A modified silicone defoamer and a method for preparing the same

Abstract

The application discloses a modified organosilicon defoaming agent and a preparation method thereof, and relates to the technical field of defoaming. The modified organosilicon defoaming agent and the preparation method thereof comprise the following components by mass ratio: 89.57 g of liquid mercaptan silicone oil, 20.30 g of triethylamine, 89.57 g of dimethyl sulfoxide, 3.45 g of a methyl-terminated allyl polyoxyethylene ether, 13.80 g of a methyl-terminated allyl polyoxypropylene ether, 0.34 g of azobisdimethyl isobutyronitrile, 32.25 g of butyl acetate, 19.29 g of 2-bromoisobutyrate methyl ester, a magnesium sulfate and sodium chloride aqueous solution, a coupling agent and a thickening agent. The modified organosilicon defoaming agent has good defoaming performance and bubble inhibiting performance, has strong compatibility with different emulsions, and has defoaming performance and bubble inhibiting performance equivalent to polyether defoaming agents in a water-based resin system.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of defoaming, in particular to a modified silicone defoamer and a preparation method thereof. BACKGROUND

[0002] A large amount of foam in industrialization will affect the process control and product quality. To reduce or eliminate foam, the most direct method is to use defoamer. Among them, the organic silicon defoamer has low surface tension, stable chemical properties, high safety performance and good defoaming and foam suppressing performance; the biggest advantage of polyether defoamer is strong foam suppressing ability, high temperature resistance, strong acid and alkali resistance and the like.

[0003] The present application inventors found that in the practical use process, the following problems exist: the existing technology of organic silicon type defoamer has low toxicity, oxidation resistance and strong bubble breaking ability, but the foam suppressing ability is low, so the consumption is large. Although the polyether defoamer has strong foam suppressing ability, the bubble breaking rate is low.

[0004] Therefore, it is necessary to provide a modified silicone defoamer and a preparation method thereof to solve the above technical problems. SUMMARY

[0005] The purpose of the present application is to provide a modified silicone defoamer and a preparation method thereof to solve the problems in the background art.

[0006] In order to achieve the above purpose, the present application adopts the following technical scheme:

[0007] A modified silicone defoamer and a preparation method thereof, according to the mass ratio, comprising the following components: 89.57g of liquid mercapto silicone oil, 20.30g of triethylamine, 89.57g of dimethyl sulfoxide, 10.24g of carbon disulfide, 3.45g of methyl-terminated allyl polyoxyethylene ether, 13.80g of methyl-terminated allyl polyoxypropylene ether, 0.34g of azobis isobutyronitrile, 32.25g of butyl acetate, 19.29g of 2-bromoisobutyrate, a magnesium sulfate and sodium chloride aqueous solution, a coupling agent and a thickening agent.

[0008] As a further scheme of the present application, the liquid mercapto silicone oil comprises the following components according to the mass ratio: 64.00g of octamethylcyclotetrasiloxane, 22.44g of mercaptopropylmethyldimethoxysilane, 16.42g of hexamethyldisiloxane, 2.01g of water, 1.68g of toluenesulfonic acid, magnesium sulfate and sodium carbonate.

[0009] As a further scheme of the present application, the magnesium sulfate is anhydrous magnesium sulfate, and the sodium carbonate is anhydrous sodium carbonate.

[0010] As a further scheme of the present application, the water is deionized water.

[0011] As a further scheme of the present application, the thickening agent is one or both of hydroxyethyl cellulose and hydroxypropyl cellulose.

[0012] As a further scheme of the present application, the coupling agent is isopropyl dioleate.

[0013] A preparation method of a modified organosilicon defoaming agent, and the specific steps are as follows:

[0014] S1、将64.00g八甲基环四硅氧烷、22.44g巯丙基甲基二甲氧基硅烷、16.42g六甲基二硅氧烷和2.01g水置于有N2保护且有回流装置的四口烧瓶中，25℃搅拌10min后加入 1.68g甲苯磺酸，于70℃油浴下反应10h；

[0015] S2, the reaction liquid in S1 is cooled to room temperature, the water layer is removed by liquid separation, anhydrous sodium carbonate is added to the organic layer to adjust the pH value to 7.0 ± 0.1, anhydrous magnesium sulfate is added, and then the mixture is filtered under suction to obtain a clear and transparent liquid mercaptosilicone oil with a yield of 85.6%;

[0016] S3、将89.57g液体巯基硅油、20.30g三乙胺、89.57g二甲亚砜，置于有N2保护的四口烧瓶中，25℃下搅拌均匀后加入10.24g二硫化碳，10min后加入19.29g的2-溴代 异丁酸甲酯，室温继续反应16h，得到黄色或橙黄色的浑浊液体；

[0017] S4, the liquid in S3 is extracted with n-hexane, the lower layer solution is removed, the upper layer liquid is washed with saturated sodium chloride aqueous solution once, and then washed with water for 3 times, anhydrous magnesium sulfate is added after water washing, and then the mixture is filtered under suction, rotary evaporation is performed, and a clear and transparent light yellow or yellow liquid is obtained with a yield of 86.3%;

[0018] S5、将S4中15.00g的黄色液体与3.45g甲基封端的烯丙基聚氧乙烯醚、13.80g甲基封端的烯丙基聚氧丙烯醚、0.12g偶氮二异丁腈、32.25g乙酸丁酯，置于装有N2保护、 回流装置的四口烧瓶中，然后加入偶联剂和增稠剂于75℃油浴下反应1h，待反应后再补充加入0.22g的偶氮二异丁腈继续反应7h；

[0019] S6, the liquid after the reaction in S5 is subjected to reduced pressure distillation to remove butyl acetate, and a light yellow or yellow liquid is obtained with a yield of 91.8%, and the modified organosilicon defoaming agent is prepared.

[0020] Compared with the related art, the modified organosilicon defoaming agent and the preparation method thereof have the following beneficial effects:

[0021] The modified organosilicon defoaming agent has good defoaming performance and foam suppressing performance, has strong compatibility with different emulsions, and has defoaming performance and foam suppressing performance comparable to polyether defoaming agents in a water-based resin system, and the defoaming agent has better stability after defoaming, is not easy to foam in moderate stirring, and the preparation method is simple and easy to operate and is easy to popularize. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 A step diagram of the preparation method of the modified organosilicon defoaming agent is provided. DETAILED DESCRIPTION

[0023] For the convenience of understanding the present application, the present application will be described more fully below with reference to the accompanying drawings, in which typical embodiments of the present application are shown.

[0024] Embodiment one:

[0025] A modified silicone defoamer and a preparation method thereof, according to the mass ratio, comprising the following components: 89.57g of liquid mercapto silicone oil, 20.30g of triethylamine, 89.57g of dimethyl sulfoxide, 10.24g of carbon disulfide, 3.45g of methyl-terminated allyl polyoxyethylene ether, 13.80g of methyl-terminated allyl polyoxypropylene ether, 0.34g of azobis isobutyronitrile, 32.25g of butyl acetate, 19.29g of 2-bromoisobutyrate methyl, aqueous solution of magnesium sulfate and sodium chloride, coupling agent and thickening agent.

[0026] As a further aspect of the present application, the liquid mercapto silicone oil comprises the following components according to the mass ratio: 64.00g of octamethylcyclotetrasiloxane, 22.44g of mercaptopropylmethyldimethoxysilane, 16.42g of hexamethyldisiloxane, 2.01g of water, 1.68g of toluenesulfonic acid, magnesium sulfate and sodium carbonate.

[0027] As a further aspect of the present application, the magnesium sulfate is anhydrous magnesium sulfate, and the sodium carbonate is anhydrous sodium carbonate.

[0028] As a further aspect of the present application, the water is deionized water.

[0029] As a further aspect of the present application, the thickening agent is one or both of hydroxyethyl cellulose and hydroxypropyl cellulose.

[0030] As a further aspect of the present application, the coupling agent is isopropyl dioleoyl acyloxy titanate.

[0031] A method for making a modified silicone defoamer, the specific steps are as follows:

[0032] S1、将64.00g八甲基环四硅氧烷、22.44g巯丙基甲基二甲氧基硅烷、16.42g六甲基二硅氧烷和2.01g水置于有N2保护且有回流装置的四口烧瓶中，25℃搅拌10min后加入 1.68g甲苯磺酸，于70℃油浴下反应10h；

[0033] S2, cool the reaction liquid in S1 to room temperature, remove the water layer by liquid separation, add anhydrous sodium carbonate to the organic layer to adjust the pH value to 7.0 ± 0.1, add anhydrous magnesium sulfate, and then filter to obtain a clear and transparent liquid mercapto silicone oil with a yield of 85.6%;

[0034] S3、将89.57g液体巯基硅油、20.30g三乙胺、89.57g二甲亚砜，置于有N2保护的四口烧瓶中，25℃下搅拌均匀后加入10.24g二硫化碳，10min后加入19.29g的2-溴代 异丁酸甲酯，室温继续反应16h，得到黄色或橙黄色的浑浊液体；

[0035] S4, extract the liquid in S3 with n-hexane, remove the lower solution, wash the upper liquid with saturated sodium chloride aqueous solution once, wash with water for 3 times, add anhydrous magnesium sulfate after water washing, dry, extract, and get clear and transparent light yellow or yellow liquid, the yield is 86.3%;

[0036] S5、将S4中15.00g的黄色液体与3.45g甲基封端的烯丙基聚氧乙烯醚、13.80g甲基封端的烯丙基聚氧丙烯醚、0.12g偶氮二异丁腈、32.25g乙酸丁酯，置于装有N2保护、 回流装置的四口烧瓶中，然后加入偶联剂和增稠剂于75℃油浴下反应1h，待反应后再补充加入0.22g的偶氮二异丁腈继续反应7h；

[0037] S6, remove butyl acetate in the liquid after the reaction in S5 by reduced pressure distillation, get light yellow or yellow liquid, the yield is 91.8%, and the modified organic silicon defoaming agent can be prepared.

[0038] Example two:

[0039] A modified organic silicon defoaming agent and a preparation method thereof, according to the mass ratio, comprising the following components: 89.57g liquid mercapto silicone oil, 20.50g triethylamine, 90.72g dimethyl sulfoxide, 10.37g carbon disulfide, 3.45g methyl-terminated allyl polyoxyethylene ether, 13.80g methyl-terminated allyl polyoxypropylene ether, 0.34g azobisdimethyl isobutyronitrile, 32.55g butyl acetate, 19.40g 2-bromoisobutyrate methyl, magnesium sulfate and sodium chloride aqueous solution, coupling agent and thickening agent.

[0040] As a further scheme of the application, the liquid mercapto silicone oil comprises the following components according to the mass ratio: 64.22g octamethylcyclotetrasiloxane, 22.56g mercaptopropylmethyldimethoxysilane, 16.52g hexamethyldisiloxane, 2.12g water, 1.68g toluenesulfonic acid, magnesium sulfate and sodium carbonate.

[0041] As a further scheme of the application, the magnesium sulfate is anhydrous magnesium sulfate, and the sodium carbonate is anhydrous sodium carbonate.

[0042] As a further scheme of the application, the water is deionized water.

[0043] As a further scheme of the application, the thickening agent is one or both of hydroxyethyl cellulose and hydroxypropyl cellulose.

[0044] As a further scheme of the application, the coupling agent is isopropyl dioleoyl acyloxy titanate.

[0045] A preparation method of a modified organic silicon defoaming agent, the specific steps are as follows:

[0046] S1、将64.22g八甲基环四硅氧烷、22.56g巯丙基甲基二甲氧基硅烷、16.52g六甲基二硅氧烷和2.01g水置于有N2保护且有回流装置的四口烧瓶中，25℃搅拌10min后加入 1.68g甲苯磺酸，于70℃油浴下反应10h；

[0047] S2, the reaction solution in S1 is cooled to room temperature, and the water layer is removed by liquid separation. The organic layer is added with anhydrous sodium carbonate to adjust the pH value to 7.0 ± 0.1, and anhydrous magnesium sulfate is added. Filtration is performed to obtain a clear and transparent mercaptosilicone oil with a yield of 85.6%;

[0048] S3、将89.57g液体巯基硅油、20.50g三乙胺、90.72g二甲亚砜，置于有N2保护的四口烧瓶中，25℃下搅拌均匀后加入10.37g二硫化碳，10min后加入19.40g的2-溴代 异丁酸甲酯，室温继续反应16h，得到黄色或橙黄色的浑浊液体；

[0049] S4, the liquid in S3 is extracted with n-hexane, and the lower solution is removed. The upper liquid is washed with saturated sodium chloride aqueous solution once and washed with water for 3 times. After water washing, anhydrous magnesium sulfate is added for drying. Filtration is performed, and rotary evaporation is performed to obtain a clear and transparent light yellow or yellow liquid with a yield of 86.3%;

[0050] S5、将S4中15.00g的黄色液体与3.45g甲基封端的烯丙基聚氧乙烯醚、13.80g甲基封端的烯丙基聚氧丙烯醚、0.12g偶氮二异丁腈、32.55g乙酸丁酯，置于装有N2保护、 回流装置的四口烧瓶中，然后加入偶联剂和增稠剂于75℃油浴下反应1h，待反应后再补充加入0.22g的偶氮二异丁腈继续反应7h；

[0051] S6, the liquid after the reaction in S5 is distilled under reduced pressure to remove butyl acetate to obtain a light yellow or yellow liquid with a yield of 91.8%. The modified organosilicon defoaming agent can be prepared.

[0052] The above examples are only used to illustrate the technical solutions of the present application, but not to limit the same. Although the present application has been described in detail with reference to the foregoing examples, it should be understood by those skilled in the art that the technical solutions recorded in the foregoing examples can be modified, or some technical features can be replaced by equivalent ones. These modifications or replacements will not change the essence of the corresponding technical solutions out of the protection scope of the technical solutions of the embodiments of the present application.

Claims

1. A modified organosilicon defoamer, characterized in that, According to mass proportions, the following components are included: 89.57g liquid mercaptosilicone oil, 20.30g triethylamine, 89.57g dimethyl sulfoxide, 10.24g carbon disulfide, 3.45g methyl-terminated allyl polyoxyethylene ether, 13.80g methyl-terminated allyl polyoxypropylene ether, 0.34g azobisisobutyronitrile, 32.25g butyl acetate, 19.29g methyl 2-bromoisobutyrate, magnesium sulfate and sodium chloride aqueous solution, coupling agent and thickener.

2. The modified organosilicon defoamer according to claim 1, characterized in that, The liquid mercaptosilicone oil comprises the following components by mass percentage: 64.00g octamethylcyclotetrasiloxane, 22.44g mercaptopropylmethyldimethoxysilane, 16.42g hexamethyldisiloxane, 2.01g water, 1.68g toluenesulfonic acid, magnesium sulfate, and sodium carbonate.

3. The modified organosilicon defoamer according to claim 2, characterized in that, The magnesium sulfate is anhydrous magnesium sulfate, and the sodium carbonate is anhydrous sodium carbonate.

4. The modified organosilicon defoamer according to claim 2, characterized in that, The water is deionized water.

5. The modified organosilicon defoamer according to claim 1, characterized in that, The thickener is one or both of hydroxyethyl cellulose and hydroxypropyl cellulose.

6. The modified organosilicon defoamer according to claim 1, characterized in that, The coupling agent is isopropyl dioleoyloxytitanate.

7. The method for preparing a modified organosilicon defoamer according to claim 3, characterized in that, A method for preparing a modified organosilicon defoamer, the specific steps of which are as follows: S1. Place 64.00g of octamethylcyclotetrasiloxane, 22.44g of mercaptopropylmethyldimethoxysilane, 16.42g of hexamethyldisiloxane and 2.01g of water in a four-necked flask with N2 protection and a reflux device. Stir at 25°C for 10 min, then add 1.68g of toluenesulfonic acid and react in an oil bath at 70°C for 10 h. S2. Cool the reaction solution in S1 to room temperature, separate the aqueous layer, add anhydrous sodium carbonate to the organic layer to adjust the pH to 7.0, add anhydrous magnesium sulfate, filter, and obtain a clear and transparent liquid mercaptosilicone oil with a yield of 85.6%. S3. Place 89.57g of liquid mercaptosilicone oil, 20.30g of triethylamine, and 89.57g of dimethyl sulfoxide in a four-necked flask protected with N2. Stir well at 25°C, then add 10.24g of carbon disulfide. After 10 minutes, add 19.29g of methyl 2-bromoisobutyrate. Continue the reaction at room temperature for 16 hours to obtain a yellow or orange-yellow turbid liquid. S4. Extract the liquid from S3 with n-hexane to remove the lower layer. Wash the upper layer once with saturated sodium chloride aqueous solution, then wash three times with water. After washing with water, add anhydrous magnesium sulfate to dry, filter, and rotary evaporate to obtain a clear, transparent pale yellow or yellow liquid with a yield of 86.3%. S5. Place 15.00g of the yellow liquid from S4, 3.45g of methyl-terminated allyl polyoxyethylene ether, 13.80g of methyl-terminated allyl polyoxypropylene ether, 0.12g of azobisisobutyronitrile, and 32.25g of butyl acetate into a four-necked flask equipped with N2 protection and a reflux device. Then add coupling agent and thickener and react in an oil bath at 75°C for 1 hour. After the reaction, add 0.22g of azobisisobutyronitrile and continue the reaction for 7 hours. S6. After the reaction in S5 is completed, remove butyl acetate by vacuum distillation to obtain a pale yellow or yellow liquid with a yield of 91.8%, which can be used to prepare a modified organosilicon defoamer.

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