Preparation method for non-silicon emulsion defoaming agent

Abstract

A preparation method for a non-silicon emulsion defoaming agent, which method comprises: (1) uniformly mixing and stirring a specified amount of a higher fatty alcohol fatty acid ester, a fatty alcohol polyoxyethylene ether and a polyol to form a mixture M; (2) mixing and heating a specified amount of a higher fatty alcohol and paraffin to 70-100℃, uniformly stirring and mixing same, maintaining the temperature constant, slowly adding the mixture M thereto, and stirring same until uniformly mixed; (3) cooling same to room temperature, adding an anionic surfactant thereto, uniformly stirring and mixing the mixture, slowly adding water to the mixture, and then further emulsifying the mixture by means of a high-speed shearing device; and (4) finally adding a thickening agent thereto, and adjusting the mixture to the required viscosity.

Description

Preparation method of non-silicon emulsion defoamer Technical Field

[0001] The invention relates to a preparation method of a non-silicon emulsion defoamer. The defoamer is a fine chemical additive. Therefore, the invention belongs to the technical field of fine chemicals. Background Art

[0002] Based on their key active ingredients, defoamers can be primarily categorized as silicone defoamers and non-silicone defoamers. Silicone defoamers are characterized by low dosage, low surface tension, lack of physiological activity, and high safety. However, in some cases, these low surface tension and excellent spreading properties can be disadvantages. This is because once the silicone demulsifies, it can easily form silicon spots on the surface or cause pump blockage, adversely affecting industrial production. Non-silicone defoamers primarily include polyether defoamers, mineral oil defoamers, and fatty alcohol defoamers. Compared to silicone defoamers, non-silicone defoamers exhibit excellent compatibility with industrial additives and do not affect the stability of the foaming system. Among them, fatty alcohol defoamers not only have good compatibility, but also have good degassing properties, which can eliminate fine bubbles in the application system. They have good application performance in some special industries, such as papermaking and papermaking. This is because the foaming white water in the process of papermaking and papermaking contains many fine fibers and fillers. Fatty alcohol defoamers can not only eliminate surface foam, but also remove fine bubbles in fibers and fillers, avoiding spots, light spots and small holes on the paper surface, and improving production efficiency.

[0003] Researchers at home and abroad have conducted a lot of research on fatty alcohol emulsion defoamers, mainly focusing on stability and foam removal and suppression performance. CN106075961A introduces a water-soluble homopolymer-stabilized fatty alcohol emulsion defoamer and its preparation method. By adding a water-soluble homopolymer, the emulsion phase separation is reduced and gelation and viscosity increase are suppressed. This solves the problem of emulsion phase separation, gel block formation and thickening during storage of fatty alcohol emulsions. However, the foam removal and suppression performance of this product is poor and it does not have a good market advantage. CN107059474A introduces a high-carbon alcohol defoamer, which is composed of rice bran wax, wax, alkane or vegetable oil, surfactant, bactericide and water, wherein rice bran wax is the active ingredient of the defoamer. Rice bran wax contains a large amount of hexacosanol, octacosanol, triacontanol and corresponding alcohol esters, and has a good foam removal and suppression effect. However, the composition of this product is too complex, and the emulsification process is demanding and the viscosity changes greatly, which makes it easy to form a paste. CN109432830A introduces a method for preparing a high-carbon alcohol-based high-temperature defoaming agent, which uses high-carbon alcohol, mineral oil, fatty alcohol polyether polyol, and polyether-modified silicone oil as emulsified substances to obtain emulsion A, which is then compounded with emulsion B made of microcrystalline wax, and stirred at above 180°C to obtain the final emulsion. The emulsification method uses a method of mixing the active substance and the emulsifier separately to make the emulsification more complete, but the emulsion product has a large viscosity, poor dispersibility, and is more likely to form a paste. CN107137959B separately prepares separately emulsified fatty alcohol emulsion, oil emulsion, and paraffin emulsion, and finally compounds the three emulsions to make the final emulsion to improve the stability of the emulsion. However, the three emulsions need to be prepared separately during the preparation of the product, which is a relatively cumbersome process. In CN11790183A, paraffin wax, fatty alcohol, fatty acid ester, and white carbon are melted and stirred as the oil phase, then hot water is added, stirred, and emulsified using a colloid mill to obtain a fatty alcohol emulsion. The addition of white carbon improves the stability of the emulsion, but the addition of white carbon affects the compatibility of the defoamer. In the preparation process of the fatty alcohol emulsion, CN104707368A uses the synergistic effects of hydrophilic and lipophilic surfactants, Guerbet alcohols, biopolysaccharide alcohols, and viscosity control agents to form a stable emulsion system. However, the introduction of Guerbet alcohols and biopolysaccharide alcohols increases costs.

[0004] Summary of the Invention

[0005] The present invention adopts the D-phase emulsification method to prepare a stable emulsion. First, emulsifier A and emulsifier B are mixed to form a composite emulsifier, which is further mixed evenly with a polyol. Then, the oil phase is slowly added to the above system under stirring conditions, and the water phase is continuously added to obtain an emulsion. Finally, an anionic surfactant is added to further improve the stability of the emulsion.

[0006] Technical Solution

[0007] The preparation method of the non-silicon emulsion defoamer described in the present invention is composed of the following components:

[0008] A. Higher fatty alcohols

[0009] The fatty alcohol is a C12-C30 fatty alcohol selected from one or a mixture of synthetic fatty alcohols and natural fatty alcohols; specifically, selected from C12 alcohol, C14 alcohol, C16 alcohol, C18 alcohol, C20 alcohol, C22 alcohol, C24 alcohol, C26 alcohol, C28 alcohol, C30 alcohol; and mixed fatty alcohols containing different numbers of carbon atoms, such as C12-18 mixed alcohol, C16-18 mixed alcohol, and C16-22 mixed alcohol, one or more of which are selected. The amount of the fatty alcohol used accounts for 15-25% of the total weight of the defoamer.

[0010] B. Paraffin

[0011] The paraffin is selected from microcrystalline paraffin and liquid paraffin. The amount of the paraffin accounts for 2-8% of the total mass of the defoamer.

[0012] C. Surfactant 1

[0013] The surfactant 1 of the present invention is a higher fatty alcohol fatty acid ester, which is obtained by transesterification of C20-C30 fatty alcohol and C2-C10 fatty acid ester; the amount of the higher fatty alcohol fatty acid ester accounts for 3-5% of the total mass of the defoamer.

[0014] D. Surfactant 2

[0015] The surfactant 2 is a fatty alcohol polyoxyethylene ether, and the general structural formula is RO(EO) m H, wherein R is a 5-10 alkyl group, and m is an integer of 10-40; the amount of surfactant 2 accounts for 0.5-3% of the total mass of the defoaming agent.

[0016] E. Polyol

[0017] The polyol is selected from one or more of propylene glycol, glycerol and ethylene glycol, and its usage accounts for 0.5-3% of the total mass of the defoamer.

[0018] F. Anionic surfactant

[0019] The anionic surfactant is selected from one or more of sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl phosphate, and sodium dodecyl diphenyl ether disulfonate. The amount of the anionic surfactant used accounts for 0.03-0.1% of the total mass of the defoamer.

[0020] G. Thickener

[0021] The thickener is selected from one or more of xanthan gum, guar gum, xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyacrylic acid, and polyacrylamide. The thickener is preferably polyacrylic acid. The amount of the thickener accounts for 0.02% to 0.1% of the total mass of the defoamer.

[0022] H. Water

[0023] The water described in the present invention is deionized water, and its usage accounts for 60-75% of the total mass of the defoaming agent.

[0024] The preparation method of the non-silicon emulsion defoamer of the present invention is as follows:

[0025] (1) Mixing and stirring prescribed amounts of surfactant 1, surfactant 2, and polyol to form a mixture M;

[0026] (2) Mix the specified amount of higher fatty alcohol and paraffin wax, heat to 70-100°C, stir and mix evenly, keep the temperature constant, slowly add mixture M, and stir to mix evenly;

[0027] (3) Cooling to room temperature, adding anionic surfactant, stirring and mixing evenly, slowly adding water to the above mixture, and then further emulsifying through a high-speed shearing device;

[0028] (4) Finally, add thickener and adjust to the desired viscosity. DETAILED DESCRIPTION

[0029] Example 1

[0030] (1) 5g surfactant 1 (obtained by transesterification of 20-carbon fatty alcohol and methyl acetate), 3g C5H 11 O(EO) 35 H and 2 g of propylene glycol were mixed and stirred to form a mixture M1;

[0031] (2) Mix 15g of C12-C18 mixed fatty alcohol and 8g of microcrystalline wax and heat to 70-100°C, stir and mix evenly, keep the temperature constant, slowly add mixture M1, and stir to mix evenly;

[0032] (3) Cool to room temperature, add 0.1 g of sodium lauryl sulfate, stir and mix evenly, slowly add 66.8 g of water to the above mixture, and then further emulsify it through a high-speed shear device;

[0033] (4) Finally, add 0.1 g of xanthan gum and guar gum mixture as thickener and adjust to the desired viscosity.

[0034] Example 2

[0035] (1) 3 g of surfactant 1 (obtained by transesterification of 22-carbon fatty alcohol and methyl valerate), 1 g of C6H 13 O(EO) 25 H and 2 g of propylene glycol were mixed and stirred to form a mixture M2;

[0036] (2) Mix 20g of C16-C18 mixed fatty alcohol and 6g of liquid paraffin, heat to 70-100°C, stir and mix evenly, keep the temperature constant, slowly add mixture M2, and stir to mix evenly;

[0037] (3) Cool to room temperature, add 0.05 g of sodium dodecylbenzenesulfonate, stir and mix evenly, slowly add 67.9 g of water to the above mixture, and then further emulsify it through a high-speed shear device;

[0038] (4) Finally, add 0.05g of xanthan gum as thickener and adjust to the desired viscosity.

[0039] Example 3

[0040] (1) 4 g surfactant 1 (obtained by transesterification of 25-carbon fatty alcohol and methyl octanoate), 0.5 g C7H 15 O(EO) 10 H and 0.5 g of ethylene glycol were mixed and stirred to form a mixture M3;

[0041] (2) Mix 25g of C16-C22 mixed fatty alcohol and 2g of microcrystalline wax and heat to 70-100°C, stir and mix evenly, keep the temperature constant, slowly add mixture M3, and stir to mix evenly;

[0042] (3) Cool to room temperature, add 0.03 g of sodium lauryl phosphate, stir and mix evenly, slowly add 67.95 g of water to the above mixture, and then further emulsify it through a high-speed shear device;

[0043] (4) Finally, add 0.02g of a mixture of hydroxymethyl cellulose and hydroxyethyl cellulose as a thickener and adjust the viscosity to the desired value.

[0044] Example 4

[0045] (1) 5g surfactant 1 (obtained by transesterification of octadecyl alcohol and methyl decanoate), 1.8g C8H 17 O(EO) 15 H, 3g of propylene glycol and ethylene glycol mixture were mixed and stirred to form mixture M4;

[0046] (2) Mix 24g of C22 alcohol and 6g of liquid paraffin and heat to 70-100°C, stir and mix evenly, keep the temperature constant, slowly add mixture M4, and stir to mix evenly;

[0047] (3) Cool to room temperature, add 0.1 g of sodium dodecyl diphenyl ether disulfonate, stir and mix evenly, slowly add 60 g of water to the above mixture, and then further emulsify it through a high-speed shear device;

[0048] (4) Finally, add 0.1g of methyl cellulose thickener and adjust to the desired viscosity.

[0049] Example 5

[0050] (1) 3g surfactant 1 (obtained by transesterification of 30-carbon fatty alcohol and methyl propionate), 1g C9H 19 O(EO) 40 H, 0.8 g of propylene glycol and glycerol mixture were mixed and stirred to form mixture M5;

[0051] (2) Mix 22.13 g of a mixture of C12 alcohol and C14 alcohol and 3 g of microcrystalline wax and heat to 70-100°C. Stir and mix until uniform. Maintaining the temperature, slowly add the mixture M5 and stir until uniform.

[0052] (3) Cool to room temperature, add 0.04 g of a mixture of sodium lauryl sulfate and sodium dodecylbenzene sulfonate, stir and mix evenly, slowly add 70 g of water to the above mixture, and then further emulsify it through a high-speed shear device;

[0053] (4) Finally, add 0.03 g of a mixture of polyacrylic acid and polyacrylamide as a thickener and adjust the viscosity to the desired value.

[0054] Example 6

[0055] (1) 3 g of surfactant 1 (obtained by transesterification of 22-carbon fatty alcohol and methyl butyrate), 0.5 g of C 10 H 21 O(EO) 20 H, 0.5 g of propylene glycol and ethylene glycol mixture were mixed and stirred to form a mixture M6;

[0056] (2) 18.95 g of a mixture of C28 alcohol and C30 alcohol and 2 g of microcrystalline wax were mixed and heated to 70-100° C., stirred and mixed evenly, and the temperature was kept constant. Mixture M6 was slowly added and stirred to mix evenly;

[0057] (3) Cool to room temperature, add 0.03 g of a mixture of sodium lauryl phosphate and sodium lauryl diphenyl ether disulfonate, stir and mix evenly, slowly add 75 g of water to the above mixture, and then further emulsify it through a high-speed shear device;

[0058] (4) Finally, add 0.02g of polyacrylic acid thickener and adjust to the desired viscosity.

[0059] Comparative Example 1 - Compared with Example 1, the polyol was removed

[0060] (1) 5g surfactant 1 (obtained by transesterification of 20-carbon fatty alcohol and methyl acetate), 5g C5H 11 O(EO) 35 H mixed and stirred evenly to form a mixture M7;

[0061] (2) Mix 15g of C12-C18 mixed fatty alcohol and 8g of microcrystalline wax and heat to 70-100°C, stir and mix evenly, keep the temperature constant, slowly add mixture M7, and stir to mix evenly;

[0062] (3) Cool to room temperature, add 0.1 g of sodium lauryl sulfate, stir and mix evenly, slowly add 66.8 g of water to the above mixture, and then further emulsify it through a high-speed shear device;

[0063] (4) Finally, add 0.1 g of xanthan gum and guar gum mixture as thickener and adjust to the desired viscosity.

[0064] Comparative Example 2 - Compared with Example 2, the surfactant 1 was removed.

[0065] (1) 4gC6H 13 O(EO) 25 H and 2 g of propylene glycol were mixed and stirred to form a mixture M8;

[0066] (2) Mix 20g of C16-C18 mixed fatty alcohol and 6g of liquid paraffin and heat to 70-100°C, stir and mix evenly, keep the temperature constant, slowly add mixture M8, and stir to mix evenly;

[0067] (3) Cool to room temperature, add 0.05 g of sodium dodecylbenzenesulfonate, stir and mix evenly, slowly add 67.9 g of water to the above mixture, and then further emulsify it through a high-speed shear device;

[0068] (4) Finally, add 0.05g of xanthan gum as thickener and adjust to the desired viscosity.

[0069] Comparative Example 3 - Comparison with Example 3, removing surfactant 2

[0070] (1) 4.5 g of surfactant 1 (obtained by transesterification of 25-carbon fatty alcohol and methyl octanoate) and 0.5 g of ethylene glycol were mixed and stirred to form a mixture M9;

[0071] (2) Mix 25g of C16-C22 mixed fatty alcohol and 2g of microcrystalline wax and heat to 70-100°C, stir and mix evenly, keep the temperature constant, slowly add mixture M9, and stir to mix evenly;

[0072] (3) Cool to room temperature, add 0.03 g of sodium lauryl phosphate, stir and mix evenly, slowly add 67.95 g of water to the above mixture, and then further emulsify it through a high-speed shear device;

[0073] (4) Finally, add 0.02g of a mixture of hydroxymethyl cellulose and hydroxyethyl cellulose as a thickener and adjust the viscosity to the desired value.

[0074] Comparative Example 4 - Compared with Example 4, the anionic emulsifier was removed

[0075] (1) 5g surfactant 1 (obtained by transesterification of octadecyl alcohol and methyl decanoate), 1.8g C8H 17 O(EO) 15 H, 3g of propylene glycol and ethylene glycol mixture were mixed and stirred to form mixture M4;

[0076] (2) Mix 24g of C22 alcohol and 6g of liquid paraffin and heat to 70-100°C, stir and mix evenly, keep the temperature constant, slowly add mixture M4, and stir to mix evenly;

[0077] (3) Cool to room temperature, slowly add 60.1 g of water to the above mixture, and then further emulsify it through a high-speed shear device;

[0078] (4) Finally, add 0.1g of methyl cellulose thickener and adjust to the desired viscosity.

[0079] Performance Testing

[0080] 1. Emulsion stability test

[0081] The emulsions prepared in the above examples and comparative examples were subjected to six-month viscosity tracking tests at 5°C, 25°C, and 40°C. Viscosity was measured using an NDJ-8 digital viscometer with a #2 rotor at 6 rpm. See Table 1 below for details (viscosity measured in mPa.s; "-" indicates the emulsion is a paste and cannot flow):

[0082] Table 1 Changes in emulsion viscosity at different storage temperatures

[0083] Viscosity tracking data indicates that the defoamer prepared in the present invention exhibits minimal viscosity change after six months of storage at 5°C, 25°C, and 40°C, demonstrating good storage stability. In contrast, the viscosity of the fatty alcohol emulsions prepared in Comparative Examples 1-4 increased to varying degrees after six months.

[0084] 2. Test method for anti-foaming performance:

[0085] The performance of the defoaming agent is determined by the circulating bubbling method. Add 600 ml of white water to the circulating bubbling equipment and heat it to the required temperature. Turn on the flow pump and circulate at a flow rate of 8 / L min until the foam volume reaches 300 ml. Add 6 ul of defoaming agent and record the change of foam volume over time. Within the same time, the smaller the volume, the better the defoaming and antifoaming performance; the longer the time for the foam to reach 300 ml again, the better the antifoaming performance.

[0086] The fatty alcohol emulsion prepared by the invention exhibits good foam elimination and suppression performance at 30° C. and 55° C.

Claims

1. A method for preparing a non-silicon emulsion defoamer, comprising the following components: A. Higher fatty alcohol The fatty alcohol is a C12-C30 fatty alcohol, selected from one or a mixture of synthetic fatty alcohols and natural fatty alcohols; specifically selected from C12 alcohol, C14 alcohol, C16 alcohol, C18 alcohol, C20 alcohol, C22 alcohol, C24 alcohol, C26 alcohol, C28 alcohol, C30 alcohol; and mixed fatty alcohols containing different numbers of carbon atoms, such as C12-18 mixed alcohol, C16-18 mixed alcohol, C16-22 mixed alcohol, one or more of which are selected; the amount of the fatty alcohol accounts for 15-25% of the total mass of the defoamer; B. Paraffin The paraffin is selected from microcrystalline paraffin and liquid paraffin; the amount of paraffin accounts for 2-8% of the total mass of the defoamer; C. Surfactant 1 The surfactant 1 is a higher fatty alcohol fatty acid ester, which is obtained by transesterification of C20-C30 fatty alcohol and C2-C10 fatty acid ester; the amount of the higher fatty alcohol fatty acid ester accounts for 3-5% of the total mass of the defoamer; D. Surfactant 2 The surfactant 2 is a fatty alcohol polyoxyethylene ether, and has a general structural formula of RO(EO)mH, wherein R is a 5-10 alkyl group, and m is an integer of 10-40; the amount of the surfactant 2 accounts for 0.5-3% of the total mass of the defoamer; E. Polyol The polyol is selected from one or more of propylene glycol, glycerol, and ethylene glycol. The amount accounts for 0.5-3% of the total mass of the defoamer; F. Anionic surfactant The anionic surfactant is selected from one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium dodecyl phosphate, and sodium dodecyl diphenyl ether disulfonate; the amount of the anionic surfactant is 0.03-0.1% of the total mass of the defoamer; G. Thickener The thickener is selected from one or more of xanthan gum, guar gum, xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyacrylic acid, and polyacrylamide, and the amount of the thickener accounts for 0.02% to 0.1% of the total mass of the defoamer; H. Water The water is deionized water, and its usage accounts for 60-75% of the total mass of the defoamer.

2. The method for preparing a non-silicon emulsion defoamer according to claim 1, characterized in that: The preparation method of the non-silicon emulsion defoamer is as follows: (1) mixing and stirring prescribed amounts of surfactant 1, surfactant 2, and polyol to form a mixture M; (2) Mix a specified amount of higher fatty alcohol and paraffin wax, heat to 70-100° C., stir and mix evenly, keep the temperature constant, slowly add the mixture M, and stir to mix evenly; (3) cooling to room temperature, adding anionic surfactant, stirring and mixing evenly, slowly adding water to the above mixture, and then further emulsifying through a high-speed shearing device; (4) Finally, add thickener and adjust to the desired viscosity.

3. The method for preparing a non-silicon emulsion defoamer according to claim 1, characterized in that: The thickener is polyacrylic acid.

Images