvent to obtain amino silicone oil modified epoxy castor oil;
(2) adding mineral oil, amino silicone oil modified epoxy castor oil, a defoaming substance, a defoaming auxiliary agent, hydrophobic white carbon black and an emulsifier into a reaction kettle in sequence according to a ratio, stirring and dispersing the system uniformly, heating to 70-80 ℃, stirring for 1-2 hours, then preserving heat for 1-2 hours, cooling to 40-50 ℃, stirring for 1-2 hours, and finally cooling to room temperature to obtain the mineral oil defoaming agent.
8. The method of claim 7, wherein: in the step (1), the molar use ratio of the epoxy castor oil to the amino silicone oil is 1: 3-5;
and/or, in the step (1), the amount of the basic catalyst required by the reaction of 1mol of epoxy castor oil and amino silicone oil is 0.5-1.0 mL;
and/or, in the step (1), the alkaline catalyst is selected from at least one of sodium hydroxide and potassium hydroxide;
and/or in the step (1), the organic solvent is selected from one of absolute ethyl alcohol, N-dimethylformamide, tetrahydrofuran, benzene and toluene.
9. The method of claim 7, wherein: in the step (1), the preparation method of the epoxy castor oil comprises the following steps: under the action of an acid catalyst, heating formic acid or acetic acid, hydrogen peroxide and castor oil for reaction, transferring a product into a separating funnel after the reaction is finished, separating to obtain an upper oil phase, washing the upper oil phase with water, removing a water phase, and then carrying out alkali washing, water washing and reduced pressure distillation to obtain the epoxy castor oil.
10. The method of claim 9, wherein: the molar ratio of the formic acid or the acetic acid to the hydrogen peroxide to the castor oil is 3: 8-10: 6-8;
and/or the heating reaction temperature is 60-70 ℃, and the heating reaction time is 3-6 hours;
and/or the acid catalyst is concentrated sulfuric acid, and the amount of the concentrated sulfuric acid required by adding 1mol of formic acid or acetic acid is 0.3-0.5 mL;
and/or the mass fraction of the concentrated sulfuric acid is 95-98%.
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