Preparation method of silyl ether composition

Abstract

The invention relates to a preparation method of a silyl ether composition. The silyl ether composition is prepared from alkyl phenyl silicone oil, polyether, silicon dioxide, an acrylic polymer, a basic catalyst and other raw materials through a certain process. The silyl ether composition can be directly diluted with mineral oil and polyether to obtain a stable mixture which is used as a defoaming agent, and the problem that organic silicon is incompatible with polyether and mineral oil is solved.

Description

Technical Field

[0001] This invention relates to a method for preparing a silicon ether composition, belonging to the field of fine chemical technology. Background Technology

[0002] Organosilicon is an important new type of material that emerged in the mid-20th century. After decades of development, it has now permeated many sectors of the national economy. Graft modification or physical compounding of organosilicon polymers with polyethers is an important direction, as it can be used as a raw material for defoamers, emulsifiers, leveling agents, wetting agents, and other additives. Depending on the specific application scenario, sometimes polyether silicone oil is prepared by hydrosilylation of polyether and hydrogen-containing silicone oil; sometimes silicone oil and polyether are compounded and emulsified to obtain the desired product; and sometimes, to achieve a certain function, organosilicon and polyether are compounded using special methods while maintaining a phase-free state. In reality, achieving a phase-free state is very difficult and requires specific modification of the organosilicon to achieve the desired result.

[0003] Defoamers are also an important direction for the combined use of organosilicon and polyether. Polyether-modified silicone oil, silicone paste and polyether compound emulsion, and even silicone paste and polyether-modified silicone oil and polyether are three common forms. For example, CN113069796A introduces a silicone paste prepared by using end-group isomeric alcohol ether-terminated polyether-modified silicone oil and silica, and using this silicone paste to defoam in water-based coating systems. CN109651617A describes a method for preparing an emulsion using hydroxyl-containing polyether-modified organosilicon, which exhibits excellent defoaming properties in water-based coatings. CN108299938A describes a method for preparing a defoamer by reacting polyether-modified silicone oil with silazane-modified nano-silica to form a silicone paste, and then mixing and emulsifying the silicone paste with sorbitol, Tween 60, sodium carboxymethyl cellulose, and the silicone paste. This method has a short defoaming time, a long foam suppression time, and no oil floating phenomenon. CN201010211308.5 describes a method to solve this problem by adding polysiloxane during the synthesis of silicone polyether and then heating and holding it at a certain temperature to increase the viscosity of the silicone polyether. However, the resulting product still has poor stability. CA2238225A1 describes a method to disperse low-viscosity silicone paste in polypropylene glycol by means of high-speed stirring and the action of carbomer. The resulting product has a higher viscosity and is prone to precipitation after long-term storage. The aforementioned patents all employ different methods to address the stability issues of polyether and organosilicon mixtures, but they cannot fundamentally resolve the compatibility issues between different substances.

[0004] Through extensive experimental research, the inventors of this patent discovered that certain specially structured alkylphenyl silicone oils, polyethers, and acrylic polymers have excellent compatibility. By adding silica and an alkaline catalyst, a silicone ether composition was obtained. This silicone ether composition can be directly diluted with mineral oil and polyether to obtain a stable mixture that can be used as an antifoaming agent, thus solving the problem of incompatibility between organosilicon, polyether, and mineral oil. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing a silicone ether composition, which is stable during storage and does not separate into phases; it can be directly diluted with polyether and mineral oil to obtain polyether defoamers and mineral oil defoamers.

[0006] The components used to prepare the silyl ether composition of the present invention include (A) alkylphenyl silicone oil, (B) polyether, (C) silica, (D) acrylic polymer and (E) alkaline catalyst.

[0007] A. Alkylphenyl silicone oil

[0008] The alkylphenyl silicone oil is prepared by hydrosilylation reaction of hydrogen-containing silicone oil with α-olefin and α-methylstyrene under the action of platinum metal; the hydrogen-containing silicone oil used to prepare the alkylphenyl silicone oil has a dynamic viscosity of 20-1000 mPa·s at 25°C and a hydrogen content of 0.3-1.2%.

[0009] The general structural formula of the alkylphenyl silicone oil is as follows:

[0010]

[0011] In formula (Ⅰ), a, b and c are the degrees of polymerization of the three silicon repeating segments, a is 5 to 250, b is 15 to 70, c is 1 to 5, and d is the number of repeats of -CH2-, which is an integer from 4 to 22.

[0012] The ratio of carbon atoms to silicon atoms in the alkylphenyl silicone oil structure should meet the following condition: carbon atoms /

[0013] The number of silicon atoms is greater than 3.6.

[0014] The method for calculating the ratio of carbon atoms to silicon atoms is as follows:

[0015]

[0016] The amount of the alkylphenyl silicone oil used is 5-30% of the total mass of the silicone ether composition.

[0017] B. Polyether

[0018] The general structural formula of the polyether is as follows:

[0019] RO(EO)e (PO) f R 1

[0020] (II)

[0021] In formula (II), the subscript e represents the degree of polymerization of ethylene oxide (EO), with a value of 0 or 1–15; the subscript f represents the degree of polymerization of propylene oxide (PO), with a value of 1–50; R represents a hydrocarbon group with 12–30 carbon atoms; R 1 It can be a hydrogen atom, methyl, ethyl, propyl, butyl, acetyl, propionylbutyryl, or have the structural formula -OCR 2 The alkyl carbonyl functional group, wherein R 2 It consists of saturated unsaturated fatty acids with 11 to 17 carbon atoms.

[0022] The amount of polyether used is 20-70% of the total mass of the silicone ether composition.

[0023] C. Silicon dioxide

[0024] Silicon dioxide is classified into two types according to its manufacturing method: precipitated silicon dioxide and fumed silicon dioxide. It is also classified into two types according to its surface properties: hydrophilic silicon dioxide and hydrophobic silicon dioxide.

[0025] Hydrophobic silica is obtained by heating and stirring hydrophilic silica and a hydrophobic agent in a reaction vessel. Materials that make silica surfaces hydrophobic include low-viscosity trimethylsiloxy-terminated polydimethylsiloxane, low-viscosity hydroxyl-terminated polydimethylsiloxane, hexamethyldisilazane, hexamethyldisilazane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, tetrachlorosilane, stearic acid, stearyl alcohol, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, and hexamethylcyclotrisiloxane.

[0026] The silicon dioxide described in this invention has a specific surface area of ​​60-150 m². 2 / g precipitated hydrophobic silica and specific surface area 200~500m 2 The composition is a fumed hydrophobic silica composition, wherein the hydrophobic treatment agent is a fatty alcohol with 6 to 24 carbon atoms.

[0027] The amount of silica used is 1-8% of the total mass of the silane ether composition.

[0028] D. Acrylic polymers

[0029] The acrylic polymer has the following structure:

[0030]

[0031] In formula (Ⅲ), the subscript g represents the degree of polymerization of the monomer, and the molecular weight of the acrylic polymer is between 3000 and 6000; R 3 It is one or more of the following: a straight-chain or branched alkyl group with 1 to 18 carbon atoms, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyisopropyl, 2-hydroxyisopropyl, 3-hydroxyisopropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, and 4-hydroxybutyl, and at least one hydroxyl group is present in the acrylic polymer.

[0032] In the preparation of the acrylic polymer, the mass ratio of acrylic acid to acrylate is 5:95 to 10:90, and the ratio between different acrylates is not limited; the amount of monomers used to form the acrylic polymer is 40 to 70% of the total mass of the acrylic polymer.

[0033] The catalyst used in preparing the acrylic polymer is a free radical-generating catalyst, selected from, but not limited to, redox catalyst systems of 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2,4-dimethylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), benzoyl peroxide, bromate / sulfide, and persulfate / ferrous oxide, preferably 2,2'-azobis(2-methylpropionitrile); the amount of catalyst used is 0.2% to 2% of the total mass of the acrylic polymer.

[0034] The solvents used in preparing the acrylic polymer are not limited to one or more of the following: diisodecyl phthalate, diisooctyl phthalate, dihexyl phthalate, diisooctyl adipate, bis-2-ethylhexyl adipate, dioctyl adipate, 2-ethyl-1-hexanol, polybutene with a molecular weight of 300-1300, polyethylene glycol, polypropylene glycol, fatty alcohol polyethers with 12-24 carbon atoms and their esters; the amount of solvent used is 30-58% of the total mass of the acrylic polymer.

[0035] The preparation method of the acrylic polymer is as follows:

[0036] Under nitrogen protection, solvent and catalyst are added to a reaction flask, and the temperature is raised to 60–90°C with stirring to dissolve or disperse them. Simultaneously, acrylate monomers are premixed in a beaker, and then the premixed monomer mixture is added dropwise to the flask at a rate of 1–3 g / min, maintaining the temperature of the reactants in the flask at 70–95°C. Finally, catalyst is added to the flask, and the reaction is maintained at 100–110°C for 1–4 hours, followed by cooling to room temperature to obtain the acrylic polymer.

[0037] The amount of the acrylic polymer used is 10-50% of the total mass of the silicone ether composition.

[0038] E. Alkaline catalyst

[0039] The alkaline catalyst includes sodium hydroxide, potassium hydroxide, cesium hydroxide, potassium silylate, sodium silylate, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, β-hydroxyethyltrimethylamine, and tetramethylammonium hydroxide.

[0040] The amount of alkaline catalyst used is 0.1% to 1% of the silane ether composition.

[0041] The method for preparing the silyl ether composition of the present invention is as follows:

[0042] First, add polyether to a container at room temperature and turn on the stirring speed to 200-1000 rpm. Then add precipitated hydrophobic silica and increase the stirring speed to 2000-4000 rpm. Stir for 0.5-2 hours to obtain a mixture of "polyether-precipitated hydrophobic silica".

[0043] The second step involves adding alkylphenyl silicone oil and an alkaline catalyst to another container at room temperature, heating the mixture to 100–150°C and stirring at 1000–3000 rpm, adding fumed hydrophobic silica, and then maintaining the temperature and stirring for 0.5–4 hours. Once the viscosity of the resulting mixture becomes 3–6 times its original value, a mixture of "polyether-precipitated hydrophobic silica" is added all at once. After mixing evenly, an acrylic polymer is added and stirred until homogeneous to obtain the silicone ether composition. Specific implementation methods

[0044] Example 1

[0045] The general formula for alkylphenyl silicone oils is as follows:

[0046]

[0047] The selection of alkylphenyl silicone oils is shown in Table 1 below:

[0048] Table 1 Selection of Alkylbenzene Silicone Oils

[0049]

[0050] Example 2

[0051] Preparation of acrylic polymer D1:

[0052] Under nitrogen protection, 30 parts of diisooctyl phthalate and 0.5 parts of 2',2-azobis(2-methylpropionitrile) were added to a reaction flask, and the mixture was heated to 68°C and stirred until dissolved. Simultaneously, 3.45 parts of acrylic acid, 62.1 parts of methyl acrylate, and 3.45 parts of 2-hydroxyethyl acrylate monomer were premixed in a beaker. The premixed monomer mixture was then added dropwise to the flask at a rate of 1.8 g / min, maintaining the temperature of the reactants in the flask at 75–78°C. Finally, 0.5 parts of the catalyst 2',2-azobis(2-methylpropionitrile) were added to the flask, and the reaction was maintained at 101°C for 3.5 h. The mixture was then cooled to room temperature to obtain acrylic polymer D1, with a molar molecular weight of 5178 as determined by GPC.

[0053] Example 3

[0054] Preparation of acrylic polymer D2:

[0055] Under nitrogen protection, 56 parts of structural formula C were added to the reaction flask. 12 H 25 O(EO)5(PO) 15 H, a fatty alcohol polyether, and 1.2 parts of benzoyl peroxide were dissolved by stirring at 87°C. Simultaneously, 3.36 parts of acrylic acid, 19.74 parts of isooctyl acrylate, and 18.9 parts of 3-hydroxybutyl acrylate monomer were premixed in a beaker. The premixed monomer mixture was then added dropwise to the flask at a rate of 1.1 g / min, maintaining the reactant temperature at 71–72°C. Finally, 0.8 parts of benzoyl peroxide catalyst were added to the flask, and the reaction was carried out at 106°C for 1.2 h. The mixture was then cooled to room temperature to obtain acrylic polymer D2, with a molar molecular weight of 3166 as determined by GPC.

[0056] Comparative Example 1

[0057] Preparation of acrylic polymer D2-1:

[0058] Under nitrogen protection, 56.6 parts of structural formula C were added to the reaction flask. 12 H 25 O(EO)5(PO) 15 H, a fatty alcohol polyether, and 1.2 parts of benzoyl peroxide were dissolved by stirring at 87°C. Simultaneously, 3.36 parts of acrylic acid, 19.74 parts of isooctyl acrylate, and 18.9 parts of 3-hydroxybutyl acrylate monomer were premixed in a beaker. The premixed monomer mixture was then added dropwise to the flask at a rate of 1.1 g / min, maintaining the reactant temperature at 71–72°C. Finally, 0.2 parts of benzoyl peroxide catalyst were added to the flask, and the reaction was maintained at 100°C for 0.5 h. The mixture was then cooled to room temperature to obtain acrylic polymer D2-1, with a GPC molar molecular weight of 2538.

[0059] Comparative Example 2

[0060] Preparation of acrylic polymer D2-2:

[0061] Under nitrogen protection, 56 parts of structural formula C were added to the reaction flask. 12 H 25 O(EO)5(PO) 15 H, a fatty alcohol polyether, and 1.2 parts of benzoyl peroxide were dissolved by stirring at 87°C. Simultaneously, 3.36 parts of acrylic acid and 38.64 parts of isooctyl acrylate monomer were premixed in a beaker, and then the premixed monomer mixture was added dropwise to the flask at a rate of 1.1 g / min, maintaining the temperature of the reactants in the flask at 71–72°C. Finally, 0.8 parts of benzoyl peroxide catalyst were added to the flask, and the reaction was carried out at 106°C for 1.2 h. After cooling to room temperature, acrylic polymer D2-2 was obtained, with a molar molecular weight of 4682 as determined by GPC.

[0062] Example 4

[0063] Preparation of acrylic polymer D3:

[0064] Under nitrogen protection, 50 parts of polypropylene glycol (molecular weight 1200) and 0.2 parts of ferric persulfate / ferrous sulfate were added to a reaction flask, and the mixture was heated to 62°C and stirred to ensure uniform dispersion. Simultaneously, 5.0 parts of acrylic acid, 2.5 parts of isooctadecyl acrylate, and 42.2 parts of 2-hydroxyisopropyl acrylate monomer were premixed in a beaker. The premixed monomer mixture was then added dropwise to the flask at a rate of 2.8 g / min, maintaining the reactant temperature in the flask at 92–94°C. Finally, 0.1 parts of the ferric persulfate / ferrous sulfate catalyst were added to the flask, and the reaction was maintained at 108°C for 4 hours. The mixture was then cooled to room temperature to obtain acrylic polymer D3, with a molar molecular weight of 4269 as determined by GPC.

[0065] Example 5

[0066] Preparation of acrylic polymer D4:

[0067] Under nitrogen protection, 38.5 parts of polybutene (molecular weight 1000) and 0.8 parts of 2,2'-azobis(2,4-dimethylpropionitrile) were added to a reaction flask, and the mixture was heated to 72°C and stirred to ensure uniform dispersion. Simultaneously, 3.6 parts of acrylic acid, 11.3 parts of isododecyl acrylate, and 45.1 parts of 3-hydroxypropyl acrylate monomer were premixed in a beaker. The premixed monomer mixture was then added dropwise to the flask at a rate of 1.6 g / min, maintaining the reactant temperature in the flask at 88–90°C. Finally, 0.7 parts of the catalyst 2,2'-azobis(2,4-dimethylpropionitrile) were added to the flask, and the reaction was maintained at 104°C for 2.5 h. The mixture was then cooled to room temperature to obtain acrylic polymer D4, with a GPC molar molecular weight of 5835.

[0068] Comparative Example 3

[0069] Preparation of acrylic polymer D4-1:

[0070] Under nitrogen protection, 38 parts of polybutene (molecular weight 1000) and 0.8 parts of 2,2'-azobis(2,4-dimethylpropionitrile) were added to a reaction flask, and the mixture was heated to 72°C and stirred to ensure uniform dispersion. Simultaneously, 3.6 parts of acrylic acid, 11.3 parts of isododecyl acrylate, and 45.1 parts of 3-hydroxypropyl acrylate monomer were premixed in a beaker. The premixed monomer mixture was then added dropwise to the flask at a rate of 1.6 g / min, maintaining the reactant temperature in the flask at 88–90°C. Finally, 1.2 parts of the catalyst 2,2'-azobis(2,4-dimethylpropionitrile) were added to the flask, and the reaction was maintained at 104°C for 2.5 h. The mixture was then cooled to room temperature to obtain acrylic polymer D4-1, with a GPC molar molecular weight of 7645.

[0071] Example 6

[0072] Step 1: Add 22 parts of polyether (initiator cetyl alcohol, e=2, f=34, R) to the container at room temperature. 1 =H), turn on the stirring speed to 300 rpm, and then add 2 parts of precipitated hydrophobic silica (specific surface area 80 m²). 2 / g, with hexanol as the hydrophobic treatment agent), increase the speed to 2500 rpm and stir for 1.5 h to obtain a mixture of "polyether-precipitated hydrophobic silica";

[0073] The second step involves adding 24.5 parts of alkylphenyl silicone oil A1 and 0.5 parts of alkaline catalyst potassium hydroxide to another container at room temperature. The mixture is then heated to 130°C and stirred at 1200 rpm. Finally, 3 parts of fumed hydrophobic silica (with a specific surface area of ​​380 m²) are added. 2 / g, the hydrophobic treatment agent is decanol), after the fumed silica is added, it is kept warm and stirred for 2.5h. The viscosity of the resulting mixture becomes 3.5 times that of the original (the viscosity changes from the original 547mPa·s to 1914mPa·s). Then, the "polyether-precipitated hydrophobic silica" mixture is added to it all at once. After mixing evenly, 48 parts of acrylic polymer D2 are added to it and stirred evenly to obtain the silicone ether composition SP1.

[0074] Comparative Example 4:

[0075] Step 1: Add 22 parts of polyether (initiator cetyl alcohol, e=2, f=34, R) to the container at room temperature. 1 =H), turn on the stirring speed to 300 rpm, and then add 2 parts of precipitated hydrophobic silica (specific surface area 80 m²). 2 / g, with hexanol as the hydrophobic treatment agent), increase the speed to 2500 rpm and stir for 1.5 h to obtain a mixture of "polyether-precipitated hydrophobic silica";

[0076] The second step involves adding 24.5 parts of alkylphenyl silicone oil A1 and 0.5 parts of alkaline catalyst potassium hydroxide to another container at room temperature. The mixture is then heated to 130°C and stirred at 1200 rpm. Finally, 3 parts of fumed hydrophobic silica (with a specific surface area of ​​380 m²) are added. 2 / g, the hydrophobic treatment agent is decanol), after the fumed silica is added, it is kept warm and stirred for 2.5h. The viscosity of the resulting mixture becomes 3.5 times that of the original (the viscosity changes from the original 547mPa·s to 1914mPa·s). Then, the "polyether-precipitated hydrophobic silica" mixture is added to it all at once. After mixing evenly, 48 parts of acrylic polymer D2-1 are added to it and stirred evenly to obtain the silicone ether composition SP1-1.

[0077] Comparative Example 5:

[0078] Step 1: Add 22 parts of polyether (initiator cetyl alcohol, e=2, f=34, R) to the container at room temperature. 1 =H), turn on the stirring speed to 300 rpm, and then add 2 parts of precipitated hydrophobic silica (specific surface area 80 m²). 2 / g, with hexanol as the hydrophobic treatment agent), increase the speed to 2500 rpm and stir for 1.5 h to obtain a mixture of "polyether-precipitated hydrophobic silica";

[0079] The second step involves adding 24.5 parts of alkylphenyl silicone oil A1 and 0.5 parts of alkaline catalyst potassium hydroxide to another container at room temperature. The mixture is then heated to 130°C and stirred at 1200 rpm. Finally, 3 parts of fumed hydrophobic silica (with a specific surface area of ​​380 m²) are added. 2 / g, the hydrophobic treatment agent is decanol), after the fumed silica is added, it is kept warm and stirred for 2.5h. The viscosity of the resulting mixture becomes 3.5 times that of the original (the viscosity changes from the original 547mPa·s to 1914mPa·s). Then, the "polyether-precipitated hydrophobic silica" mixture is added to it all at once. After mixing evenly, 48 parts of acrylic polymer D2-2 are added to it and stirred evenly to obtain the silicone ether composition SP1-2.

[0080] Example 7

[0081] Step 1: Add 68 parts of polyether (initializer is octadecyl alcohol, e=0, f=50, R) to the container at room temperature. 1 =acetyl), start the stirring speed at 600 rpm, and then add 0.6 parts of precipitated hydrophobic silica (specific surface area 65 m²). 2 / g, with octadecyl alcohol as the hydrophobic treatment agent, the stirring speed was increased to 3800 rpm, and the mixture was stirred for 2 hours to obtain a "polyether-precipitated hydrophobic silica" mixture;

[0082] The second step involves adding 6 parts of alkylphenyl silicone oil A3 and 0.2 parts of alkaline catalyst cesium hydroxide to another container at room temperature. The mixture is then heated to 145°C and stirred at 1800 rpm. Finally, 0.6 parts of fumed hydrophobic silica (with a specific surface area of ​​480 m²) are added. 2 / g, the hydrophobic treatment agent is docosyl alcohol), after the fumed silica is added, it is kept warm and stirred for 4 hours. The viscosity of the resulting mixture becomes 6 times that of the original (the viscosity changes from the original 159 mPa·s to 946 mPa·s). Then, the "polyether-precipitated hydrophobic silica" mixture is added to it all at once. After mixing evenly, 24.6 parts of acrylic polymer D4 are added to it and stirred evenly to obtain the silicone ether composition SP2.

[0083] Example 8

[0084] Step 1: Add 51 parts of polyether (initializer is dodecyltetradecyl alcohol, e=13, f=3, R) to the container at room temperature. 1 =—OCH 33 C 16 Start the stirring speed at 900 rpm, then add 3 parts of precipitated hydrophobic silica (specific surface area 140 m²). 2 / g, with dodecyl alcohol as the hydrophobic treatment agent, the stirring speed was increased to 3200 rpm and stirred for 0.5 h to obtain a mixture of "polyether-precipitated hydrophobic silica";

[0085] In the second step, at room temperature, 28 parts of alkylphenyl silicone oil A2 and 1 part of alkaline catalyst sodium methoxide were added to another container, heated to 105°C, and stirred at 2900 rpm. Then, 5 parts of fumed hydrophobic silica (specific surface area 210 m²) were added. 2 / g, the hydrophobic treatment agent is hexadecyl alcohol), after the fumed silica is added, the mixture is kept warm and stirred for 0.5h. The viscosity of the resulting mixture becomes 4 times that of the original (the viscosity changes from the original 1309 mPa·s to 5189 mPa·s). Then, the "polyether-precipitated hydrophobic silica" mixture is added to it all at once, and after mixing evenly, 12 parts of acrylic polymer D3 are added and stirred evenly to obtain the silicone ether composition SP3. Comparative Example 6:

[0086] Step 1: Add 51 parts of polyether (initializer is dodecyltetradecyl alcohol, e=13, f=3, R) to the container at room temperature. 1 =—OCH 33 C 16 Start the stirring speed at 900 rpm, then add 3 parts of precipitated hydrophobic silica (specific surface area 140 m²).2 / g, with dodecyl alcohol as the hydrophobic treatment agent, the stirring speed was increased to 3200 rpm and stirred for 0.5 h to obtain a mixture of "polyether-precipitated hydrophobic silica";

[0087] The second step involves adding 28 parts of alkylphenyl silicone oil A2-1 and 1 part of alkaline catalyst sodium methoxide to another container at room temperature. The mixture is then heated to 105°C and stirred at 2900 rpm. Finally, 5 parts of fumed hydrophobic silica (with a specific surface area of ​​210 m²) are added. 2 / g, the hydrophobic treatment agent is hexadecyl alcohol), after the fumed silica is added, keep warm and stir for 0.5h. The viscosity of the resulting mixture becomes 4 times that of the original (the viscosity changes from the original 1309mPa·s to 5189mPa·s). Then, the "polyether-precipitated hydrophobic silica" mixture is added to it all at once. After mixing evenly, 12 parts of acrylic polymer D3 are added to it and stirred evenly to obtain the silicone ether composition SP3-1.

[0088] Comparative Example 7

[0089] Step 1: Add 51 parts of polyether (initializer is dodecyltetradecyl alcohol, e=13, f=3, R) to the container at room temperature. 1 =—OCH 33 C 16 Start the stirring speed at 900 rpm, then add 3 parts of precipitated hydrophobic silica (specific surface area 140 m²). 2 / g, with dodecyl alcohol as the hydrophobic treatment agent, the stirring speed was increased to 3200 rpm and stirred for 0.5 h to obtain a mixture of "polyether-precipitated hydrophobic silica";

[0090] In the second step, at room temperature, 28 parts of alkylphenyl silicone oil A2-2 and 1 part of alkaline catalyst sodium methoxide were added to another container, heated to 105°C, and stirred at 2900 rpm. Then, 5 parts of fumed hydrophobic silica (specific surface area 210 m²) were added. 2 / g, the hydrophobic treatment agent is hexadecyl alcohol), after the fumed silica is added, keep warm and stir for 0.5h. The viscosity of the resulting mixture becomes 4 times that of the original (the viscosity changes from the original 1309mPa·s to 5189mPa·s). Then, the "polyether-precipitated hydrophobic silica" mixture is added to it all at once. After mixing evenly, 12 parts of acrylic polymer D3 are added to it and stirred evenly to obtain the silicone ether composition SP3-2.

[0091] Example 9

[0092] Step 1: Add 45 parts of polyether (initializer is octadecyl alcohol, e=6, f=35, R) to the container at room temperature. 1=Isopropyl), start the stirring speed at 650 rpm, and then add 4 parts of precipitated hydrophobic silica (specific surface area 110 m²). 2 / g, with octadecyl alcohol as the hydrophobic treatment agent, the stirring speed was increased to 2500 rpm and stirred for 1 h to obtain a mixture of "polyether-precipitated hydrophobic silica";

[0093] The second step involves adding 18 parts of alkylphenyl silicone oil A5 and 0.5 parts of alkaline catalyst sodium hydroxide to another container at room temperature. The mixture is then heated to 125°C and stirred at 2400 rpm. One part of fumed hydrophobic silica (with a specific surface area of ​​280 m²) is then added to this mixture. 2 / g, the hydrophobic treatment agent is hexadecyl alcohol), after the fumed silica is added, it is kept warm and stirred for 2.5h. The viscosity of the resulting mixture becomes 4.9 times that of the original (the viscosity changes from the original 78mPa·s to 382mPa·s). Then, the "polyether-precipitated hydrophobic silica" mixture is added to it all at once. After mixing evenly, 30.5 parts of acrylic polymer D1 are added to it and stirred evenly to obtain the silicone ether composition SP4.

[0094] Example 10

[0095] Step 1: Add 35 parts of polyether (initiator is cetearyl alcohol, e=9, f=46, R) to the container at room temperature. 1 =methyl), start the stirring speed at 850 rpm, and then add 2 parts of precipitated hydrophobic silica (specific surface area 135 m²). 2 / g, with octadecyl alcohol as the hydrophobic treatment agent, the stirring speed was increased to 2800 rpm and stirred for 1.5 h to obtain a mixture of "polyether-precipitated hydrophobic silica";

[0096] In the second step, at room temperature, 24 parts of alkylphenyl silicone oil A4 and 0.8 parts of alkaline catalyst potassium silanolate were added to another container, heated to 118°C, and stirred at 2000 rpm. Then, 4 parts of fumed hydrophobic silica (with a specific surface area of ​​350 m²) were added. 2 / g, the hydrophobic treatment agent is hexadecyl alcohol), after the fumed silica is added, the mixture is kept warm and stirred for 3 hours. The viscosity of the resulting mixture becomes 5.7 times the original (the viscosity changes from the original 142 mPa·s to 809 mPa·s). Then, the "polyether-precipitated hydrophobic silica" mixture is added to it all at once, and after mixing evenly, 34.2 parts of acrylic polymer D4 are added to it and stirred evenly to obtain the silicone ether composition SP5. Comparative Example 8:

[0097] Step 1: Add 35 parts of polyether (initiator is cetearyl alcohol, e=9, f=46, R) to the container at room temperature. 1 =methyl), start the stirring speed at 850 rpm, and then add 2 parts of precipitated hydrophobic silica (specific surface area 135 m²).2 / g, with octadecyl alcohol as the hydrophobic treatment agent, the stirring speed was increased to 2800 rpm and stirred for 1.5 h to obtain a mixture of "polyether-precipitated hydrophobic silica";

[0098] In the second step, at room temperature, 24 parts of alkylphenyl silicone oil A4 and 0.8 parts of alkaline catalyst potassium silanolate were added to another container, heated to 118°C, and stirred at 2000 rpm. Then, 4 parts of fumed hydrophobic silica (with a specific surface area of ​​350 m²) were added. 2 / g, the hydrophobic treatment agent is hexadecyl alcohol), after the fumed silica is added, it is kept warm and stirred for 3 hours. The viscosity of the resulting mixture becomes 5.7 times that of the original (the viscosity changes from the original 142 mPa·s to 809 mPa·s). Then, the "polyether-precipitated hydrophobic silica" mixture is added to it all at once. After mixing evenly, 34.2 parts of acrylic polymer D4-1 are added to it and stirred evenly to obtain the silicone ether composition SP5-1.

[0099] Comparative Example 9:

[0100] Step 1: Add 35 parts of polyether (initiator is cetearyl alcohol, e=9, f=46, R) to the container at room temperature. 1 =methyl), start the stirring speed at 850 rpm, and then add 2 parts of precipitated hydrophobic silica (specific surface area 135 m²). 2 / g, with octadecyl alcohol as the hydrophobic treatment agent, the stirring speed was increased to 2800 rpm and stirred for 1.5 h to obtain a mixture of "polyether-precipitated hydrophobic silica";

[0101] In the second step, at room temperature, 24 parts of alkylphenyl silicone oil A4 and 0.8 parts of alkaline catalyst potassium silanolate were added to another container, heated to 118°C, and stirred at 2000 rpm. Then, 4 parts of fumed hydrophobic silica (with a specific surface area of ​​350 m²) were added. 2 / g, the hydrophobic treatment agent is cetyl alcohol), after the fumed silica is added, the mixture is kept warm and stirred for 3 hours. The viscosity of the resulting mixture becomes 5.7 times the original (the viscosity changes from the original 142 mPa·s to 809 mPa·s). Then, the "polyether-precipitated hydrophobic silica" mixture is added to it all at once, and after mixing evenly, 34.2 parts of alkylphenyl silicone oil A4 are added and stirred evenly to obtain the silicone ether composition SP5-2. Comparative Example 10:

[0102] Step 1: Add 35 parts of polyether (initiator is cetearyl alcohol, e=9, f=46, R) to the container at room temperature. 1 =methyl), start the stirring speed at 850 rpm, and then add 2 parts of precipitated hydrophobic silica (specific surface area 135 m²). 2 / g, with octadecyl alcohol as the hydrophobic treatment agent, the stirring speed was increased to 2800 rpm and stirred for 1.5 h to obtain a mixture of "polyether-precipitated hydrophobic silica";

[0103] In the second step, at room temperature, 24 parts of acrylic polymer D4 and 0.8 parts of alkaline catalyst potassium silanolate were added to another container, heated to 118°C, and stirred at 2000 rpm. Then, 4 parts of fumed hydrophobic silica (with a specific surface area of ​​350 m²) were added. 2 / g, the hydrophobic treatment agent is hexadecyl alcohol), after the fumed silica is added, it is kept warm and stirred for 3 hours. The viscosity of the resulting mixture becomes 5.7 times that of the original (the viscosity changes from the original 142 mPa·s to 809 mPa·s). Then, the "polyether-precipitated hydrophobic silica" mixture is added to it all at once. After mixing evenly, 34.2 parts of acrylic polymer D4 are added to it and stirred evenly to obtain the silicone ether composition SP5-1.

[0104] The properties of the silyl ether compositions prepared by the method of this invention are mainly evaluated from the following aspects:

[0105] 1. Centrifugal stability:

[0106] The silyl ether compositions SP1 to SP5 prepared by the patented method, as well as the comparative compositions SP1-1, SP1-2, SP3-1, SP3-2, and SP5-1, were centrifuged at 3000 rpm for 15 min in a centrifuge. The results are shown in Table 2 below.

[0107] 2. Compatibility test with mineral oil:

[0108] Weigh 25g of industrial No. 10 white oil and 25g of silicone ether composition into a beaker, stir evenly, and then centrifuge at 3000rpm for 15min. The results are shown in Table 2 below.

[0109] 3. Foam control performance:

[0110] Using a composition of 90% PPG2000 polyether and 10% silicone ether by mass as raw materials, the defoamer to be tested was obtained by stirring at 500 rpm for 10 minutes.

[0111] Test method: The air blowing method was used for testing. 100g of commercially available steel plate cleaning alkaline water and 0.1g of the defoamer sample to be tested were weighed and placed in a 500mL graduated cylinder. The cylinder was placed in a 70℃ water bath, and air was blown into the mixture at a flow rate of 1.5L / min. The time it took for the foam to reach the 500mL mark was recorded. The longer the time, the better the foam suppression performance. The results are shown in Table 2.

[0112] Table 2 Comparison of foam control performance of silicone ether compositions

[0113]

[0114]

[0115] As can be seen from the data in Table 2, the foam control performance of silicone ether compositions SP1–SP5 and comparative compositions SP1-1, SP1-2, SP3-1, SP3-2, and SP5-1, when compounded with PPG2000, differs somewhat. This may be because the silicone ether compositions of the patented method and scope have good compatibility with polyethers, and the alkylphenyl silicone oil and acrylic polymer are dispersed in the polyether as fine particles, which can fully exert their foam-suppressing performance. A comparison of SP5, SP5-1, SP5-2, and SP5-3 reveals a certain synergistic effect between the acrylic polymer and alkylphenyl silicone oil, affecting their stability, compatibility with white oil, and foam-suppressing performance.

Claims

1. A method for preparing a silyl ether composition, characterized in that, The raw materials for preparing the silicone ether composition are: alkylphenyl silicone oil A, polyether B, silica C, acrylic polymer D, and alkaline catalyst E; A. Alkylphenyl silicone oil The general structural formula of the alkylphenyl silicone oil is as follows: In formula (Ⅰ), a, b and c are the degrees of polymerization of the three silicon repeating segments, a is 5 to 250, b is 15 to 70; c is 1 to 5; d is the number of repeats of —CH2—, which is an integer from 4 to 22. The amount of the alkylphenyl silicone oil used is 5-30% of the total mass of the silicone ether composition; B. Polyether The general structural formula of the polyether is as follows: RO(EO) e (SHELF) f R 1 (II) In formula (II), the subscript e represents the degree of polymerization of ethylene oxide (EO), with a value of 0 or 1 to 15; the subscript f represents the degree of polymerization of propylene oxide (PO), with a value of 1 to 50; R represents a hydrocarbon group with 12 to 30 carbon atoms; R 1 It can be a hydrogen atom, methyl, ethyl, propyl, butyl, acetyl, propionylbutyryl, or have the structural formula -OCR 2 The alkyl carbonyl functional group, wherein R 2 These are saturated unsaturated fatty acids with 11 to 17 carbon atoms; The amount of polyether used is 20-70% of the total mass of the silicone ether composition; C. Silicon dioxide The silica mentioned has a specific surface area of ​​60-150 m². 2 / g precipitated hydrophobic silica and specific surface area 200~500m 2 / g of fumed hydrophobic silica composition, wherein the hydrophobic treatment agent is a fatty alcohol with 6 to 24 carbon atoms; The amount of silica used is 1-8% of the total mass of the silane ether composition; D. Acrylic polymers The acrylic polymer has the following structure: In formula (Ⅲ), the subscript g represents the degree of polymerization of the monomer, and the molecular weight of the acrylic polymer is between 3000 and 6000; R 3 It is one or more of the following: straight-chain or branched alkyl groups with 1 to 18 carbon atoms, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyisopropyl, 2-hydroxyisopropyl, 3-hydroxyisopropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, and 4-hydroxybutyl; and at least one hydroxyl group is present in the acrylic polymer. The amount of the acrylic polymer used is 10-50% of the total mass of the silicone ether composition; E. Alkaline catalyst The alkaline catalyst includes sodium hydroxide, potassium hydroxide, cesium hydroxide, potassium silylate, sodium silylate, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, β-hydroxyethyltrimethylamine, and tetramethylammonium hydroxide; The amount of alkaline catalyst used is 0.1% to 1% of the silane ether composition; The preparation method of the aforementioned silyl ether composition is as follows: First, add polyether to a container at room temperature and turn on the stirring speed at 200-1000 rpm. Then add precipitated hydrophobic silica and increase the stirring speed to 2000-4000 rpm. Stir for 0.5-2 hours to obtain a "polyether-precipitated hydrophobic silica" mixture. The second step involves adding alkylphenyl silicone oil and an alkaline catalyst to another container at room temperature, heating the mixture to 100–150°C and stirring at 1000–3000 rpm, adding fumed hydrophobic silica, and then maintaining the temperature and stirring for 0.5–4 hours. Once the viscosity of the resulting mixture becomes 3–6 times its original value, a "polyether-precipitated hydrophobic silica" mixture is added all at once. After mixing evenly, an acrylic polymer is added and stirred until homogeneous to obtain the silicone ether composition.

2. The method for preparing a silyl ether composition according to claim 1, characterized in that, The ratio of carbon atoms to silicon atoms in the alkylphenyl silicone oil structure should meet the following requirement: carbon atoms / silicon atoms > 3.6; The method for calculating the ratio of carbon atoms to silicon atoms is as follows:

3. The method for preparing a silicon ether composition according to claim 1, characterized in that, The hydrogen-containing silicone oil used to prepare alkylphenyl silicone oil has a dynamic viscosity of 20–1000 mPa·s at 25°C and a hydrogen content of 0.3–1.2%.

4. The method for preparing a silicon ether composition according to claim 1, characterized in that, The mass ratio of acrylic acid monomers to acrylates in the preparation of the acrylic polymer is 5:95 to 10:90, and the ratio between different acrylates is not limited; the amount of different monomers is 40 to 70% of the total mass of the acrylic polymer.

5. The method for preparing a silyl ether composition according to claim 1, characterized in that, The catalyst used in preparing the acrylic polymer is a free radical-generating catalyst selected from redox catalyst systems such as 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2,4-dimethylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), benzoyl peroxide, bromate / sulfide, and persulfate / ferrous oxide; the amount of catalyst used is 0.2% to 2% of the total mass of the acrylic polymer.

6. The method for preparing a silyl ether composition according to claim 1, characterized in that, The solvent used in preparing the acrylic polymer is selected from one or a mixture of several of the following: diisodecyl phthalate, diisooctyl phthalate, dihexyl phthalate, diisooctyl adipate, bis-2-ethylhexyl adipate, dioctyl adipate, 2-ethyl-1-hexanol, polybutene with a molecular weight of 300-1300, polyethylene glycol, polypropylene glycol, fatty alcohol polyethers with 12-24 carbon atoms and their esters; the amount of solvent used is 30-58% of the total mass of the acrylic polymer.

7. The method for preparing a silyl ether composition according to claim 1, characterized in that, The preparation method of the acrylic polymer is as follows: Under nitrogen protection, solvent and catalyst are added to the reaction flask, and the temperature is raised to 60-90℃ and stirred to dissolve or disperse them. At the same time, acrylate monomers are premixed in a beaker, and then the premixed monomer mixture is added dropwise to the flask at a rate of 1-3 g / min, keeping the temperature of the reactants in the flask at 70-95℃. Finally, catalyst is added to the flask, and the temperature is maintained at 100-110℃ for 1-4 hours before cooling to room temperature to obtain the acrylic polymer.

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