High-temperature-resistant modified organic silicon defoaming agent as well as preparation method and application thereof

Abstract

The invention provides a high-temperature-resistant modified organic silicon defoaming agent as well as a preparation method and application thereof. The high-temperature-resistant modified organic silicon defoaming agent comprises the following components in parts by mass: 30-50 parts of organic silicon oil, 15-25 parts of modified organic silicon oil, 3-8 parts of an emulsifier, 2-5 parts of a surfactant, 3-6 parts of a thickening agent, 0.1-1 part of a preservative, 0.5-3 parts of silicon dioxide and 50-80 parts of deionized water. The high-temperature-resistant modified organic silicon defoaming agent prepared by using the components and content provided by the invention has good defoaming property and foam inhibition property at low temperature even if the content is relatively low, also has good defoaming property and foam inhibition property even if the temperature is relatively high, and compared with a defoaming agent in the prior art, the high-temperature-resistant modified organic silicon defoaming agent has the advantages that the defoaming property is good; the high-temperature-resistant modified organic silicon defoaming agent provided by the invention is still relatively high in defoaming property and foam inhibition property under the condition of relatively low content.

Description

Technical Field

[0001] The invention belongs to the technical field of defoaming, and specifically relates to a high temperature resistant modified organosilicon defoaming agent and a preparation method and application thereof. Background Art

[0002] Defoamers are substances that can reduce the surface tension of water, solutions, suspensions, etc., prevent the formation of foam, or reduce or eliminate existing foam. Defoamers can not only effectively eliminate the foam generated in industrial production, improve the efficiency of industrial production, but also improve the production quality of products. Therefore, there is a huge demand for defoamers in the market.

[0003] The existing defoamers mainly include silicone defoamers, polyether defoamers, fatty alcohol defoamers, etc. Among them, silicone defoamers are widely used in coatings, inks, metalworking fluids and other fields due to their fast defoaming speed and long antifoaming time. In addition, silicone defoamers have been widely studied by scholars or corporate R&D personnel, and patents with announcement numbers of "CN111871010B" and "CN103074784B" have been applied for. However, all of them have defects such as high usage of silicone defoamers and poor defoaming and antifoaming properties at high temperatures.

[0004] In view of the problems existing in the existing silicone defoamers, how to ensure that the silicone defoamers have good defoaming and antifoaming properties, and even if the silicone defoamers are used in high temperature environments, they still have good defoaming and antifoaming properties, and even if the amount of defoamers used is reduced, they still have good defoaming and antifoaming properties, which are problems to be solved urgently in the present invention. Summary of the invention

[0005] The object of the present invention is to provide a high temperature resistant modified organosilicon defoamer and a preparation method and application thereof, so as to solve the problems raised in the above background technology.

[0006] To achieve the above object, the present invention provides the following technical solutions: On the one hand, the present invention provides a high temperature resistant modified silicone defoamer, which comprises the following components in parts by weight:

[0007] 30-50 parts of organic silicone oil, 15-25 parts of modified organic silicone oil, 3-8 parts of emulsifier, 2-5 parts of surfactant, 3-6 parts of thickener, 0.1-1 parts of preservative, 0.5-3 parts of silicon dioxide, and 50-80 parts of deionized water.

[0008] As a further improvement, the surfactant comprises polyoxyethylene sorbitan monolaurate and a sulfonic acid surfactant.

[0009] As a further improvement, the raw materials for preparing the sulfonic acid surfactant include nonylphenol, tetra-n-butylammonium bromide, 1,4-dibromobutane, anhydrous dichloromethane and chlorosulfonic acid.

[0010] As a further improvement, the mass ratio of the polyoxyethylene sorbitan monolaurate to the sulfonic acid surfactant is 1:(1.2-1.5).

[0011] As a further improvement, the emulsifier includes but is not limited to sorbitan fatty acid esters, sorbitan monooleate polyoxyethylene ether, and sorbitan oleate.

[0012] As a further improvement, thickeners include, but are not limited to, hydroxyethyl cellulose, xanthan gum, and polyacrylates.

[0013] As a further improvement, preservatives include but are not limited to sodium benzoate, kason, and kason.

[0014] As a further improvement, the raw materials for preparing the modified silicone oil include terminal epoxy silicone oil, polyether diamine and tetradecyl ethylene oxide.

[0015] As a further improvement, the preparation method of the modified silicone oil comprises the following steps:

[0016] (3.1) After adding terminal epoxy silicone oil, polyether diamine and organic solvent into the reactor, heating to 80-85° C., reacting, cooling to room temperature after the reaction is completed, and setting aside;

[0017] (3.2) Mix tetradecyl ethylene oxide and isopropyl alcohol and set aside;

[0018] (3.3) The substance obtained in step (3.2) is added dropwise to step (3.1), and the temperature is raised to 80-85° C. to carry out a reaction. After the reaction is completed, the modified silicone oil is obtained by rotary evaporation.

[0019] As a further improvement, the number average molecular weight of the epoxy-terminated silicone oil is 5000-8000.

[0020] As a further improvement, the molecular weight of the polyether diamine is 800-1500.

[0021] As a further improvement, the method for preparing the sulfonic acid surfactant comprises the following steps:

[0022] (1.1) nonylphenol, tetra-n-butylammonium bromide and sodium hydroxide solution are placed in a first reaction kettle and stirred and heated to a suitable temperature, 1,4-dibromobutane is added to the first reaction kettle for heating reaction, and after the reaction is completed, the reaction is cooled, extracted, washed, dried and filtered to obtain an intermediate;

[0023] (1.2) The intermediate obtained in step (1.1) is placed in a second reaction kettle, and a mixture of anhydrous dichloromethane and chlorosulfonic acid is dripped into the second reaction kettle for low-temperature reaction. After the reaction is completed, the mixture is purified to obtain a sulfonic acid-type surfactant.

[0024] On the other hand, the present invention also provides a method for preparing a high temperature resistant modified silicone defoamer, comprising the following steps:

[0025] (2.1) Add silicone oil, modified silicone oil, surfactant and silicon dioxide into a reactor, raise the temperature of the reactor to 80-125°C, and stir until mixed;

[0026] (2.2) Add thickener and preservative to the material in step (2.1), heat to 220-250°C, and stir thoroughly until mixed;

[0027] (2.3) After the mixed substance in step (2.2) is cooled to 90-100° C., an emulsifier and deionized water are added and mixed to obtain a high temperature resistant modified silicone defoaming agent.

[0028] On the other hand, the present invention also provides an application of high temperature resistant modified organic silicon defoamer in textile auxiliaries.

[0029] Compared with the prior art, the beneficial effects of the present invention are: the high-temperature resistant modified silicone defoamer prepared using the components and contents provided in the present application has good defoaming and antifoaming properties at low temperatures even when the content is low, and has good defoaming and antifoaming properties even at high temperatures. Compared with the defoamers in the prior art, the high-temperature resistant modified silicone defoamer provided in the present application still has high defoaming and antifoaming properties when the content is low. DETAILED DESCRIPTION

[0030] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0031] In the following examples, except for the sulfonic acid surfactant and the modified silicone oil, the other compound monomers and related reagents used can be purchased from the market, wherein the silicone oil was purchased from Jinan Hongtai Chemical Co., Ltd. with a CAS number of 9006-65-9; the epoxy-terminated silicone oil was purchased from Jining Tangyi Chemical Co., Ltd. with a CAS number of 70131-67-8; the polyether diamine was purchased from Shanghai Wandao Chemical Co., Ltd. with a model of Jeffamine ED-2003; the polyoxyethylene sorbitan monooleate was purchased from Jining Tangyi Chemical Co., Ltd. with a product number of S12705115; the polyoxyethylene sorbitan monolaurate was purchased from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd. with a product number of lnb-1672; the hydroxyethyl cellulose was purchased from Jinan Zhengyin Chemical Co., Ltd. with a CAS number of 9004-62-0, and the xanthan gum was purchased from Guangdong Hongyou Biotechnology Co., Ltd. with a CAS number of 11138-66-2.

[0032] The preparation method of sulfonic acid type surfactant comprises the following steps:

[0033] (1.1) 0.25 kg of nonylphenol, 0.2 kg of tetra-n-butylammonium bromide and 1000 mL of 20% sodium hydroxide solution are placed in a first reaction kettle, stirred and heated to 70° C., 0.12 kg of 1,4-dibromobutane is added to the first reaction kettle and heated to 95° C. to react. After the reaction is completed, the mixture is cooled to room temperature and extracted three times with ether. The extract is first washed twice with 3% acetic acid solution, then washed three times with water, dried with anhydrous magnesium sulfate, filtered and evaporated with a rotary evaporator to obtain an intermediate;

[0034] (1.2) 0.2 kg of the intermediate obtained in step (1.1) was placed in a second reaction kettle, and a mixture of 500 mL of anhydrous dichloromethane and 350 mL of chlorosulfonic acid was dripped into the second reaction kettle. The temperature of the second reaction kettle was controlled to 0° C. and the reaction was carried out for 6.5 hours. After the reaction was completed, the generated hydrogen chloride and excess chlorosulfonic acid were removed, and petroleum ether was first added to chromatograph the crude product from the solution, and then recrystallized three times with petroleum ether and dichloromethane to obtain a sulfonic acid surfactant.

[0035] The preparation method of modified silicone oil comprises the following steps:

[0036] (3.1) After adding 0.5 mol of terminal epoxy silicone oil (number average molecular weight of 7000), 0.65 mol of polyether diamine (number average molecular weight of 900) and 3.2 kg of isopropanol into a reactor, the temperature was raised to 82° C., and the reaction was carried out. After the reaction was carried out for 5 hours, the mixture was cooled to room temperature and set aside;

[0037] (3.2) Mix 0.15 mol of tetradecyl ethylene oxide and 0.5 kg of isopropanol and set aside;

[0038] (3.3) The substance obtained in step (3.2) is dripped into step (3.1) through a constant pressure funnel. The dripping time is 5 minutes. After the dripping is completed, the temperature is raised to 82°C for reaction. After the reaction is completed for 2 hours, the reaction is completed, and the isopropanol is spiraled out to obtain modified silicone oil.

[0039] The high temperature resistant modified silicone defoamer of Examples 1-5 and Comparative Examples 1-3 is prepared in the following steps:

[0040] (2.1) Add silicone oil, modified silicone oil, surfactant and silicon dioxide into a reactor, raise the temperature of the reactor to 120°C, and stir until mixed;

[0041] (2.2) Add thickener and preservative to the material in step (2.1), heat to 230°C, and stir thoroughly until mixed;

[0042] (2.3) After the mixed substance in step (2.2) is cooled to 100° C., an emulsifier and deionized water are added and mixed to obtain a high temperature resistant modified silicone defoaming agent.

[0043] The required components and the contents of each component in Examples 1-6 and Comparative Examples 1-2 are shown in Table 1-2:

[0044] Table 1

[0045]

[0046]

[0047] Table 2

[0048]

[0049] The high temperature resistant modified silicone defoamers prepared in Examples 1-6 and Comparative Examples 1-2 were tested for defoaming and antifoaming properties at 25°C and 100°C, respectively. The silicone defoamer used in Comparative Example 2 was purchased from Guangzhou Zhongwan New Materials Co., Ltd., with the product number W-700. The specific test method is as follows, and the test results are shown in Table 3. The test method is as follows:

[0050] (1) Defoaming performance test

[0051] At 25°C and 100°C, respectively, 25 mL and 2 wt% aqueous sodium dodecylbenzene sulfonate solution were poured into a 100 mL measuring cylinder, and the volume was shaken up and down for several times until the foaming liquid reached 100 mL. A defoamer with a content of 0.1 wt% of the foaming liquid was added, and a stopwatch was started until the foam completely disappeared. The shorter the time, the better the defoaming performance of the defoamer. The experiment was repeated three times and the average value was taken.

[0052] (2) Test of anti-foaming performance:

[0053] At 25°C and 100°C, add 100mL of 2wt% sodium dodecylbenzene sulfonate aqueous solution to a 1L measuring cylinder, and add 0.1wt% defoamer to the foaming liquid. Pass ammonia into the foaming liquid, and record the time when the foam reaches the 300mL mark. The longer the time, the better the anti-foaming performance. Repeat the experiment three times and take the average value. The test results are shown in Table 3, as follows:

[0054] Table 3

[0055]

[0056] From the comparison between Example 1 and Comparative Example 1 in Table 3, it can be seen that when the surfactant is polyoxyethylene sorbitan monolaurate and a sulfonic acid surfactant, and contains both silicone oil and modified silicone oil, the prepared high temperature resistant modified silicone defoamer has improved defoaming and antifoaming properties at low temperatures, and the defoaming and antifoaming properties at higher temperatures are also significantly improved;

[0057] From the comparison between Example 1 and Comparative Example 2 in Table 3, it can be seen that the high temperature resistant modified silicone defoamer prepared by the present application has better defoaming and antifoaming properties at low temperatures than the prior art, and also has better defoaming and antifoaming properties at higher temperatures;

[0058] From the comparison between Example 1 and Example 6 in Table 3, it can be seen that when the surfactant is polyoxyethylene sorbitan monolaurate and a sulfonic acid type surfactant, the obtained high temperature resistant modified silicone defoamer has better defoaming and antifoaming properties at low temperatures, and even if the temperature is increased, the defoaming and antifoaming properties are still good;

[0059] From the comparison between Example 1 and Examples 4-5 in Table 3, it can be seen that when the mass ratio of polyoxyethylene sorbitan monolaurate and sulfonic acid type surfactant is within an appropriate range, the defoaming and antifoaming properties of the prepared high temperature resistant modified silicone defoamer at low temperatures are further improved, and the defoaming and antifoaming properties are further improved when the use temperature is high;

[0060] From the comparison of Examples 1-3 in Table 3, it can be seen that the high temperature resistant modified silicone defoamer prepared using the components and contents provided in the present application has good defoaming and antifoaming properties at low temperatures, and also has good defoaming and antifoaming properties at higher temperatures.

[0061] The high temperature resistant modified silicone defoamers prepared in Examples 1-6 and Comparative Examples 1-2 were tested for defoaming and antifoaming properties at a temperature of 100° C. with different defoamer usage contents. The specific test method is as follows. The test results are shown in Table 4.

[0062] (3) Defoaming performance test

[0063] At 100°C, pour 25mL of a 2wt% aqueous solution of sodium dodecylbenzenesulfonate into a 100mL measuring tube and shake it up and down several times to make the foaming liquid reach 100mL. Add 0.1wt% and 0.15wt% defoaming agents to the foaming liquid respectively, and start a stopwatch until the foam disappears completely. The shorter the time, the better the defoaming performance of the defoaming agent. Repeat the experiment three times and take the average value.

[0064] (4) Test of anti-foaming performance:

[0065] At 100°C, add 100mL of 2wt% sodium dodecylbenzene sulfonate aqueous solution into a 1L measuring cylinder, and add 0.1wt% of the foaming liquid and 0.15wt% of the defoamer. Pass ammonia into the foaming liquid and record the time when the foam reaches the 300mL mark. The longer the time, the better the anti-foaming performance. Repeat the experiment three times and take the average value.

[0066] Table 4

[0067]

[0068] It can be seen from Example 1 and Comparative Example 1 in Table 4 that when the surfactant is polyoxyethylene sorbitan monolaurate and a sulfonic acid surfactant, and contains both silicone oil and modified silicone oil, the prepared high temperature resistant modified silicone defoamer has good defoaming and antifoaming properties even at high temperatures when the content is low;

[0069] It can be seen from Example 1 and Comparative Example 2 in Table 4 that the high temperature resistant modified silicone defoamer prepared by the present application has better defoaming and antifoaming properties at higher temperatures when the content is lower than that of the prior art;

[0070] From the comparison between Example 1 and Examples 4-6 in Table 4, it can be seen that when the surfactant is polyoxyethylene sorbitan monolaurate and a sulfonic acid surfactant, and the mass ratio of polyoxyethylene sorbitan monolaurate and the sulfonic acid surfactant is within an appropriate range, when the content of the obtained high temperature resistant modified silicone defoamer is low, the defoaming property and the antifoaming property at high temperature are further improved;

[0071] From the comparison of Examples 1-3 in Table 4, it can be seen that the high temperature resistant modified silicone defoamer prepared using the components and contents provided in the present application has good defoaming and antifoaming properties even when the content is low and even when the temperature is high. Compared with the defoamers in the prior art, the high temperature resistant modified silicone defoamer provided in the present application still has high defoaming and antifoaming properties when the content is low.

[0072] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A high temperature resistant modified silicone defoamer, Features: The high temperature resistant modified silicone defoamer comprises the following components in parts by mass: 30-50 parts of organic silicone oil, 15-25 parts of modified organic silicone oil, 3-8 parts of emulsifier, 2-5 parts of surfactant, 3-6 parts of thickener, 0.1-1 parts of preservative, 0.5-3 parts of silicon dioxide, and 50-80 parts of deionized water.

2. The high temperature resistant modified silicone defoamer according to claim 1, Features: The surfactant comprises polyoxyethylene sorbitan monolaurate and a sulfonic acid type surfactant.

3. The high temperature resistant modified silicone defoamer according to claim 2, Features: The raw materials for preparing the sulfonic acid surfactant include nonylphenol, tetra-n-butylammonium bromide, 1,4-dibromobutane, anhydrous dichloromethane and chlorosulfonic acid.

4. The high temperature resistant modified silicone defoamer according to claim 3, Features: The mass ratio of the polyoxyethylene sorbitan monolaurate to the sulfonic acid type surfactant is 1: (1.2-1.5)。 5. The high temperature resistant modified silicone defoamer according to claim 3, Features: The raw materials for preparing the modified organic silicone oil include terminal epoxy silicone oil, polyether diamine and tetradecyl ethylene oxide.

6. The high temperature resistant modified silicone defoamer according to claim 1, Features: The number average molecular weight of the epoxy-terminated silicone oil is 5000-8000.

7. The high temperature resistant modified silicone defoamer according to claim 6, Features: The molecular weight of the polyether diamine is 800-1500.

8. The high temperature resistant modified silicone defoamer according to claim 3, Features: The preparation method of the sulfonic acid surfactant comprises the following steps: (1.1) nonylphenol, tetra-n-butylammonium bromide and sodium hydroxide solution are placed in a first reaction kettle and stirred and heated to a suitable temperature, 1,4-dibromobutane is added to the first reaction kettle for heating reaction, and after the reaction is completed, the reaction is cooled, extracted, washed, dried and filtered to obtain an intermediate; (1.2) The intermediate obtained in step (1.1) is placed in a second reaction kettle, and a mixture of anhydrous dichloromethane and chlorosulfonic acid is dripped into the second reaction kettle for low-temperature reaction. After the reaction is completed, the mixture is purified to obtain a sulfonic acid-type surfactant.

9. A method for preparing a high temperature resistant modified organosilicon defoamer according to any one of claims 1 to 8, Features: The following steps are involved: (2.1) Add silicone oil, modified silicone oil, surfactant and silicon dioxide into a reactor, raise the temperature of the reactor to 80-125°C, and stir until mixed; (2.2) Add thickener and preservative to the material in step (2.1), heat to 220-250° C., and stir thoroughly until mixed; (2.3) After the mixed substance in step (2.2) is cooled to 90-100° C., an emulsifier and deionized water are added and mixed to obtain a high temperature resistant modified silicone defoaming agent.

10. Use of the high temperature resistant modified silicone defoamer according to any one of claims 1 to 8 in textile auxiliaries.

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