Process for preparing an amide mineral oil type antifoam

Abstract

The present application aims to provide a preparation method of an amide mineral oil type defoaming agent, which comprises the following steps: firstly, mixing hydrophobic white carbon black and fatty acid amide in part of mineral oil, grinding by a colloid mill, reducing the late large particle phenomenon of the fatty acid amide, improving the defoaming performance, heating the dispersion liquid to 5-10 DEG C above the melting point of the fatty acid amide after grinding, then adding the dispersion liquid into the mineral oil and rapidly cooling, reducing the temperature to 5-10 DEG C above the condensation point of the fatty acid amide, avoiding the system viscosity rising and stratification caused by the fatty acid amide gel, and improving the stability of the product.

Description

Technical Field

[0001] This patent mainly relates to a method for preparing an amide-based mineral oil defoamer. Defoamers belong to fine chemicals, therefore, this invention belongs to the field of fine chemical technology. Background Technology

[0002] Defoamers are fine chemicals widely used in various industrial fields. When using them, defoamers must not only possess excellent defoaming and foam-suppressing properties and stability, but also excellent compatibility with other additives. Defoamers are mainly divided into silicone defoamers and non-silicone defoamers. Non-silicone defoamers are generally composed of fatty alcohols, fatty acid esters, metal soaps, fatty acid amides, polyethers, mineral oils, etc. Because their surface tension is higher than that of silicone oils, they do not easily spread on the foam surface, and therefore their defoaming and foam-suppressing performance is generally not as good as that of silicone defoamers. However, they have better compatibility with organic systems, and therefore are often used in coatings, inks, papermaking, adhesives, and other systems.

[0003] There is a wealth of literature introducing amide-based mineral oil defoamers. US4094812 describes a type containing... α Methods for preparing mineral oil-based defoamers containing hydroxylamine derivatives; US3652452 describes a defoamer composed of rapidly cooled amines and organic hydrocarbons; CN101445760 describes a defoamer composed of ethylene bis-stearamide, organic hydrocarbons, and hydrophilic silica; CN101003644 describes a defoamer for peritoneal adhesives composed of organic hydrocarbons and fatty acid amides; CN101445760A utilizes inorganic particles and / or fatty acid amides as the main defoaming agents, and increases product stability by adding hydrophilic inorganic particles to increase the viscosity of the system; CN1762531A utilizes fatty acid amides, silicone resins, silica, etc. as defoaming agents, and adds specially modified silicone polyethers to improve the defoaming and foam-suppressing performance and safety stability of the defoamer.

[0004] In the preparation of mineral oil-based defoamers, when fatty acid amides are used as hydrophobic particles, large amide particles appear in the resulting defoamer, affecting its defoaming and foam-suppressing performance. Through extensive experimental research, the inventors of this patent discovered that mixing fatty acid amides and hydrophobic silica as defoaming substances and grinding them at high speed reduces the large particle phenomenon of fatty acid amides. At the same time, temperature control of the heating and cooling of the mixture improves the stability and defoaming and foam-suppressing performance of the defoamer. The final defoamer has good application effects in papermaking black liquor, coatings, coating, sewage treatment, latex, and cleaning processes. Summary of the Invention

[0005] The present application aims to provide a preparation method of an amide mineral oil type defoaming agent. First, hydrophobic white carbon black and fatty acid amide are mixed in part of mineral oil and ground by a colloid mill to reduce the late large particle phenomenon of fatty acid amide, improve the defoaming performance, and then the dispersion liquid after grinding is heated to 5-10℃ above the melting point of fatty acid amide, and then the dispersion liquid is added to the mineral oil for rapid cooling, the temperature is reduced to 5-10℃ above the condensation point of fatty acid amide, to avoid the system viscosity rising and stratification caused by fatty acid amide gel, and improve the stability of the product.

[0006] The amide mineral oil type defoaming agent provided by the present application is composed of the following components:

[0007] A, mineral oil

[0008] The mineral oil is used as a carrier and is selected from kerosene, diesel oil, engine oil, white oil, liquid wax and alkylbenzene; these mineral oils are liquid at room temperature and are used in an amount of 60-80% of the total mass of the defoaming agent; the mineral oil is composed of two parts A1 and A2: mineral oil A1, which is used in an amount of 30-50% of the total mass of the mineral oil; and mineral oil A2, which is used in an amount of 50-70% of the total mass of the mineral oil; the mineral oil A1 and the mineral oil A2 can be the same or different.

[0009] B, defoaming substance

[0010] The defoaming substance is composed of fatty acid amide and white carbon black.

[0011] B1: fatty acid amide, which is selected from one or more of ethylene bis-stearamide (abbreviated as EBS), ethylene bis-palmitamide, ethylene bis-myristamide, ethylene bis-lauramide, ethylene bis-oleamide, propylene bis-stearamide, propylene bis-palmitamide, propylene bis-myristamide, propylene bis-lauramide, propylene bis-oleamide, butylene bis-stearamide, butylene bis-palmitamide, butylene bis-myristamide, butylene bis-lauramide and butylene bis-oleamide; preferably ethylene bis-stearamide and ethylene bis-lauramide; the amount of fatty acid amide is 3-10% of the total mass of the defoaming agent.

[0012] B2: white carbon black

[0013] The white carbon black is selected from precipitated hydrophobic white carbon black and fumed hydrophobic white carbon black, and preferably fumed hydrophobic white carbon black, which has a specific surface area of 20-500 m 2 / g; and is used in an amount of 0.5-10% of the total mass of the defoaming agent.

[0014] C, defoaming aid

[0015] The defoaming aid is a polyether, and the general structure of the polyether is as follows:

[0016] RO(EO) x(PO) y H

[0017] wherein subscript x is an integer from 1 to 100, y is an integer from 1 to 200; R is an alkyl group; the alkyl group is a branched or straight chain alkyl group having a carbon number of 4 to 20, including butyl, iso-butyl, octyl, iso-octyl, dodecyl, tetradecyl, hexadecyl, octadecyl; the defoaming aid accounts for 1 to 20% of the total mass of the defoaming agent.

[0018] D, emulsifier

[0019] The emulsifier is a non-ionic surfactant, and the non-ionic surfactant is selected from the group consisting of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ether, polyoxyethylene fatty amine compound, castor oil polyoxyethylene ether, polyoxyethylene sorbitan monolaurate (Tween-20), polyoxyethylene sorbitan monopalmitate (Tween-40), polyoxyethylene sorbitan monostearate (Tween-60), polyoxyethylene sorbitan monooleate (Tween-80), polyoxyethylene sorbitan trioleate (Tween-85), sorbitan monolaurate (Span-20), sorbitan monopalmitate (Span-40), sorbitan monostearate (Span-60), sorbitan monooleate (Span-80), used alone or in combination; the amount of emulsifier is 3 to 20% of the total mass of the defoaming agent.

[0020] On the basis of the above-mentioned substances, an amide mineral oil defoaming agent is prepared, and the implementation steps are as follows:

[0021] (1) Mix and stir the mineral oil A1, the defoaming aid C, the defoaming substance B1 and the defoaming substance B2 uniformly, and then continue to disperse by colloid mill grinding; form a mixture X;

[0022] (2) Heat the mixture X in a closed container, and based on the melting point B1 mp of the defoaming substance B1, raise the temperature to [B1 mp +(5-10)]℃, and after stirring for a period of time, add the heated mixture X into the mineral oil A2 and cool quickly, based on the condensation point B1 fp of the defoaming substance B1, lower the temperature to [B1 fp +(5-10)]℃, and form a mixture Y;

[0023] (3) Continue to add the emulsifier to the mixture Y, and lower to room temperature while stirring, to obtain the mineral oil defoaming agent. DETAILED DESCRIPTION Example 1

[0024] (1) Mix 30g of white oil, 10g of defoaming aid C 18H 37 O(EO) 20 (PO) 40 H, 10 g defoaming substance ethylene bis-stearamide, 10 g defoaming substance fumed hydrophobic white carbon black (specific surface area 200 m 2 / g) are mixed and stirred uniformly, and then ground by a colloid mill to continue dispersing; to form a mixture X1;

[0025] (2) The mixture X1 is heated in a closed container, and the temperature is raised to (B1 mp + 5) °C based on the melting point B1 mp of the defoaming substance ethylene bis-stearamide, and after stirring for a period of time, the heated mixture X1 is added to 30 g white oil and rapidly cooled, and the temperature is lowered to (B1 fp + 8) °C based on the condensation point B1 fp of the defoaming substance ethylene bis-stearamide, to form a mixture Y1;

[0026] (3) 10 g of the emulsifier fatty alcohol polyoxyethylene ether is continuously added to the mixture Y1, and the temperature is lowered to room temperature while stirring, to obtain the mineral oil defoaming agent. Example 2

[0027] (1) 28 g of kerosene, 20 g of the defoaming aid C 20 H 41 O(EO)5(PO) 20 H, 5 g of the defoaming substance ethylene bis-lauramide, 2 g of the defoaming substance fumed hydrophobic white carbon black (specific surface area 500 m 2 / g) are mixed and stirred uniformly, and then ground by a colloid mill to continue dispersing; to form a mixture X2;

[0028] (2) The mixture X2 is heated in a closed container, and the temperature is raised to (B1 mp + 6) °C based on the melting point B1 mp of the defoaming substance ethylene bis-lauramide, and after stirring for a period of time, the heated mixture X2 is added to 42 g of kerosene and rapidly cooled, and the temperature is lowered to (B1 fp + 9) °C based on the condensation point B1 fp of the defoaming substance ethylene bis-lauramide, to form a mixture Y2;

[0029] (3) 3 g of the emulsifier fatty acid polyoxyethylene ether and castor oil polyoxyethylene ether mixture is continuously added to the mixture Y2, and the temperature is lowered to room temperature while stirring, to obtain the mineral oil defoaming agent. Example 3

[0030] (1) 24 g of machine oil, 1 g of the defoaming aid C 16 H33 O (EO) 30 (PO) 60 H, 3 g of defoaming aid ethylene bis-palmitic acid amide and ethylene bis-myristic acid amide mixture, 0.5 g of defoaming aid precipitated hydrophobic white carbon black (specific surface area 300 m 2 / g) were mixed and stirred uniformly, and then ground by a colloid mill to continue the dispersion; to form mixture X3;

[0031] (2) The mixture X3 was heated in a closed container, and the temperature was raised to (B1 mp + 7) °C based on the melting point B1 mp of the defoaming aid ethylene bis-palmitic acid amide and ethylene bis-myristic acid amide mixture, and after stirring for a period of time, the heated mixture X3 was added to 56 g of white oil and rapidly cooled to (B1 fp + 10) °C based on the condensation point B1 fp of the defoaming aid ethylene bis-palmitic acid amide and ethylene bis-myristic acid amide mixture, to form mixture Y3;

[0032] (3) 15.5 g of a mixture of emulsifiers Tween-20 and Span-20 were further added to the mixture Y3, and the temperature was lowered to room temperature while stirring, to obtain the mineral oil defoaming agent. Example 4

[0033] (1) 20 g of liquid wax, 3 g of defoaming aid C 14 H 29 O (EO) 10 (PO) 25 H, 8 g of defoaming aid ethylene bis-oleic acid amide and propylene bis-stearic acid amide mixture, 4 g of defoaming aid precipitated hydrophobic white carbon black (specific surface area 20 m 2 / g) were mixed and stirred uniformly, and then ground by a colloid mill to continue the dispersion; to form mixture X4;

[0034] (2) The mixture X4 was heated in a closed container, and the temperature was raised to (B1 mp + 8) °C based on the melting point B1 mp of the defoaming aid ethylene bis-oleic acid amide and propylene bis-stearic acid amide mixture, and after stirring for a period of time, the heated mixture X4 was added to 45 g of alkylbenzene and rapidly cooled to (B1 fp + 7) °C based on the condensation point B1 fp of the defoaming aid ethylene bis-oleic acid amide and propylene bis-stearic acid amide mixture, to form mixture Y4;

[0035] (3) Continue to add 20g of a mixture of emulsifiers Tween-40 and Spande-40 to mixture Y4, and cool to room temperature while stirring to obtain the mineral oil defoamer. Example 5

[0036] (1) Add 30g alkylbenzene and 8g defoaming agent C 12 H 23 O(EO) 20 (PO) 50 H, 6g of defoaming agent, a mixture of propylene bispalmitamide and propylene bismyristamide, and 8g of defoaming agent, fumed silica (specific surface area 50m²). 2 Mix (g) thoroughly and then further disperse by grinding with a colloid mill to form mixture X5;

[0037] (2) Heat mixture X5 in a sealed container to determine the melting point B1 of the mixture of the defoaming substances propylene bispalmitamide and propylene bismyristamide. mp Based on ℃, raise the temperature to (B1) mp After stirring at +9)℃ for a period of time, add the heated mixture X5 to 40g of white oil and cool rapidly to determine the condensation point B1 of the mixture of the defoaming substances propylene bispalmitamide and propylene bismyristamide. fp Based on ℃, cool down to (B1) fp +6)℃, forming mixture Y5;

[0038] (3) Continue to add 8g of a mixture of emulsifiers Tween-60 and Spande-60 to mixture Y5, and cool to room temperature while stirring to obtain the mineral oil defoamer. Example 6

[0039] (1) Add 35g of white oil and 15g of defoaming agent C8H 17 O(EO) 15 (PO) 35 H, 4g of defoaming agent (a mixture of propylene dilaurate and propylene dioleate), 1g of defoaming agent (hydrophobic silica produced by fumed silica method, with a specific surface area of ​​100m²). 2 Mix (g) thoroughly and then further disperse by grinding with a colloid mill to form mixture X6;

[0040] (2) Heat mixture X6 in a sealed container to determine the melting point B1 of the mixture of the defoaming substances propylene dilaurylamide and propylene dioleoylamine. mp Based on ℃, raise the temperature to (B1) mp +10)℃, after stirring for a period of time, add the heated mixture X6 to 40g of liquid wax and cool rapidly to determine the condensation point B1 of the mixture of defoaming substances propylene dilaurylamide and propylene dioleoylamine.fp °C as a reference, to (B1 fp +5) °C, to form mixture Y6;

[0041] (3) Continue to add 5 g of a mixture of emulsifiers Tween-80 and Span-80 to mixture Y6 while stirring and allow to cool to room temperature to obtain the mineral oil antifoam agent. Example 7

[0042] (1) Mix 35 g of liquid wax, 15 g of antifoam aid C4H9O(EO) 15 (PO) 35 H, 4 g of antifoam substance butylene bis-stearamide and butylene bis-palmitamide mixture, 1 g of antifoam substance precipitated hydrophobic silica (with a specific surface area of 400 m 2 / g) and stir until uniform, then continue to disperse by grinding in a colloid mill; to form mixture X7;

[0043] (2) Heat mixture X7 in a closed container to the melting point B1 mp °C as a reference for the antifoam substance butylene bis-stearamide and butylene bis-palmitamide mixture, raise the temperature to (B1 mp +8) °C, after stirring for a period of time, add the heated mixture X7 to 40 g of liquid wax and cool rapidly to the condensation point B1 fp °C as a reference for the antifoam substance butylene bis-stearamide and butylene bis-palmitamide mixture, to (B1 fp +6) °C, to form mixture Y7;

[0044] (3) Continue to add 5 g of a mixture of emulsifiers Tween-85 and Span-80 to mixture Y7 while stirring and allow to cool to room temperature to obtain the mineral oil antifoam agent.

[0045] Comparative Example 1

[0046] (1) Mix 30 g of white oil, 10 g of antifoam aid C 18 H 37 O(EO) 20 (PO) 40 H, 10 g of antifoam substance ethylene bis-stearamide, 10 g of antifoam substance fumed hydrophobic silica (with a specific surface area of 200 m 2 / g) and stir until uniform, then continue to disperse by grinding in a colloid mill; to form mixture X1; (2) Heat mixture X1 in a closed container to the melting point B1 mp °C as a reference for the antifoam substance ethylene bis-stearamide, raise the temperature to less than (B1 mp+5) °C, after stirring for a period of time, the heated mixture X1 is added to 30 g of white oil and rapidly cooled to defoaming point B1 of the defoaming substance ethylene bis-stearamide fp °C as a reference, the temperature is lowered to (B1 fp +8) °C, forming mixture Y8;

[0047] (3) 10 g of the emulsifier fatty alcohol polyoxyethylene ether is continuously added to the mixture Y8 while stirring and lowered to room temperature to obtain the mineral oil defoamer. Comparative Example 2

[0048] (1) 28 g of kerosene, 20 g of the defoaming aid C 20 H 41 O (EO) 5 (PO) 20 H, 5 g of the defoaming substance ethylene bis-lauramide, 2 g of the defoaming substance fumed hydrophobic silica (specific surface area 500 m 2 / g) are mixed and stirred until homogeneous, then ground by means of a colloid mill to continue the dispersion; forming mixture X2;

[0049] (2) The mixture X2 is heated in a closed container to the melting point B1 of the defoaming substance ethylene bis-lauramide mp °C as a reference, the temperature is raised to greater than (B1 mp +10) °C, after stirring for a period of time, the heated mixture X2 is added to 42 g of kerosene and rapidly cooled to the condensation point B1 of the defoaming substance ethylene bis-lauramide fp °C as a reference, the temperature is lowered to (B1 fp +9) °C, forming mixture Y9;

[0050] (3) 3 g of the emulsifier mixture of fatty acid polyoxyethylene ether and castor oil polyoxyethylene ether is continuously added to the mixture Y9 while stirring and lowered to room temperature to obtain the mineral oil defoamer. Comparative Example 3

[0051] (1) 20 g of liquid wax, 3 g of the defoaming aid C 14 H 29 O (EO) 10 (PO) 25 H, 8 g of the defoaming substance mixture of ethylene bis-oleic acid amide and propylene bis-stearamide, 4 g of the defoaming substance precipitated hydrophobic silica (specific surface area 20 m 2 / g) are mixed and stirred until homogeneous, then ground by means of a colloid mill to continue the dispersion; forming mixture X4;

[0052] (2) The mixture X4 is heated in a closed container to the melting point B1 of the defoaming substance mixture of ethylene bis-oleic acid amide and propylene bis-stearamide mp°C as a reference, the temperature is raised to (B1 mp +8) °C, after stirring for a period of time, the heated mixture X4 is added to 45 g of alkyl benzene and quickly cooled to condensation point B1 fp °C as a reference, the temperature is lowered to (B1 fp +4) °C, forming mixture Y10;

[0053] (3) Continue to add 20 g of a mixture of emulsifiers Tween-40 and Span-40 to mixture Y10, while stirring and lowering to room temperature to obtain the mineral oil defoamer. Comparative Example 4

[0054] (1) Mix 30 g of alkyl benzene, 8 g of defoaming aid C 12 H 23 O (EO) 20 (PO) 50 H, 6 g of defoaming substance propylene bis-palmitic acid amide and propylene bis-myristic acid amide mixture, 8 g of defoaming substance fumed hydrophobic white carbon black (specific surface area of 50 m 2 / g) and stir until uniform, then continue to disperse by grinding with a colloid mill; form mixture X5;

[0055] (2) Heat mixture X5 in a closed container to the melting point B1 mp °C as a reference, the temperature is raised to (B1 mp +9) °C, after stirring for a period of time, the heated mixture X5 is added to 40 g of white oil and quickly cooled to condensation point B1 fp °C as a reference, the temperature is lowered to (B1 fp +11) °C, forming mixture Y11;

[0056] (3) Continue to add 8 g of a mixture of emulsifiers Tween-60 and Span-60 to mixture Y11, while stirring and lowering to room temperature to obtain the mineral oil defoamer.

[0057] Test Methods

[0058] (1) Defoaming Performance Test

[0059] Test method: in 1000ml stainless steel cup, add self-made water-based paint 200g, then add 0.3% defoaming agent, use laboratory high-speed disperser, at 1000rpm speed, high-speed dispersion for 10min, stop immediately after pouring into 1000ml measuring cylinder, record the weight and volume of liquid, calculate the specific gravity, the larger the specific gravity value, the smaller the gas content, indicating that the defoaming agent has good defoaming performance.

[0060] (2) Compatibility test

[0061] Test method: after placing the above high-speed dispersed paint for 10min, take out a little and place on glass plate, use 75um wet film maker to evenly scrape the paint, observe the state of the coating film, and use grade to express, the higher the grade, the better the compatibility.

[0062] Table 1 coating grade classification

[0063]

[0064] (3) Use Formulaction / Turbiscan Tower / multiple light scattering stability analyzer to test the stability of the sample, the test temperature is 40℃, the sample amount is 20g, the smaller the TSI index in the test result, the better the stability of the sample.

[0065] The test results are as follows:

[0066] (1) Defoaming performance test results:

[0067]

[0068] (2) Compatibility test results:

[0069]

[0070] (3) Stability test results:

[0071]

Claims

1. A method for preparing an amide mineral oil type defoamer, comprising the following components: A, mineral oil; B, defoaming substance; C, defoaming aid; and D, emulsifier. The mineral oil is used as a carrier and is selected from one or more of kerosene, diesel oil, engine oil, white oil, liquid wax, and alkyl benzene; the mineral oil is liquid at room temperature and is used in an amount of 60-80% of the total mass of the defoamer; the mineral oil is composed of two parts, mineral oil A1 and mineral oil A2, which are the same or different. The defoaming substance is composed of a fatty acid amide and white carbon black. The fatty acid amide is selected from one or more of ethylene bis-stearamide (abbreviated as EBS), ethylene bis-palmitamide, ethylene bis-myristamide, ethylene bis-lauramide, ethylene bis-oleamide, propylene bis-stearamide, propylene bis-palmitamide, propylene bis-myristamide, propylene bis-lauramide, propylene bis-oleamide, butylene bis-stearamide, butylene bis-palmitamide, butylene bis-myristamide, butylene bis-lauramide, and butylene bis-oleamide; the fatty acid amide is used in an amount of 3-10% of the total mass of the mineral oil type defoamer. The white carbon black is used in an amount of 0.1-1% of the total mass of the mineral oil type defoamer. The defoaming aid is a polyether having the following general structure: wherein subscript x is an integer of 1-100, subscript y is an integer of 1-200, and R is an alkyl group having 4-20 carbon atoms; the alkyl group is a branched or straight chain alkyl group including butyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; the defoaming aid is used in an amount of 1-20% of the total mass of the defoamer. The white carbon black is selected from the group consisting of precipitated hydrophobic white carbon black and fumed hydrophobic white carbon black, and has a specific surface area of 20-500 m 2 / g; and the amount is 0.5-10% of the total mass of the defoaming agent. The emulsifier is a non-ionic surfactant selected from fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ether, polyoxyethylene fatty amine compound, castor oil polyoxyethylene ether, polyoxyethylene sorbitan monolaurate (Tween-20), polyoxyethylene sorbitan monopalmitate (Tween-40), polyoxyethylene sorbitan monostearate (Tween-60), polyoxyethylene sorbitan monooleate (Tween-80), polyoxyethylene sorbitan trioleate (Tween-85), sorbitan monolaurate (Span-20), sorbitan monopalmitate (Span-40), sorbitan monostearate (Span-60), and sorbitan monooleate (Span-80), which are used alone or in combination; the emulsifier is used in an amount of 3-20% of the total mass of the defoamer. The method for preparing the amide mineral oil type defoamer is as follows: RO (EO) x (PO) y H (1) mixing and stirring mineral oil A1, defoaming aid C, defoaming substance B1, and defoaming substance B2 uniformly, and then grinding and dispersing further by a colloid mill to form a mixture X; (3) adding emulsifier to the mixture Y while stirring and cooling to room temperature to obtain the mineral oil defoamer. The amount of mineral oil A1 is 30-50% of the total mass of the mineral oil; the amount of mineral oil A2 is 50-70% of the total mass of the mineral oil. The fatty acid amide is ethylene bis-stearamide or ethylene bis-lauramide. The white carbon black is a hydrophobic white carbon black prepared by a vapor phase method. (2) The mixture X is heated in a closed vessel to the melting point of the antifoam substance B1 B1 mp °C, the temperature is raised to [B1 mp + (5-10)] °C, after stirring for a certain period of time, the heated mixture X is added to the mineral oil A2 and rapidly cooled to the condensation point of the antifoam substance B1 B1 fp °C, the temperature is lowered to [B1 fp + (5-10)] °C, to form the mixture Y; ​ 2. The preparation method of the amide-based mineral oil defoamer as described in claim 1, characterized in that, ​ 3. The preparation method of the amide-based mineral oil defoamer as described in claim 1, characterized in that, ​ 4. The preparation method of the amide-based mineral oil defoamer as described in claim 1, characterized in that, ​

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