阅读说明：本技术 一种有机硅乳液消泡剂及其制备方法 (Organic silicon emulsion defoaming agent and preparation method thereof ) 是由 苏芳 黄伟 曹添 胡佳新 于 2020-06-12 设计创作，主要内容包括：本发明的目的是提供一种有机硅乳液消泡剂及其制备方法。使用含氢硅油和白炭黑反应生成白炭黑硅膏来部分代替高粘度有机硅组合物,降低高粘度有机硅组合物带来的产品漂油、析出等相容性问题,通过引入助乳化剂来制备有机硅乳液消泡剂,制备的有机硅乳液消泡剂在应用体系中具有很好的相容性、耐高温性和消抑泡性能。(The invention aims to provide an organic silicon emulsion defoaming agent and a preparation method thereof. The high-viscosity silicone composition is partially replaced by white carbon black silicon paste generated by the reaction of hydrogen-containing silicone oil and white carbon black, the compatibility problems of product floating oil, precipitation and the like caused by the high-viscosity silicone composition are reduced, the silicone emulsion defoamer is prepared by introducing the co-emulsifier, and the prepared silicone emulsion defoamer has good compatibility, high temperature resistance and defoaming performance in an application system.)

1. An organic silicon emulsion defoaming agent and a preparation method thereof are characterized by comprising the following components:

A. silicon polyether:

the structural formula of the silicon polyether is as follows: (CH)₃)₃SiO{(CH₃)₂SiO) _x (CH₃GSiO) _y }(CH₃)₃，GIs polyether group, and the structural formula is as follows: - (CH)₂) _z (EO) _g (PO) _h R, wherein R is-H or-CH₃or-COCH₃(ii) a Subscriptx，y，z，g，hIn order to be the degree of polymerization,xis an integer of 10 to 500;yis an integer of 1 to 50;zis an integer of 2 to 6;gis an integer of 1 to 40;his an integer of 1 to 60; the using amount of the silicon polyether accounts for 5-15% of the total mass of the organic silicon emulsion defoaming agent;

B. high viscosity silicone composition:

the high-viscosity organosilicon composition is prepared by treating polyorganosiloxane, white carbon black, silicone resin and a catalyst by a certain process, and the preparation method is a technique known by technical personnel; the dynamic viscosity of the high-viscosity organic silicon composition at 25 ℃ is 200,000-900,000 mPa & s, and the using amount of the high-viscosity organic silicon composition accounts for 5-15% of the total mass of the organic silicon emulsion defoaming agent;

white carbon silicon paste

The white carbon black silicon paste is prepared by adding 2-8% of hydrophilic white carbon black and 92-98% of high hydrogen-containing silicone oil into a reactor, and stirring at 130-180 ℃ for 1-3 h; the usage amount of the white carbon black silicon paste accounts for 5-10% of the total mass of the organic silicon emulsion defoaming agent;

D. emulsifier

The emulsifier is a nonionic surfactant, and is specifically selected from nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, lauric acid polyoxyethylene ether, oleic acid polyoxyethylene ether, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, sorbitan trioleate, sorbitan monostearate polyoxyethylene ether ester, sorbitan monooleate polyoxyethylene ether ester, sorbitan tristearate polyoxyethylene ether ester and castor oil polyoxyethylene ether, and the used nonionic surfactant can be used independently or in a mixed manner, and accounts for 0.5-5% of the total mass of the silicone emulsion defoamer;

auxiliary emulsifier

The auxiliary emulsifier is selected from one or more of n-butyl alcohol, ethylene glycol, propylene glycol, glycerol and polyglycerol ester, and the mass of the auxiliary emulsifier accounts for 0.5-5% of the total mass of the silicone emulsion defoamer;

F. thickening agent

The thickening agent is an acrylic acid alkali swelling thickening agent, the pH value of the thickening agent is adjusted by alkali, so that the system is thickened, the viscosity of the system is improved, and the using amount of the thickening agent accounts for 0.5-3% of the total mass of the organosilicone emulsion defoaming agent;

G. water (W)

The deionized water accounts for 60-80% of the total mass of the organic silicon emulsion defoaming agent;

the preparation method of the organic silicon emulsion defoaming agent comprises the following steps:

at room temperature, firstly, stirring and mixing the high-viscosity organic silicon composition, the white carbon black silicon paste, the silicon polyether and the emulsifier at a high speed for 0.5-1.5 h;

raising the temperature to 60-90 ℃, adding the auxiliary emulsifier while stirring, and stirring and mixing for 0.5-1 h;

thirdly, after stirring, further emulsifying the mixture by a homogenizer;

adding a thickening agent and deionized water into the mixture emulsified by the homogenizer, stirring uniformly, and adjusting the pH value to 7.0 to obtain the organic silicon emulsion defoaming agent.

Technical Field

The invention relates to an organic silicon emulsion defoaming agent and a preparation method thereof, which relate to the preparation of fine chemical additives and belong to the technical field of fine chemical preparations.

Background

The organic silicon emulsion defoaming agent is one of important organic silicon defoaming agent products, is widely applied to industry due to the unique performance and characteristics of the organic silicon emulsion defoaming agent, is widely applied to industrial fields of papermaking, spinning, sizing agents, coatings, buildings, leather, medicines, cosmetics and the like, and has continuously expanded application fields and great application potential. In the above application fields, the use of silicones in the form of aqueous emulsions is most economical, convenient and safe, while complying with the requirements of environmental protection.

For example, when the organosilicon defoamer with poor stability is specifically applied, the silicone defoamer is easy to float and separate out, so that 'silicon spots' are formed, the normal operation of industrial production is seriously influenced, and the economic great loss is caused. Therefore, the stability of the silicone emulsion is of considerable importance.

The emulsifier, which is a key component of silicone emulsions, is primarily used to disperse the active material. A large number of experimental experiences show that the main functions of the organic silicon emulsion are influenced by excessive emulsifier; if the emulsifier is too little, the resulting silicone emulsion is very unstable and may be lost. Patents CN102284198 and CN102527096A propose polyether modified polysiloxane, which has certain emulsifiability by grafting hydrophilic polyether segment on polysiloxane main chain by Si-C or Si-O-C bond; EP0341952 uses a combination of polyorganosiloxane and polyether-modified polysiloxane to further improve the defoaming and foam suppressing properties of the emulsion. Patents CN1807512 and CN101298027 describe the preparation of more stable silicone emulsions by dispersing a high viscosity silicone mixture in water by adding some auxiliary substances; patent CN102002242A describes a method for improving emulsion stability by introducing higher fatty alcohol polyether; patent CN101003008 describes the preparation of stable emulsions by chemical modification of hydroxyl-containing polyether molecules as emulsifiers to produce new capped polyethers which are then used in the emulsion preparation.

The silicone emulsion is prepared by emulsifying the silicone polyether with different structures, and the defoaming and foam inhibiting performance, compatibility and stability of the product cannot be considered at the same time.

Disclosure of Invention

The invention aims to provide an organic silicon emulsion defoaming agent and a preparation method thereof. The high-viscosity silicone composition is partially replaced by white carbon black silicon paste generated by the reaction of hydrogen-containing silicone oil and white carbon black, the compatibility problems of product floating oil, precipitation and the like caused by the high-viscosity silicone composition are reduced, the silicone emulsion defoamer is prepared by introducing the co-emulsifier, and the prepared silicone emulsion defoamer has good compatibility, high temperature resistance and defoaming performance in an application system.

The organic silicon emulsion defoaming agent prepared by the invention comprises the following components:

A. silicon polyether:

the structural formula of the silicon polyether is as follows: (CH)₃)₃SiO{(CH₃)₂SiO) _x (CH₃GSiO) _y }(CH₃)₃G is a polyether group, and the structural formula is as follows: - (CH)₂) _z (EO) _g (PO) _h R, wherein R is-H or-CH₃or-COCH₃(ii) a Subscriptx，y，z，g，hIn order to be the degree of polymerization,xis an integer of 10 to 500;yis an integer of 1 to 50;zis an integer of 2 to 6;gis an integer of 1 to 40;his an integer of 1 to 60; the using amount of the silicon polyether accounts for 5-15% of the total mass of the organic silicon emulsion defoaming agent.

B. High viscosity silicone composition:

the high-viscosity organosilicon composition is prepared by treating polyorganosiloxane, white carbon black, silicone resin and a catalyst by a certain process, and the preparation method is a technique known by technical personnel. The high-viscosity organic silicon composition has the dynamic viscosity of 200,000-900,000 mPa & s at 25 ℃, and the dosage of the high-viscosity organic silicon composition accounts for 5-15% of the total mass of the organic silicon emulsion defoaming agent.

C. White carbon silicon paste

The white carbon black silicon paste is prepared by adding 2-8% of hydrophilic white carbon black and 92-98% of high hydrogen-containing silicone oil into a reactor, and stirring at 130-180 ℃ for 1-3 h; the usage amount of the white carbon black silicon paste accounts for 5-10% of the total mass of the organic silicon emulsion defoaming agent.

D. Emulsifier

The emulsifier in the invention is a nonionic surfactant, and is specifically selected from nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, lauric acid polyoxyethylene ether, oleic acid polyoxyethylene ether, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, sorbitan trioleate, sorbitan monostearate polyoxyethylene ether ester, sorbitan monooleate polyoxyethylene ether ester, sorbitan tristearate polyoxyethylene ether ester and castor oil polyoxyethylene ether. The nonionic surfactants used may be used alone or in admixture. The dosage of the organic silicon emulsion defoaming agent accounts for 0.5-5% of the total mass of the organic silicon emulsion defoaming agent.

E. Auxiliary emulsifier

The auxiliary emulsifier is one or more selected from n-butyl alcohol, ethylene glycol, propylene glycol, glycerol and polyglycerol ester, and the mass of the auxiliary emulsifier accounts for 0.5-5% of the total mass of the silicone emulsion defoaming agent.

F. Thickening agent

The thickening agent is an acrylic acid alkali swelling thickening agent, and the thickening agent is used for thickening a system by adjusting the pH value through alkali and improving the viscosity of the system. The amount of the thickening agent accounts for 0.5-3% of the total mass of the organic silicon emulsion defoaming agent.

G. Water (W)

The deionized water accounts for 60-80% of the total mass of the organic silicon emulsion defoaming agent.

The preparation method of the organic silicon emulsion defoaming agent comprises the following steps:

firstly, stirring and mixing a high-viscosity organic silicon composition, white carbon black silicon paste, silicon polyether and an emulsifier at a high speed for 0.5-1.5 hours at room temperature;

raising the temperature to 60-90 ℃, adding the auxiliary emulsifier while stirring, and stirring and mixing for 0.5-1 h;

thirdly, after stirring, further emulsifying the mixture by a homogenizer;

adding a thickening agent and deionized water into the mixture emulsified by the homogenizer, stirring uniformly, and adjusting the pH value to 7.0 to obtain the organic silicon emulsion defoaming agent.

Detailed Description

(1) Preparation of white carbon silica paste

White carbon silica paste C1: adding 2 mass percent of hydrophilic white carbon black and 98 mass percent of high hydrogen-containing silicone oil into a reactor, and stirring for 3 hours at the temperature of 130 ℃ to obtain white carbon black silicon paste

White carbon silica paste C2: adding 8 mass percent of hydrophilic white carbon black and 92 mass percent of high hydrogen-containing silicone oil into a reactor, and stirring for 1h at the temperature of 180 ℃ to obtain white carbon black silicon paste

White carbon silica paste C3: adding 4 mass percent of hydrophilic white carbon black and 96 mass percent of high hydrogen-containing silicone oil into a reactor, and stirring for 2 hours at the temperature of 150 ℃ to obtain white carbon black silicon paste

White carbon silica paste C4: adding 6 mass percent of hydrophilic white carbon black and 94 mass percent of high hydrogen-containing silicone oil into a reactor, and stirring for 2 hours at the temperature of 170 ℃ to obtain white carbon black silicon paste

White carbon silica paste C5: adding 3 mass percent of hydrophilic white carbon black and 97 mass percent of high hydrogen-containing silicone oil into a reactor, and stirring for 1.5 hours at the temperature of 140 ℃ to obtain white carbon black silicon paste

(2) Preparation of high viscosity silicone compositions

With reference to the preparation process of example 1 in patent US4639489, the following silicone compositions of different viscosities were prepared, in particular as follows:

TABLE 1 high viscosity Silicone compositions

(3) Preparation of silicon polyethers

TABLE 2 preparation of silicon polyethers

Preparation of organosilicon emulsion defoaming agent

Example 1

At room temperature, firstly stirring and mixing 5g of high-viscosity organic silicon composition B1, 8.5g of white carbon black silicon paste C1, 5g of silicon polyether E1 and 0.5g of nonylphenol polyoxyethylene ether at a high speed for 0.5 h; raising the temperature to 90 ℃, adding 0.5g of n-butanol while stirring, and stirring and mixing for 0.5 h; after stirring, further emulsifying the mixture by a homogenizer; and adding 0.5g of acrylic acid alkali swelling thickener and 80g of deionized water into the mixture emulsified by the homogenizer, uniformly stirring, and adjusting the pH value to 7.0 to obtain the organic silicon emulsion defoaming agent.

Example 2

At room temperature, firstly stirring and mixing 15g of high-viscosity organic silicon composition B2, 8.5g of white carbon silica paste C2, 15g of silicon polyether E2, 0.2g of oleic acid polyoxyethylene ether and 0.3g of sorbitan monostearate at a high speed for 1.5 h; raising the temperature to 60 ℃, adding 0.5g of glycol while stirring, and stirring and mixing for 1 h; after stirring, further emulsifying the mixture by a homogenizer; and adding 0.5g of acrylic acid alkali swelling thickener and 60g of deionized water into the mixture emulsified by the homogenizer, uniformly stirring, and adjusting the pH value to 7.0 to obtain the organic silicon emulsion defoaming agent.

Example 3

At room temperature, firstly stirring and mixing 7g of high-viscosity organosilicon composition B3, 8g of white carbon black silicon paste C3, 7g of silicon polyether E3 and 5g of sorbitan monostearate polyoxyethylene ether ester for 1 hour at high speed; raising the temperature to 75 ℃, adding 5g of propylene glycol while stirring, and stirring and mixing for 1 h; after stirring, further emulsifying the mixture by a homogenizer; adding 3g of acrylic acid-alkali swelling thickener and 65 g of deionized water into the mixture emulsified by the homogenizer, uniformly stirring, and adjusting the pH value to 7.0 to obtain the organic silicon emulsion defoaming agent.

Example 4

At room temperature, firstly stirring and mixing 7g of high-viscosity organic silicon composition B4, 5g of white carbon black silicon paste C4, 10g of silicon polyether E4, 1.5g of sorbitan tristearate polyoxyethylene ether ester and 1.5g of castor oil polyoxyethylene ether at a high speed for 1 h; raising the temperature to 80 ℃, adding 3g of glycerol while stirring, and stirring and mixing for 0.5 h; after stirring, further emulsifying the mixture by a homogenizer; adding 2g of acrylic acid-base swelling thickener and 70g of deionized water into the mixture emulsified by the homogenizer, uniformly stirring, and adjusting the pH value to 7.0 to obtain the organic silicon emulsion defoaming agent.

Example 5

At room temperature, firstly stirring and mixing 8g of high-viscosity organic silicon composition B1, 10g of white carbon black silicon paste C5, 8g of silicon polyether E1 and 1g of castor oil polyoxyethylene ether at a high speed for 1.5 h; raising the temperature to 70 ℃, adding 1g of polyglycerol ester while stirring, and stirring and mixing for 1 h; after stirring, further emulsifying the mixture by a homogenizer; adding 1g of acrylic acid-alkali swelling thickener and 71g of deionized water into the mixture emulsified by the homogenizer, uniformly stirring, and adjusting the pH value to 7.0 to obtain the organic silicon emulsion defoaming agent.

Comparative example 1

At room temperature, firstly stirring and mixing 13.5g of high-viscosity organic silicon composition B1, 5g of silicon polyether E1 and 0.5g of nonylphenol polyoxyethylene ether at a high speed for 0.5 h; raising the temperature to 90 ℃, adding 0.5g of n-butanol while stirring, and stirring and mixing for 0.5 h; after stirring, further emulsifying the mixture by a homogenizer; and adding 0.5g of acrylic acid alkali swelling thickener and 80g of deionized water into the mixture emulsified by the homogenizer, uniformly stirring, and adjusting the pH value to 7.0 to obtain the organic silicon emulsion defoaming agent.

Comparative example 2-

At room temperature, firstly stirring and mixing 15g of high-viscosity organic silicon composition B2, 8.5g of white carbon silica paste C2, 15g of silicon polyether E2, 0.2g of oleic acid polyoxyethylene ether and 0.8g of sorbitan monostearate at a high speed for 1.5 h; after stirring, further emulsifying the mixture by a homogenizer; and adding 0.5g of acrylic acid alkali swelling thickener and 60g of deionized water into the mixture emulsified by the homogenizer, uniformly stirring, and adjusting the pH value to 7.0 to obtain the organic silicon emulsion defoaming agent.

Comparative example 3

At room temperature, firstly stirring and mixing 7g of high-viscosity organosilicon composition B3, 8g of white carbon silica paste C3, 7g of silicon polyether E3, 5g of sorbitan monostearate polyoxyethylene ether ester and 5g of propylene glycol at a high speed for 1 hour; after stirring, further emulsifying the mixture by a homogenizer; adding 3g of acrylic acid-alkali swelling thickener and 65 g of deionized water into the mixture emulsified by the homogenizer, uniformly stirring, and adjusting the pH value to 7.0 to obtain the organic silicon emulsion defoaming agent.

Method for testing organic silicon emulsion defoaming agent

(1) High temperature stability of the aqueous dilution:

adding 1% of organic silicon emulsion defoaming agent into 99% of water, heating, observing the liquid level condition of the water diluent, recording the temperature when the liquid level begins to generate oil point, namely the floating oil temperature of the defoaming agent, wherein the higher the floating oil temperature is, the better the high temperature resistance is.

TABLE 3 high temperature stability of the aqueous dilution

(2) Testing the compatibility of the defoaming agent:

100ml of the slurry of the application system is added into a 150ml cup, 1 percent of the organic silicon emulsion defoaming agent is added, and the cup is sealed. And forcibly shaking for 5 minutes, sealing the cup, putting the cup into a water bath kettle at 70 ℃, keeping the temperature for 1 hour, taking out the cup, and observing the liquid level condition and the inner wall condition of the cup when the temperature is reduced to normal temperature, wherein the less the precipitation is, the better the compatibility is.

TABLE 4 thermal stability in the slurries

(3) The defoaming and foam inhibiting performance of the organic silicon defoaming agent is as follows:

and adding 160ml of prepared foaming liquid into a 250ml measuring cylinder with a plug, adding 0.05g of organic silicon emulsion defoaming agent, shaking the bottles up and down at the speed of 2 s/time, shaking the bottles 10 times for each group, recording the defoaming time of each group, and the shorter the defoaming time is, the better the defoaming and foam inhibition performance is.

TABLE 5 defoaming agent defoaming and foam suppressing Properties