Preparation method of organic silicon emulsion

Abstract

The invention provides a preparation method of an organic silicon emulsion. The preparation method comprises the following steps: uniformly mixing silicon polyether and a first part of ester synergist for later use; firstly, the organic silicon composition, the emulsifier and the second part of the ester synergist are mixed and emulsified at a high speed, then a mixture of the silicon polyether and the first part of the ester synergist is continuously added for secondary emulsification dispersion, the ester synergist has an emulsification dispersion effect and is divided into two parts for use, and the two parts are matched with a secondary emulsification process. Meanwhile, the ester synergist has a defoaming function, the problem of attenuation does not exist when the ester synergist is used as a molecular-level defoaming agent, and the defoaming and foam inhibition performance of the organic silicon emulsion can be improved.

Description

Technical Field

[0001] The invention relates to a method for preparing an organosilicon emulsion, which improves the anti-foaming performance and dispersibility of the organosilicon emulsion. The organosilicon emulsion of the invention belongs to a fine chemical additive, and therefore belongs to the technical field of fine chemicals. Background Art

[0002] The structure of organosilicon products contains both "organic groups" and "inorganic structures". This special composition and molecular structure makes it combine the characteristics of organic matter with the functions of inorganic matter. Compared with other polymer materials, the most outstanding properties of organosilicon products are: temperature resistance, weather resistance, electrical insulation, biological properties, low surface tension and low surface energy, so its application range is very wide.

[0003] Silicone emulsion is one of the important silicone products, composed of silicone, water and surfactants. Due to its unique properties and characteristics, it is widely used in industry. Silicone emulsion is divided into inactive silicone emulsion, active silicone emulsion, modified silicone emulsion and silicone composite emulsion, which are further divided into cationic silicone emulsion, anionic silicone emulsion, non-ionic silicone emulsion and composite ionic silicone emulsion, and also divided into water-in-oil silicone emulsion and water-in-oil silicone emulsion.

[0004] Organosilicon emulsion defoamer is one of the types of defoamers. There are many types of defoamers commonly found in the market. Organosilicon defoamers are mainly composed of polysiloxane and hydrophobic particles. Due to the uniqueness of polysiloxane in its structure, it has a lower surface tension and is not easy to react chemically with the foaming medium, so it can be used as a good defoamer. Due to its unique performance and characteristics, it is widely used in industry, including papermaking, textiles, pulp, coatings, construction, leather, medicine, cosmetics, etc., and its application fields are constantly expanding, with great application potential. In the above application fields, organosilicon is most economical, convenient, safe, and meets environmental protection requirements when used in the form of water emulsion.

[0005] Patents CN1807512 and CN101298027 introduce the preparation of a relatively stable silicone emulsion by dispersing a high-viscosity silicone mixture in water by adding some auxiliary substances; Patent CN102002242A introduces a method for improving the stability of the emulsion by introducing a high-grade fatty alcohol polyether; Patent CN101003008 introduces the preparation of a stable emulsion by chemically modifying a hydroxyl-containing polyether molecule as an emulsifier to generate a new capped polyether, which is then used in the preparation of the emulsion.

[0006] CN1613537 prepares a high temperature resistant silicone emulsion type defoamer, which has fast and lasting defoaming at high temperature, is not easy to break the emulsion when heated, is not easy to produce silicon spots, and has strong shear resistance. However, the viscosity of this silicone emulsion is large and it is not easy to disperse in the foaming medium, causing some inconvenience to the production operation process. Patent CN 101298027 introduces a method of using a high viscosity silicone emulsifier to disperse a high viscosity silicone composition, but the production of a high viscosity silicone emulsifier is relatively difficult. CN116785781A utilizes the reaction of double-bond polyether polyol and vinyl silicone oil to prepare silicon polyether, which is then emulsified to prepare polyether-modified silicone defoamer; CN116099238A synthesizes highly branched silicone defoaming actives to improve the defoaming and anti-foaming performance of the defoamer, and utilizes polyether esterification products, thickeners and water to emulsify the silicone actives, thereby improving the stability and compatibility of the product; CN115445251A discloses a butynediol ether-modified silicone defoamer and a preparation method thereof, which has the advantages of silicone defoamer such as fast defoaming speed and strong stability, and also has the advantages of butynediol ether-modified silicone such as low foaming, surface wetting, hydrophilicity and low surface tension, and the obtained defoamer has strong defoaming ability and good compatibility with coatings. The above patents all improve the stability and compatibility of silicone defoamers by improving the structural characteristics and emulsification efficiency of silicon polyethers. Summary of the invention

[0007] The invention provides a method for preparing an organosilicon emulsion. Silicone polyether and a first part of an ester synergist are uniformly mixed for standby use. First, an organosilicon composition, an emulsifier and a second part of an ester synergist are mixed and emulsified at a high speed, and then the mixture of the silicone polyether and the first part of the ester synergist is continuously added for secondary emulsification and dispersion. The ester synergist has an emulsification and dispersion function and is used in two parts in combination with a secondary emulsification process to improve the stability and compatibility of the organosilicon emulsion. Meanwhile, the ester synergist has a defoaming function and, as a molecular-level defoamer, does not have a problem of attenuation, and can improve the defoaming and antifoaming performance of the organosilicon emulsion. Technical Solution

[0008] A method for preparing an organosilicon emulsion, wherein the organosilicon emulsion is composed of the following components: A. Antifoaming Actives The defoaming active substance is prepared by known techniques of technicians, mainly composed of polyorganosiloxane, catalyst, silicone resin and silicon dioxide, and the amount of the defoaming active substance is 10-20% of the total mass of the organosilicon emulsion.

[0009] B. Emulsifier The emulsifier is a nonionic surfactant 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, castor oil polyoxyethylene ether; the emulsifier can be used alone or in combination. The amount of the emulsifier is 10-20% of the total mass of the silicone emulsion.

[0010] C. Deionized water The dosage is 50~65% of the total mass of the silicone emulsion.

[0011] D. Silicone polyether The silicone polyether The structural formula is as follows: MD a ( Me YSiO) b M Where: M is the chain link R3SiO l / 2 , D is the chain link R2SiO 2 / 2 , R2 and R3 are the same or different and are selected from a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; Me Methyl; the structural formula of Y is: –(CH2) z O(EO) g (PO) h K, K is a capping group selected from hydrogen, methyl, ethyl, propyl, and butyl; a , b , z , g , h is the degree of polymerization, a is an integer between 10 and 500, b is an integer from 1 to 50, z is an integer from 2 to 6, g An integer from 1 to 36. h It is an integer of 0 to 20. The dosage is 2 to 15% of the total mass of the organosilicon emulsion.

[0012] E. Esters The structural formula of the ester synergist is: R'(COOR'')w The ester synergist is divided into two parts for use. In the first part of the ester synergist, R' is a straight chain or branched alkyl group containing 16 to 30 carbon atoms, and R'' is a straight chain or branched alkyl group containing 4 to 10 carbon atoms; in the second part of the ester synergist, R' is a straight chain or branched alkyl group containing 1 to 15 carbon atoms, and R'' is a straight chain or branched alkyl group containing 4 to 10 carbon atoms; w is 1 or 2; the amount of the ester synergist is 5 to 15% of the total mass of the silicone emulsion; the amount of the ester synergist in the first part accounts for 10 to 30% of the total mass of the ester synergist.

[0013] F. Thickener The thickener is selected from polyacrylamide, carbomer, xanthan gum, cellulose ethers, and polyacrylates, preferably a polyacrylate thickener, and the amount of the thickener is 0.1-3% of the total mass of the silicone emulsion.

[0014] The preparation method of the organosilicon emulsion is as follows: (1) mixing the silicone polyether and the first part of the ester synergist at room temperature to obtain a mixture M; (2) mixing the defoaming active ingredient, the emulsifier, and the second part of the ester synergist, using a high shear device at a rotation speed of 1000 to 3000 rpm for 0.5 to 2 hours to obtain a mixture N; (3) Raise the temperature to 60-90°C, add mixture M to mixture N while stirring for 0.5-2h to form mixture E; (4) Keeping the temperature constant, continue to add thickener and deionized water to mixture E, and then further emulsify the mixture through a homogenizer to obtain the organosilicon emulsion defoamer. DETAILED DESCRIPTION

[0015] Antifoam Active Examples Prepared by referring to the technical solution of Example 1 of Patent ZL201410325381.0 Silicone polyether examples

[0016] Ester synergist examples

[0017] Ester synergist examples

[0018] Silicone Emulsion Example Example 1

[0019] (1) 15 g of silicone polyether 1 and 3 g of ester synergist 1 are mixed uniformly at room temperature to obtain a mixture M1; (2) 10 g of the defoaming active ingredient, 14 g of a mixture of nonylphenol polyoxyethylene ether and octylphenol polyoxyethylene ether, and 7 g of an ester synergist 7 were mixed, and mixed for 2 h at a rotation speed of 1000 rpm using a high shear device to obtain a mixture N1; (3) Raise the temperature to 60°C and add mixture M1 to mixture N1 while stirring for 2 h to form mixture E1; (4) Keeping the temperature constant, continue to add 1 g of polyacrylate and 50 g of deionized water to the mixture E1, and then further emulsify the mixture through a homogenizer to obtain the silicone emulsion defoamer. Example 2

[0020] (1) 2 g of silicone polyether 2 and 3 g of ester synergist 2 are mixed uniformly at room temperature to obtain a mixture M2; (2) 15 g of the defoaming active ingredient, 10 g of a mixture of lauric acid polyoxyethylene ether and oleic acid polyoxyethylene ether, and 12 g of an ester synergist 8 were mixed, and the mixture was mixed for 2 h at a rotation speed of 1200 rpm using a high shear device to obtain a mixture N2; (3) Raise the temperature to 70°C and add mixture M2 to mixture N2 while stirring for 1 hour to form mixture E2; (4) Keeping the temperature constant, continue to add 3 g of polyacrylamide and 55 g of deionized water to the mixture E2, and then further emulsify the above mixture through a homogenizer to obtain the silicone emulsion defoamer. Example 3

[0021] (1) 2 g of silicone polyether 3 and 1 g of ester synergist 3 are mixed uniformly at room temperature to obtain a mixture M3; (2) 20 g of the defoaming active ingredient, 12 g of a mixture of sorbitan monostearate and sorbitan monooleate, and 4 g of an ester synergist 9 were mixed, and the mixture was mixed for 0.5 h at a rotation speed of 1600 rpm using a high shear device to obtain a mixture N3; (3) Raise the temperature to 80°C and add mixture M3 to mixture N3 while stirring for 0.5 h to form mixture E3; (4) Keeping the temperature constant, continue to add 1 g of carbomer and 60 g of deionized water to the mixture E3, and then further emulsify the mixture through a homogenizer to obtain the silicone emulsion defoamer. Example 4

[0022] (1) 6 g of silicone polyether 4 and 1 g of ester synergist 4 were mixed uniformly at room temperature to obtain a mixture M4; (2) 10 g of the defoaming active ingredient, 20 g of castor oil polyoxyethylene ether, and 9 g of the ester synergist 10 were mixed, and the mixture was mixed for 1.5 h at a speed of 2000 rpm using a high shear device to obtain a mixture N4; (3) Raise the temperature to 90°C and add mixture M4 to mixture N4 while stirring for 1 hour to form mixture E4; (4) While keeping the temperature constant, continue to add 2 g of xanthan gum and 52 g of deionized water to the mixture E4, and then further emulsify the mixture through a homogenizer to obtain the organosilicon emulsion defoamer. Example 5

[0023] (1) 3 g of silicone polyether 5 and 2.9 g of ester synergist 5 were mixed uniformly at room temperature to obtain a mixture M5; (2) 10 g of the defoaming active ingredient, 10 g of a mixture of sorbitan tristearate and sorbitan trioleate, and 9 g of an ester synergist 11 were mixed, and mixed for 1 h at a rotation speed of 2500 rpm using a high shear device to obtain a mixture N5; (3) Raise the temperature to 75°C and add mixture M5 to mixture N5 while stirring for 1.5 h to form mixture E5; (4) Keeping the temperature constant, continue to add 0.1 g of cellulose ether and 65 g of deionized water to the mixture E5, and then further emulsify the mixture through a homogenizer to obtain the organosilicon emulsion defoamer. Example 6

[0024] (1) 12 g of silicone polyether 6 and 2 g of ester synergist 6 are mixed uniformly at room temperature to obtain a mixture M6; (2) 12 g of the defoaming active ingredient, 13 g of a mixture of sorbitan monostearate polyoxyethylene ether ester and sorbitan monooleate polyoxyethylene ether ester, and 6 g of an ester synergist 12 were mixed, and the mixture was mixed for 0.5 h at a speed of 3000 rpm using a high shear device to obtain a mixture N6; (3) Raise the temperature to 65°C and add mixture M6 to mixture N6 while stirring for 2 h to form mixture E6; (4) Keeping the temperature constant, continue to add 2 g of polyacrylate and 53 g of deionized water to the mixture E6, and then further emulsify the above mixture through a homogenizer to obtain the silicone emulsion defoamer.

[0025] Comparative Example 1 (1) 10 g of the defoaming active ingredient, 14 g of a mixture of nonylphenol polyoxyethylene ether and octylphenol polyoxyethylene ether, and 7 g of an ester synergist 7 were mixed, and mixed for 2 h at a rotation speed of 1000 rpm using a high shear device to obtain a mixture N1; (2) The temperature was raised to 60°C, and 18 g of silicone polyether 1 was added to the mixture N1 while stirring for 2 h to form a mixture E7; (3) Keeping the temperature constant, continue to add 1 g of polyacrylate and 50 g of deionized water to the mixture E7, and then further emulsify the mixture through a homogenizer to obtain the silicone emulsion defoamer.

[0026] Comparative Example 2 (1) 2 g of silicone polyether 2 and 15 g of ester synergist 2 are mixed uniformly at room temperature to obtain a mixture M7; (2) 15 g of the defoaming active ingredient, 10 g of the mixture of lauric acid polyoxyethylene ether and oleic acid polyoxyethylene ether were mixed, and the mixture was mixed for 2 h at a rotation speed of 1200 rpm using a high shear device to obtain a mixture N7; (3) Raise the temperature to 70°C and add mixture M2 to mixture N2 while stirring for 1 hour to form mixture E8; (4) Keeping the temperature constant, continue to add 3 g of polyacrylamide and 55 g of deionized water to the mixture E8, and then further emulsify the mixture through a homogenizer to obtain the silicone emulsion defoamer.

[0027] Comparative Example 3 (1) 2 g of silicone polyether 3 and 1 g of ester synergist 9 are mixed uniformly at room temperature to obtain a mixture M8; (2) 20 g of the defoaming active ingredient, 12 g of a mixture of sorbitan monostearate and sorbitan monooleate, and 4 g of the ester synergist 3 were mixed, and the mixture was mixed for 0.5 h at a speed of 1600 rpm using a high shear device to obtain a mixture N8; (3) Raise the temperature to 80°C and add mixture M3 to mixture N3 while stirring for 0.5 h to form mixture E9; (4) Keeping the temperature constant, continue to add 1 g of carbomer and 60 g of deionized water to the mixture E9, and then further emulsify the mixture through a homogenizer to obtain the silicone emulsion defoamer.

[0028] Comparative Example 4 (1) 6 g of silicone polyether 4 and 1 g of fatty alcohol polyoxyethylene ether were mixed uniformly at room temperature to obtain a mixture M9; (2) 10 g of defoaming active ingredient, 20 g of castor oil polyoxyethylene ether, and 9 g of lauric acid polyoxyethylene ether were mixed, and the mixture was mixed for 1.5 h at a rotation speed of 2000 rpm using a high shear device to obtain a mixture N9; (3) Raise the temperature to 90°C and add mixture M4 to mixture N4 while stirring for 1 hour to form mixture E10; (4) While keeping the temperature constant, continue to add 2 g of xanthan gum and 52 g of deionized water to the mixture E10, and then further emulsify the mixture through a homogenizer to obtain the organosilicon emulsion defoamer.

[0029] Comparative Example 5 (1) 3 g of silicone polyether 5 and 2.9 g of silicone polyether 1 were mixed uniformly at room temperature to obtain a mixture M5; (2) 10 g of the defoaming active ingredient, 10 g of a mixture of sorbitan tristearate and sorbitan trioleate, and 9 g of silicone polyether 2 were mixed, and mixed for 1 h at a rotation speed of 2500 rpm using a high shear device to obtain a mixture N5; (3) Raise the temperature to 75°C and add mixture M5 to mixture N5 while stirring for 1.5 h to form mixture E5; (4) Keeping the temperature constant, continue to add 0.1 g of cellulose ether and 65 g of deionized water to the mixture E5, and then further emulsify the mixture through a homogenizer to obtain the organosilicon emulsion defoamer. Performance Testing

[0030] Anti-foaming performance test Use a stoppered measuring cylinder to measure 50mL of the specified standard foaming medium (0.5% sodium dodecylbenzene sulfonate aqueous solution), add 0.05g of the defoamer sample at the specified temperature, cover the bottle with a stopper, shake the measuring cylinder up and down several times at a frequency of 2 times / s and a swing amplitude of (30-35) cm, let it stand and start timing, record the time it takes for the foam to disappear and the liquid surface to appear, which is the defoaming time of this shaking bottle. The shorter the defoaming time, the better the defoaming and anti-foaming performance. The test results are as follows:

[0031] Under the test conditions of room temperature and 70° C., the antifoaming performance of Examples 1-6 is better than that of Comparative Examples 1-5.

[0032] b) Stability test The stability of the sample was tested using a Formulaction / Turbiscan Tower / Multiple Light Scattering Stability Analyzer. The test temperature was 40°C and the sample amount was 20 g. The smaller the TSI index in the test results, the better the sample stability.

[0033]

[0034] It can be seen from the above table that the stability of Examples 1-6 is better than that of Comparative Examples 1-5.

Claims

1. A silicone emulsion, characterized in that It is composed of the following substances: A. Defoaming active ingredient: The defoaming active ingredient is prepared by known technology using polyorganosiloxane, catalyst, silicone resin and silicon dioxide, and the amount used is 10-20% of the total mass of the silicone emulsion; B. Emulsifier: The emulsifier is a nonionic surfactant, and the amount used is 10-20% of the total mass of the silicone emulsion C. Deionized water: The dosage is 50~65% of the total mass of the silicone emulsion; D. Silicone polyether: The dosage is 2~15% of the total mass of silicone emulsion; E. Ester synergist: The structural formula of the ester synergist is: R'(COOR'')w The ester synergist is used in two parts. In the first part of the ester synergist, R' is a straight chain or branched chain alkyl group containing 16 to 30 carbon atoms, and R'' is a straight chain or branched chain alkyl group containing 4 to 10 carbon atoms; in the second part of the ester synergist, R' is a straight chain or branched chain alkyl group containing 1 to 15 carbon atoms, and R'' is a straight chain or branched chain alkyl group containing 4 to 10 carbon atoms; w is 1 or 2; the amount of the ester synergist is 5-15% of the total mass of the silicone emulsion; F. Thickener: The dosage is 0.1~3% of the total mass of silicone emulsion.

2. The organosilicon emulsion according to claim 1, characterized in that: The emulsifier is 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 can be used alone or in combination.

3. The organosilicon emulsion according to claim 1, characterized in that: The structural formula of the silicone polyether is as follows: M.D a ( Me YSiO) b M Where: M is the chain link R3SiO l / 2 , D is the chain link R2SiO 2 / 2 , R2 and R3 are the same or different and are selected from a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; Me Methyl; the structural formula of Y is: –(CH2) z O(EO) g (PO) h K, K is a capping group selected from hydrogen, methyl, ethyl, propyl, and butyl; a , b , z , g , h is the degree of polymerization, a is an integer between 10 and 500, b is an integer from 1 to 50, z is an integer from 2 to 6, g An integer from 1 to 36. h It is an integer of 0 to 20; the dosage is 2 to 15% of the total mass of the silicone emulsion.

4. The organosilicon emulsion according to claim 1, characterized in that: The amount of the first part of the ester synergist in the ester thickener accounts for 10-30% of the total mass of the ester synergist.

5. The organosilicon emulsion according to claim 1, characterized in that: The thickener is selected from polyacrylamide, carbomer, xanthan gum, cellulose ethers and polyacrylate.

6. The organosilicon emulsion according to claim 1, characterized in that: The thickener is a polyacrylate thickener.

7. The organosilicon emulsion according to any one of claims 1 to 7, wherein the preparation method thereof is as follows: (1) mixing the silicone polyether and the first part of the ester synergist at room temperature to obtain a mixture M; (2) mixing the defoaming active ingredient, the emulsifier, and the second part of the ester synergist, using a high shear device at a rotation speed of 1000 to 3000 rpm for 0.5 to 2 hours to obtain a mixture N; (3) Raise the temperature to 60-90°C, add mixture M to mixture N while stirring for 0.5-2h to form mixture E; (4) Keeping the temperature constant, continue to add thickener and deionized water to mixture E, and then further emulsify the mixture through a homogenizer to obtain the organosilicon emulsion defoamer.

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