Multifunctional composite defoamer and preparation method thereof

Abstract

The application discloses a multifunctional composite defoaming agent and a preparation method thereof. The defoaming agent is composed of glycerol polyoxyethylene polyoxypropylene ether oleic acid ester, PEG400DO and Span-80. The glycerol polyoxyethylene polyoxypropylene ether oleic acid ester is composed of glycerol polyoxyethylene polyoxypropylene block polyether, oleic acid and p-toluenesulfonic acid. The preparation method comprises the following steps: (1) glycerol polyoxyethylene polyoxypropylene block polyether, oleic acid and p-toluenesulfonic acid are loaded into a reaction kettle, a stirrer is started, and vacuumizing is performed until heating and heat preservation are completed, and then cooling is performed to room temperature to obtain glycerol polyoxyethylene polyoxypropylene ether oleic acid ester; and (2) glycerol polyoxyethylene polyoxypropylene ether oleic acid ester, PEG400DO and Span-80 are sequentially taken to the reaction kettle, and temperature is raised and stirring is performed to obtain the multifunctional composite defoaming agent. The multifunctional composite defoaming agent has the advantages of strong bubble inhibition capacity, stable performance, non-toxicity and harmlessness, environmental friendliness, stronger activity, smaller use dosage and stronger defoaming capacity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of defoaming agent, in particular to a multifunctional composite defoaming agent and a preparation method thereof. BACKGROUND

[0002] Polyether defoaming agent has a wide range of applications, is easy to disperse in water, is non-toxic and non-irritating, and can be used in general industry and special industries such as food, fermentation and pharmaceuticals, and cannot be replaced by silicon-containing defoaming agents. However, polyether defoaming agents still face problems such as temperature limitations on use conditions, narrow application range, weak defoaming ability, and low bubble breaking rate, which requires research on the defoaming agent, continuous optimization of its performance, and improvement of the defoaming effect of such defoaming agents under more conditions to enable them to be applied in more industries.

[0003] Polyether ester defoaming agent is a polyether derivative with esterified end groups. It not only has the advantages of non-toxicity, dispersion in water, and high foam suppression ability of polyether defoaming agents, but also has further reduced hydrophilicity and increased lipophilicity after esterification, which weakens the hydrogen bond between the original polyoxyethylene chain and water molecules and is beneficial to the reduction of surface tension. It often lies flat on the gas-liquid interface in a folded structure, so the polyether ester defoaming agent has higher activity, smaller dosage, and stronger defoaming power than ordinary polyether defoaming agents. The synthesis of polyether ester is simple, and combined with some emulsifiers, dispersants and other additives, different types of composite defoaming agents can be prepared to expand the application range.

[0004] Currently, there is little research on polyether ester defoaming agents. SUMMARY

[0005] The technical problem to be solved by the present application is to overcome the problems of weak defoaming ability and low bubble breaking rate of traditional polyether defoaming agents, thereby providing a composite defoaming agent with strong defoaming ability, high bubble breaking rate, good emulsifying performance, and wide application range. Meanwhile, the present application also provides a preparation method of the defoaming agent.

[0006] In a first aspect, the present application provides a multifunctional composite defoaming agent, which is composed of glycerol polyoxyethylene polyoxypropylene ether oleic acid ester, PEG400DO and Span-80.

[0007] Further, in the multifunctional composite defoaming agent, the composition by mass percentage is: glycerol polyoxyethylene polyoxypropylene ether oleic acid ester 9-47%, PEG400DO 47-89%, and Span-80 2-6%; the sum of the above components is 100%.

[0008] Further, the raw material of the glycerol polyoxyethylene polyoxypropylene ether oleic acid ester is composed of glycerol polyoxyethylene polyoxypropylene block polyether 50-70%, oleic acid 30-50%, and p-toluene sulfonic acid, wherein the amount of p-toluene sulfonic acid is 0.1-0.2% of the total amount of glycerol polyoxyethylene polyoxypropylene block polyether and oleic acid.

[0009] Further, the oleic acid is plant oil acid or animal oil acid, such as industrial-grade tall oil acid, industrial-grade palm oil acid, industrial-grade vegetable oil acid, and industrial-grade animal oil acid.

[0010] In the second aspect, the application provides a preparation method of the multifunctional composite defoaming agent, which comprises the following steps:

[0011] (1) Put glycerol polyoxyethylene polyoxypropylene block polyether, oleic acid, and p-toluene sulfonic acid into a reaction kettle, start a stirrer, and vacuumize to -0.090 MPa, heat and keep warm, and then cool to room temperature to obtain glycerol polyoxyethylene polyoxypropylene ether oleic acid ester, and calculate the yield and esterification rate;

[0012] (2) Put glycerol polyoxyethylene polyoxypropylene ether oleic acid ester, PEG400DO, and Span-80 into the reaction kettle in sequence, heat and stir to obtain the multifunctional composite defoaming agent.

[0013] Further, in step (1), the heating temperature is 60-185°C, and the holding time is 4-7 h.

[0014] Preferably, in step (1), the heating temperature is 135-175°C, and the holding time is 4-6.5 h.

[0015] Further, in step (2), the heating and stirring are performed, wherein the heating is performed to a temperature of 50-80°C, and the stirring is performed at a stirring speed of 300-800 rpm for 0.3-1 h, and then the process is ended.

[0016] Preferably, in step (2), the heating and stirring are performed, wherein the heating is performed to a temperature of 50-65°C, and the stirring is performed at a stirring speed of 350-700 rpm for 0.3-0.6 h, and then the process is ended.

[0017] The application has the following beneficial effects:

[0018] The multifunctional composite defoaming agent of the application is an end-group esterified polyether derivative, which not only inherits the advantages of polyether defoaming agents, such as strong foam inhibition, stable performance, non-toxicity, harmlessness, and environmental friendliness, but also has a decreased surface tension and improved defoaming capacity after esterification. The multifunctional composite defoaming agent molecule lies flat on the gas-liquid interface in a folded mechanism, so that the activity is stronger, the dosage is less, and the defoaming capacity is stronger.

[0019] In addition, the multifunctional composite defoaming agent adopts a composite formula, the PEG400DO and Span-80 added have good dispersibility and emulsifiability, the synergistic effect of the obtained defoaming agent is obviously enhanced, and the defoaming and foam suppressing effects are more excellent. DETAILED DESCRIPTION

[0020] In the description of the present application, it should be noted that, in the examples, the specific conditions not specified are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not specified by the manufacturer, and are all conventional products that can be purchased on the market.

[0021] The present application will be further described in conjunction with the specific embodiments to help the skilled in the art to have a more complete, accurate and in-depth understanding of the inventive concept and technical solution of the present application. The protection scope of the present application includes but is not limited to the following examples, and any modification made to the details and forms of the technical solution of the present application without departing from the spirit and scope of the present application falls within the protection scope of the present application.

[0022] In the embodiments of the present application, the tall oil acid is an industrial grade product of Shandong Poly Chemical Co., Ltd., the palmitoleic acid is an industrial grade product of Shandong Haoyao New Material Co., Ltd., the vegetable oleic acid is an industrial grade product of Jinan Jiuruixi Chemical Co., Ltd., and the animal oleic acid is an industrial grade product of Shandong Xihui New Material Co., Ltd.

[0023] The glycerol polyoxyethylene polyoxypropylene block polyether used in the embodiments 1-5 and comparative examples 1-3 of the present application is a product sold by Zhejiang Huangma Science and Technology Co., Ltd.

[0024] In the embodiments of the present application, opening the stirrer and introducing nitrogen means that the stirring is opened at the same time as the nitrogen is introduced, and the air in the reaction kettle is discharged by continuously introducing nitrogen during the heating process.

[0025] In the embodiments of the present application, opening the stirrer and introducing nitrogen means that the oxygen content in the air is reduced to below 0.01%.

[0026] In the embodiments of the present application, opening the stirrer and vacuumizing means that the stirring is opened at the same time as the vacuumizing is carried out.

[0027] The reaction formula for preparing the glycerol polyoxyethylene polyoxypropylene ether oleate in the embodiments of the present application is as follows:

[0028] ;

[0029] In the formula, X=10-20, and y=10-20.

[0030] In the embodiments of the present application, the reaction yield for preparing the glycerol polyoxyethylene polyoxypropylene ether oleate is 96-98%.

[0031] In the embodiments of the present application, the esterification rate of the glycerol polyoxyethylene polyoxypropylene ether oleic acid ester prepared is 83-86%.

[0032] The following is a preferred embodiment of the present application.

[0033] Example 1

[0034] The present embodiment provides a preparation method of a multifunctional composite defoaming agent, comprising the following steps:

[0035] (1) Put 230 g of glycerol polyoxyethylene polyoxypropylene block polyether (68.2%), 100 g of tall oil acid (29.7%), and 0.7 g of p-toluenesulfonic acid (0.2%) into a reaction kettle, start the stirrer and vacuum to -0.090 MPa, heat to 135°C, and keep for 4 h. After cooling to room temperature, glycerol polyoxyethylene polyoxypropylene ether oleic acid ester is obtained, with a product yield of 98% and an esterification rate of 85%;

[0036] (2) Put 92 g of glycerol polyoxyethylene polyoxypropylene ether oleic acid ester (9.2%), 888 g of PEG400DO (88.8%), and 20 g of Span-80 (2%) into a reaction kettle, heat to 50°C, rotate at 350 rpm, and disperse for 0.3 h. After cooling to room temperature, multifunctional composite defoaming agent S1 is obtained.

[0037] Example 2

[0038] The present embodiment provides a preparation method of a multifunctional composite defoaming agent, comprising the following steps:

[0039] (1) Put 345 g of glycerol polyoxyethylene polyoxypropylene block polyether (69.7%), 150 g of palm oil acid (30.3%), and 1 g of p-toluenesulfonic acid (0.1%) into a reaction kettle, start the stirrer and vacuum to -0.090 MPa, heat to 145°C, and keep for 5 h. After cooling to room temperature, glycerol polyoxyethylene polyoxypropylene ether oleic acid ester is obtained, with a product yield of 97% and an esterification rate of 83%;

[0040] (2) Put 194 g of glycerol polyoxyethylene polyoxypropylene ether oleic acid ester (19.4%), 776 g of PEG400DO (77.6%), and 30 g of Span-80 (3%) into a reaction kettle, heat to 55°C, rotate at 450 rpm, and disperse for 0.4 h. After cooling to room temperature, multifunctional composite defoaming agent S2 is obtained.

[0041] Example 3

[0042] The present embodiment provides a preparation method of a multifunctional composite defoaming agent, comprising the following steps:

[0043] (1) Put 460 g of glycerol polyoxyethylene polyoxypropylene block polyether (69.7%), 200 g of vegetable oleic acid (30.3%), and 1.32 g of p-toluenesulfonic acid (0.2%) into a reaction kettle, start the stirrer and vacuum to -0.090 MPa, heat to 155°C, and keep for 5.5 h. After cooling to room temperature, glycerol polyoxyethylene polyoxypropylene ether oleic acid ester is obtained, with a product yield of 98% and an esterification rate of 86%;

[0044] (2) Put 288 g of glycerol polyoxyethylene polyoxypropylene ether oleic acid ester (28.8%), 672 g of PEG400DO (67.2%), and 40 g of Span-80 (4%) into a reaction kettle, heat to 60°C, and disperse at a speed of 500 rpm for 0.5 h. After cooling to room temperature, multifunctional composite defoaming agent S3 is obtained.

[0045] Example 4

[0046] The present embodiment provides a preparation method of a multifunctional composite defoaming agent, comprising the following steps:

[0047] (1) Put 690 g of glycerol polyoxyethylene polyoxypropylene block polyether (69.7%), 300 g of animal oleic acid (30.3%), and 1.98 g of p-toluenesulfonic acid (0.2%) into a reaction kettle, start the stirrer and vacuum to -0.090 MPa, heat to 175°C, and keep for 6.5 h. After cooling to room temperature, glycerol polyoxyethylene polyoxypropylene ether oleic acid ester is obtained, with a product yield of 97% and an esterification rate of 85%.

[0048] (2) Put 470 g of glycerol polyoxyethylene polyoxypropylene ether oleic acid ester (47%), 470 g of PEG400DO (47%), and 60 g of Span-80 (6%) into a reaction kettle, heat to 60°C, and disperse at a speed of 700 rpm for 0.6 h. After cooling to room temperature, multifunctional polyether ester defoaming agent S5 is obtained.

[0049] Comparative Example 1

[0050] The specific operation steps are consistent with those of Example 3, except that step (2) is omitted; defoaming agent S6 is obtained.

[0051] Comparative Example 2

[0052] The specific operation steps are consistent with those of Example 3, except that no Span-80 is added in step (2); defoaming agent S7 is obtained.

[0053] Comparative Example 3

[0054] The specific operation steps are consistent with those in Example 3, except that in step (2), glycerol polyoxyethylene polyoxypropylene ether oleic acid ester 528 g (52.8%) and PEG400DO 432 g (43.2%) are taken; and defoaming agent S8 is obtained.

[0055] Test Example 1

[0056] The defoaming agents of Examples 1-4 and Comparative Examples 1-3 of the present application are subjected to performance tests according to the following method; the test method is specifically as follows:

[0057] Preparation of foaming liquid: 1 g of sodium dodecyl benzene sulfonate is accurately weighed in a beaker containing 99 g of deionized water, and slowly stirred with a glass rod until the solution is colorless and transparent without white powder;

[0058] A 1% (mass percentage) aqueous solution of the defoaming agents prepared in Examples 1-4 and Comparative Examples 1-3 is prepared as a defoaming liquid;

[0059] Foam suppressing performance test method: at room temperature, 1 ml of foaming liquid, 20 ml of deionized water and 1 ml of defoaming liquid are added to a 100 ml graduated cylinder, and then shaken for 30 times with the same intensity, and immediately start the stopwatch to record the foam volume at 30 s;

[0060] Defoaming performance test method: at room temperature, 1 ml of foaming liquid and 20 ml of deionized water are added to a 100 ml graduated cylinder, and then shaken for 30 times with the same intensity, and then 1 ml of defoaming liquid is added, and immediately start the stopwatch to record the foam volume at 30 s;

[0061] The test results are shown in Table 1.

[0062] Table 1: Comparison of defoaming / foam suppressing / dispersing data of defoaming agents of various examples and comparative examples

[0063]

[0064] As can be seen from the test results in Table 1, the defoaming agent of the present application has a significant improvement in defoaming time and foam suppressing time compared with Comparative Examples 1-3, and has better defoaming and foam suppressing effects, and has good dispersing properties.

[0065] The above description is only a preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can make other different forms of changes or variations on the basis of the above description, and the changes derived from the technical scheme and inventive concept of the present application should be covered within the protection scope of the present application.

Claims

1. A multifunctional composite defoamer characterized by It is composed of glycerol polyoxyethylene polyoxypropylene ether oleic acid ester, PEG400DO and Span-80; the glycerol polyoxyethylene polyoxypropylene ether oleic acid ester accounts for 9-47%, the PEG400DO accounts for 47-89%, and the Span-80 accounts for 2-6%; the sum of the above ingredients is 100%; The glycerol polyoxyethylene polyoxypropylene ether oleic acid ester is composed of the following raw materials in percentage by mass: glycerol polyoxyethylene polyoxypropylene block polyether 50-70%, oleic acid 30-50%, and p-toluenesulfonic acid, which accounts for 0.1-0.2% of the sum of the mass of the glycerol polyoxyethylene polyoxypropylene block polyether and the oleic acid; The preparation method of the multifunctional composite defoaming agent comprises the following steps: (1) Put the glycerol polyoxyethylene polyoxypropylene block polyether, the oleic acid, and the p-toluenesulfonic acid into a reaction kettle, start the stirrer, and vacuumize to-0.090MPa, heat and keep warm, then cool to room temperature to obtain the glycerol polyoxyethylene polyoxypropylene ether oleic acid ester, and calculate the yield and the esterification rate; (2) Put the glycerol polyoxyethylene polyoxypropylene ether oleic acid ester, the PEG400DO, and the Span-80 into the reaction kettle in sequence, heat and stir to obtain the multifunctional composite defoaming agent.

2. The multifunctional composite defoamer according to claim 1, characterized in that The oleic acid is plant oleic acid or animal oleic acid.

3. The multifunctional composite defoamer according to claim 1, characterized in that In the step (1), the heating temperature is 60-185℃, and the holding time is 4-7h.

4. The multifunctional composite defoamer according to claim 1 or 3, characterized in that In the step (1), the heating temperature is 135-175℃, and the holding time is 4-6.5h.

5. The multifunctional composite defoamer according to claim 1, characterized in that In the step (2), the heating and stirring are performed, the heating refers to heating to 50-80℃, the stirring refers to high-speed dispersion under the condition of the stirring speed of 300-800rpm for 0.3-1h, and then the process is ended.

6. The multifunctional composite defoamer according to claim 1 or 5, characterized in that In the step (2), the heating and stirring are performed, the heating refers to heating to 50-65℃, the stirring refers to high-speed dispersion under the condition of the stirring speed of 350-700rpm for 0.3-0.6h, and then the process is ended.

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