Mineral oil defoamer and its preparation method

Abstract

The present invention discloses a mineral oil defoamer and a preparation method thereof, relating to the technical field of defoamers. Calculated by weight parts, the raw materials for preparing the mineral oil defoamer include 50-90 parts of mineral oil, 5-20 parts of cationic emulsifier, 5-20 parts of non-ionic emulsifier, 1-10 parts of modified silicone polyether, 0.5-5 parts of foam breaker and 0.5-5 parts of thickening stabilizer. The molecular structure of the modified silicone polyether has a polyether-silicone-alkyl structure. The present invention selects a cationic emulsifier and a non-ionic emulsifier as a compound emulsifier, which can improve the emulsifying effect and stability of the defoamer and can be applied to foam elimination in multiple industries. In addition, by adding a modified silicone polyether with a polyether-silicone-alkyl structure, its hydrophilic polyether end can improve the water solubility of the defoamer, and the hydrophobic and lipophilic alkyl structure end can combine well with the mineral oil. The silicone can improve the foam suppression and defoaming performance of the defoamer, so the compatibility of the mineral oil and the speed and persistence of foam suppression and defoaming can be optimized.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical additives, in particular to an antifoaming agent, and more particularly to a mineral oil antifoaming agent and a preparation method thereof. Background Art

[0002] During the production and application processes in fields such as coatings, textiles, medicine, fermentation, papermaking, water treatment, and petrochemical industry, a large amount of foam will be generated, which will in turn affect product quality and the production process. And the foam itself exists in a dynamically stable state and is difficult to eliminate even after long-term static settlement. Currently, the more common method to eliminate foam is to add an antifoaming agent, which is a fine chemical, specifically an additive for eliminating foam.

[0003] Currently, conventional antifoaming agents are mainly silicone antifoaming agents, polyether antifoaming agents, and polyether-modified silicone antifoaming agents. Among them, silicone antifoaming agents and polyether-modified silicone antifoaming agents contain polydimethylsiloxane (silicone oil), and their defoaming effect is very rapid and the action time is continuous. However, their compatibility is poor, which will cause serious cratering in latex paints, and even affect recoatability and poor matching. The polyether antifoaming agent has good compatibility and does not cause other drawbacks, but its effect on the foam of latex paints is not obvious and it cannot achieve the defoaming and foam suppression effects. Summary of the Invention

[0004] Based on the above problems, the purpose of the present invention is to provide a mineral oil antifoaming agent, which has the characteristics of fast defoaming, long-lasting foam suppression, good matching, no cratering, and no influence on product performance, and has a wide market application value, especially suitable for eliminating the foam of latex paints.

[0005] To achieve the above purpose, on the one hand, the present invention provides a mineral oil antifoaming agent. Calculated by weight parts, the preparation raw materials include 50 - 90 parts of mineral oil, 5 - 20 parts of cationic emulsifier, 5 - 20 parts of non-ionic emulsifier, 1 - 10 parts of modified silicone polyether, 0.5 - 5 parts of defoaming agent, and 0.5 - 5 parts of thickening and stabilizing agent. The molecular structure of the modified silicone polyether has a polyether-siloxane-alkyl structure.

[0006] The defoamer of the present invention is a mineral oil defoamer, whose main component is mineral oil. It has good compatibility with organic systems and strong matching performance, so it can be used in coating products such as latex paints to avoid defects such as cratering. At the same time, among the raw materials for preparing the mineral oil defoamer, selecting cationic emulsifier and non-ionic emulsifier as compound emulsifiers can improve the emulsifying effect and stability of the defoamer, and it can be applied to foam elimination in multiple industries. Specifically, the non-ionic emulsifier has extremely strong emulsifying effect. The cationic emulsifier carries a positive charge, and it will form an arrangement with the hydrophilic group inward and the hydrophobic group outward on the surface of the emulsifier, which can not only improve the emulsifying effect of the non-ionic emulsifier, but also greatly improve the stability of the defoamer, and prevent the precipitation of hydrophobic substances in the defoamer from the mineral oil. In addition, adding a modified silicone polyether with a polyether-siloxane-alkyl structure, the hydrophilic polyether end can improve the water solubility of the defoamer, the hydrophobic and lipophilic alkyl structure end can combine well with the mineral oil, and the siloxane can improve the defoaming and foam suppression performance of the defoamer, so the compatibility of the mineral oil and the speed and persistence of defoaming and foam suppression can be optimized.

[0007] As an embodiment, the mineral oil is selected from at least one of gasoline, kerosene, diesel oil, lubricating oil, light chemical oil, white mineral oil, solvent oil, paraffin wax, alkylbenzene and naphthenic oil.

[0008] As an embodiment, the cationic emulsifier is an alkylamine salt type emulsifier, a quaternary ammonium salt type emulsifier, a heterocyclic type emulsifier or a pyridinium salt type emulsifier.

[0009] As an embodiment, the non-ionic emulsifier is selected from at least one of glycerol monostearate, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene stearyl alcohol ether, fatty alcohol polyoxyethylene ether, condensate of alkylphenol and ethylene oxide, condensate of fatty alcohol and ethylene oxide, and condensate of castor oil, hydrogenated castor oil and ethylene oxide.

[0010] As an embodiment, the modified silicone polyether is prepared from cetyl polyethylene glycol, polypropylene glycol and dimethyl silicone oil.

[0011] As an embodiment, the HLB value of the modified silicone polyether is 4 - 6.

[0012] As an embodiment, the defoaming agent is at least one of fatty acid metal soap, white carbon black, alumina, magnesia and zinc oxide.

[0013] As an embodiment, the thickening and stabilizing agent is modified castor oil and its derivatives and / or bentonite.

[0014] On the other hand, the present invention provides a preparation method of a mineral oil defoamer, including:

[0015] (1) adding the formulated amount of mineral oil, cationic emulsifier, nonionic emulsifier, defoamer and modified silicone polyether to a reaction kettle in sequence, raising the temperature to 100-150° C. while stirring, and keeping the temperature for 1-5 hours to obtain a first mixture;

[0016] (2) cooling the first mixture to 40-60° C., adding a thickening stabilizer, and stirring and dispersing for 1-2 hours to obtain a second mixture;

[0017] (3) The second mixture is subjected to colloid milling and filtering.

[0018] In the preparation method of the mineral oil defoamer of the present invention, mineral oil, cationic emulsifier, nonionic emulsifier, defoamer and modified silicone polyether are first added and mixed in sequence, and finally a thickening stabilizer is added to improve the stability of the product system. In addition, this preparation process is simple, the production cost is low, and it has very broad market application value. DETAILED DESCRIPTION

[0019] The mineral oil defoamer of the present invention comprises, by weight, 50-90 parts of mineral oil, 5-20 parts of cationic emulsifier, 5-20 parts of nonionic emulsifier, 1-10 parts of modified silicone polyether, 0.5-5 parts of defoaming agent and 0.5-5 parts of thickening stabilizer.

[0020] The mineral oil may be, but is not limited to, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, or 90 parts. The mineral oil is selected from at least one of gasoline, kerosene, diesel, lubricating oil, chemical light oil, white mineral oil, solvent oil, paraffin, alkylbenzene, and naphthenic oil.

[0021] The cationic emulsifier can be, but is not limited to, 5 parts, 7 parts, 9 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, and 20 parts. The cationic emulsifier is an alkylamine salt type emulsifier, a quaternary ammonium salt type emulsifier, a heterocyclic type emulsifier, or a phosphonium salt type emulsifier. Specifically, the cationic emulsifier can be dodecyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl pyridinium bromide, a nitrogen-containing morpholine ring, a nitrogen-containing pyridine ring, a nitrogen-containing imidazole ring, a nitrogen-containing piperazine ring, a nitrogen-containing quinoline ring, a phosphonium salt, a sulfonium salt, an iodonium salt, and At least one salt compound.

[0022] The nonionic emulsifier may be, but is not limited to, 5 parts, 7 parts, 9 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, or 20 parts. The nonionic emulsifier is selected from at least one of glyceryl monostearate, sorbitan fatty acid esters, sorbitan polyoxyethylene fatty acid esters, polyoxyethylene stearyl ethers, fatty alcohol polyoxyethylene ethers, condensates of alkylphenols and ethylene oxide, condensates of fatty alcohols and ethylene oxide, sesame oil, and hydrogenated sesame oil and ethylene oxide condensates.

[0023] The modified silicone polyether can be, but is not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts. The modified silicone polyether can be sourced from the Degussa ABIL EM series of products. The modified silicone polyether is prepared from cetyl polyethylene glycol, polypropylene glycol, and dimethyl silicone oil. It can refer to the conventional preparation method, and only requires that the molecular structure of the synthesized modified silicone polyether has a polyether-siloxane-alkyl structure, with an HLB value of 4 to 6, preferably 5.

[0024] The defoaming agent can be, but is not limited to, 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts. The defoaming agent is at least one of fatty acid metal soaps, silica, alumina, magnesia, and zinc oxide.

[0025] The thickening stabilizer can be, but is not limited to, 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts. The thickening stabilizer is modified castor oil and its derivatives and / or bentonite, and the bentonite can be organic bentonite or tetraalkylammonium bentonite.

[0026] The preparation method of the mineral oil defoamer of the present invention can include:

[0027] (1) Add the formulated amounts of mineral oil, cationic emulsifier, non-ionic emulsifier, defoaming agent, and modified silicone polyether to the reaction kettle in sequence, raise the temperature to 100 - 150 °C while stirring, and keep warm for 1 - 5 h to obtain the first mixture;

[0028] (2) Cool the first mixture to 40 - 60 °C, then add the thickening stabilizer, and stir and disperse for 1 - 2 h to obtain the second mixture;

[0029] (3) Subject the second mixture to colloid mill and filtration.

[0030] To better illustrate the purpose, technical solution, and beneficial effects of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be noted that the methods described in the following embodiments are further explanatory descriptions of the present invention and should not be regarded as limitations to the present invention.

[0031] Example 1

[0032] The raw materials for preparing the mineral oil defoamer include, by weight, 80 parts of gasoline, 10 parts of dodecyl ammonium chloride, 5 parts of sorbitan fatty acid ester, 2 parts of modified silicone polyether, 0.5 part of silica, and 2.5 parts of modified castor oil. Among them, the modified silicone polyether has an HLB value of 5 and is prepared from cetyl polyethylene glycol, polypropylene glycol, and dimethyl silicone oil by a conventional preparation method, and has a polyether-siloxane-alkyl structure in its molecular structure.

[0033] The preparation method of this mineral oil defoamer includes:

[0034] (1) adding gasoline, lauryl ammonium chloride, sorbitan fatty acid ester, white carbon black and modified silicone polyether into a reaction kettle in sequence, raising the temperature to 130° C. while stirring, and keeping the temperature for 2 hours to obtain a first mixture;

[0035] (2) cooling the first mixture to 50° C., adding modified castor oil, and stirring and dispersing for 1 h to obtain a second mixture;

[0036] (3) The second mixture is colloidally milled and filtered.

[0037] Example 2

[0038] The raw materials used to prepare the mineral oil defoamer include, by weight, 70 parts gasoline, 14 parts dodecyl ammonium chloride, 7 parts sorbitan fatty acid ester, 5 parts modified silicone polyether, 0.7 parts white carbon black, and 3.3 parts modified castor oil. The modified silicone polyether has an HLB value of 5 and is prepared using conventional methods from cetyl polyethylene glycol, polypropylene glycol, and dimethyl silicone oil. Its molecular structure has a polyether-siloxane-alkyl structure.

[0039] The preparation method of the mineral oil defoamer comprises:

[0040] (1) adding gasoline, lauryl ammonium chloride, sorbitan fatty acid ester, white carbon black and modified silicone polyether into a reaction kettle in sequence, raising the temperature to 130° C. while stirring, and keeping the temperature for 2 hours to obtain a first mixture;

[0041] (2) cooling the first mixture to 50° C., adding modified castor oil, and stirring and dispersing for 1 h to obtain a second mixture;

[0042] (3) The second mixture is colloidally milled and filtered.

[0043] Example 3

[0044] The raw materials used to prepare the mineral oil defoamer include, by weight, 75 parts gasoline, 10 parts dodecyl ammonium chloride, 5 parts sorbitan fatty acid ester, 5 parts modified silicone polyether, 1 part white carbon black, and 4 parts modified castor oil. The modified silicone polyether has an HLB value of 5 and is prepared using conventional methods from cetyl polyethylene glycol, polypropylene glycol, and dimethyl silicone oil. Its molecular structure has a polyether-siloxane-alkyl structure.

[0045] The preparation method of the mineral oil defoamer comprises:

[0046] (1) adding gasoline, lauryl ammonium chloride, sorbitan fatty acid ester, white carbon black and modified silicone polyether into a reaction kettle in sequence, raising the temperature to 130° C. while stirring, and keeping the temperature for 2 hours to obtain a first mixture;

[0047] (2) Cool the first mixture to 50 °C, then add the modified castor oil and stir for 1 h to obtain the second mixture;

[0048] (3) Grind the second mixture with a colloid mill and filter it.

[0049] Example 4

[0050] The raw materials for preparing the mineral oil defoamer include, by weight, 80 parts of white mineral oil, 10 parts of cetyltrimethylammonium bromide, 5 parts of fatty alcohol polyoxyethylene ether, 2 parts of modified silicone polyether, 0.5 part of white carbon black, and 2.5 parts of organic bentonite. Among them, the HLB value of the modified silicone polyether is 5, which is prepared from cetyl polyethylene glycol, polypropylene glycol, and dimethyl silicone oil by a conventional preparation method, and has a polyether-siloxane-alkyl structure in the molecular structure.

[0051] The preparation method of this mineral oil defoamer includes:

[0052] (1) Add white mineral oil, cetyltrimethylammonium bromide, fatty alcohol polyoxyethylene ether, white carbon black, and modified silicone polyether to the reaction kettle in sequence, raise the temperature to 130 °C while stirring, and keep the temperature for 2 h to obtain the first mixture;

[0053] (2) Cool the first mixture to 50 °C, then add organic bentonite and stir for 1 h to obtain the second mixture;

[0054] (3) Grind the second mixture with a colloid mill and filter it.

[0055] Comparative Example 1

[0056] The raw materials for preparing the mineral oil defoamer include, by weight, 82 parts of gasoline, 10 parts of dodecyl ammonium chloride, 5 parts of sorbitan fatty acid ester, 0.5 part of white carbon black, and 2.5 parts of modified castor oil.

[0057] The preparation method of this mineral oil defoamer includes:

[0058] (1) Add gasoline, dodecyl ammonium chloride, sorbitan fatty acid ester, white carbon black, and modified silicone polyether to the reaction kettle in sequence, raise the temperature to 130 °C while stirring, and keep the temperature for 2 h to obtain the first mixture;

[0059] (2) Cool the first mixture to 50 °C, then add modified castor oil and stir for 1 h to obtain the second mixture;

[0060] (3) Grind the second mixture with a colloid mill and filter it.

[0061] Comparative Example 2

[0062] The preparation raw materials of the mineral oil defoamer include, by weight, 80 parts of gasoline, 15 parts of sodium naphthenate, 2 parts of modified silicone polyether, 0.5 part of white carbon black, and 2.5 parts of modified castor oil. Among them, the HLB value of the modified silicone polyether is 5, which is prepared from cetyl polyethylene glycol, polypropylene glycol, and dimethyl silicone oil by a conventional preparation method, and has a polyether-siloxane-alkyl structure in the molecular structure.

[0063] The preparation method of this mineral oil defoamer includes:

[0064] (1) Add gasoline, sodium naphthenate, white carbon black, and modified silicone polyether into the reaction kettle in sequence, raise the temperature to 130 °C while stirring, and keep the temperature for 2 h to obtain the first mixture;

[0065] (2) Cool the first mixture to 50 °C, then add modified castor oil, and stir and disperse for 1 h to obtain the second mixture;

[0066] (3) Grind the second mixture with a colloid mill and filter it.

[0067] Comparative Example 3

[0068] The preparation raw materials of the mineral oil defoamer include, by weight, 80 parts of gasoline, 15 parts of dodecyl ammonium chloride, 2 parts of modified silicone polyether, 0.5 part of white carbon black, and 2.5 parts of modified castor oil. Among them, the HLB value of the modified silicone polyether is 5, which is prepared from cetyl polyethylene glycol, polypropylene glycol, and dimethyl silicone oil by a conventional preparation method, and has a polyether-siloxane-alkyl structure in the molecular structure.

[0069] The preparation method of this mineral oil defoamer includes:

[0070] (1) Add gasoline, dodecyl ammonium chloride, white carbon black, and modified silicone polyether into the reaction kettle in sequence, raise the temperature to 130 °C while stirring, and keep the temperature for 2 h to obtain the first mixture;

[0071] (2) Cool the first mixture to 50 °C, then add modified castor oil, and stir and disperse for 1 h to obtain the second mixture;

[0072] (3) Grind the second mixture with a colloid mill and filter it.

[0073] Comparative Example 4

[0074] The preparation raw materials of the mineral oil defoamer include, by weight, 80 parts of gasoline, 15 parts of sorbitan fatty acid ester, 2 parts of modified silicone polyether, 0.5 part of white carbon black, and 2.5 parts of modified castor oil. Among them, the HLB value of the modified silicone polyether is 5, which is prepared from cetyl polyethylene glycol, polypropylene glycol, and dimethyl silicone oil by a conventional preparation method, and has a polyether-siloxane-alkyl structure in the molecular structure.

[0075] The preparation method of this mineral oil defoamer includes:

[0076] (1) Add gasoline, sorbitan fatty acid ester, fumed silica and modified silicone polyether into the reaction kettle in sequence, raise the temperature to 130 °C while stirring, and keep the temperature for 2 h to obtain the first mixture;

[0077] (2) Cool the first mixture to 50 °C, then add modified castor oil, and stir and disperse for 1 h to obtain the second mixture;

[0078] (3) Grind the second mixture with a colloid mill and filter it.

[0079] Perform compatibility and defoaming and foam suppression performance tests on the mineral oil defoamers in Examples 1-4 and Comparative Examples 1-4, and commercially available conventional silicone defoamers, polyether defoamers and mineral oil defoamers. The test sample is acrylic emulsion, and the test conditions are as follows. The test results are shown in Table 1.

[0080] (1) Compatibility test:

[0081] In a 250 mL beaker, weigh 100 mL of acrylic emulsion, add 1 mL of each defoamer respectively, stir magnetically for 10 min, let it stand for 10 min, then scrape it on the black and white grid paper with a 50 μm film applicator, and compare the film forming effects of the films respectively.

[0082] (2) Defoaming and foam suppression performance:

[0083] In a 250 mL beaker, weigh 150 mL of acrylic emulsion, add 1.5 mL of each defoamer respectively, disperse at a high speed of 2000 rpm for 10 min. After completion, immediately pour the emulsion into a 100 mL density cup that has been tared on an electronic scale until the cup lid just overflows, read the corresponding weight m. At this time, the density of the emulsion is m / 100 (g / mL). And the greater the density of the emulsion, the better the defoaming and foam suppression performance of the defoamer.

[0084] Table 1 Compatibility and defoaming and foam suppression performance test

[0085]

[0086]

[0087] As can be seen from the results in Table 1, compared with Comparative Examples 1-4 and commercially available conventional defoamers, the compatibility and defoaming and foam-inhibiting properties of the mineral oil defoamers of Examples 1-4 are better. This is mainly because the selection of cationic emulsifiers and non-ionic emulsifiers as compound emulsifiers in Examples 1-4 can improve the emulsification effect and stability of the defoamer. Specifically, the non-ionic emulsifier has a very strong emulsification effect. The cationic emulsifier carries a positive charge and will form an arrangement with the hydrophilic group inward and the hydrophobic group outward on the surface of the emulsifier, which can not only improve the emulsification effect of the non-ionic emulsifier, but also greatly improve the stability of the defoamer and prevent the hydrophobic substances in the defoaming agent from precipitating from the mineral oil. In addition, by adding a modified silicone polyether with a polyether-siloxane-alkyl structure, the hydrophilic polyether end can improve the water solubility of the defoamer, the hydrophobic and lipophilic alkyl structure end can combine well with the mineral oil, and the siloxane can improve the defoaming and foam-inhibiting properties of the defoamer. Therefore, the compatibility of the mineral oil and the speed and persistence of defoaming and foam inhibition can be optimized.

[0088] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, it is not limited to only the examples listed. Those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A mineral oil defoamer, characterized in that, By weight parts, the preparation raw materials include 50 - 90 parts of mineral oil, 5 - 20 parts of cationic emulsifier, 5 - 20 parts of nonionic emulsifier, 1 - 10 parts of modified silicone polyether, 0.5 - 5 parts of defoaming agent and 0.5 - 5 parts of thickening and stabilizing agent. The molecular structure of the modified silicone polyether has a polyether-siloxane-alkyl structure. The modified silicone polyether has a polyether end group and an alkyl end group. The modified silicone polyether is prepared from cetyl polyethylene glycol, polypropylene glycol and dimethyl silicone oil. The HLB value of the modified silicone polyether is 4 - 6. The defoaming agent is at least one of fatty acid metal soaps, silica, alumina, magnesia and zinc oxide.

2. The mineral oil defoamer according to claim 1, wherein The mineral oil is selected from at least one of gasoline, kerosene, diesel oil, lubricating oil, light chemical oil, white mineral oil, solvent oil, paraffin wax, alkylbenzene and naphthenic oil.

3. The mineral oil defoamer according to claim 1, wherein The cationic emulsifier is an alkylamine salt type emulsifier, a quaternary ammonium salt type emulsifier, a heterocyclic type emulsifier or a pyridinium salt type emulsifier.

4. The mineral oil defoamer according to claim 1, characterized in that, The nonionic emulsifier is selected from at least one of glycerol monostearate, sorbitan fatty acid ester, sorbitan polyoxyethylene fatty acid ester, polyoxyethylene stearyl ether, fatty alcohol polyoxyethylene ether, condensate of alkylphenol and ethylene oxide, condensate of fatty alcohol and ethylene oxide, castor oil, condensate of hydrogenated castor oil and ethylene oxide.

5. The mineral oil defoamer according to claim 1, characterized in that, The thickening and stabilizing agent is modified castor oil, derivatives of modified castor oil, bentonite, mixture of modified castor oil and bentonite, mixture of derivatives of modified castor oil and bentonite.

6. The preparation method of the mineral oil defoamer according to any one of claims 1 to 4, characterized in that, Including: (1) Add the formulated amounts of mineral oil, cationic emulsifier, nonionic emulsifier, defoaming agent and modified silicone polyether into the reaction kettle in sequence, raise the temperature to 100 - 150 °C while stirring, and keep warm for 1 - 5 h to obtain the first mixture; (2) Cool the first mixture to 40 - 60 °C, then add the thickening and stabilizing agent, and stir and disperse for 1 - 2 h to obtain the second mixture; (3) Grind the second mixture with a colloid mill and filter it.

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