Organic silicon defoaming composition

Abstract

The invention provides an organic silicon defoaming composition which is prepared by the following steps: co-modifying hydrogen-containing polysiloxane by using unsaturated polyether and cardanol to prepare modified organic silicon, dispersing, wrapping and emulsifying an organic silicon active matter at a high speed by using the modified organic silicon, and then continuously adding polyether modified organic silicon with a specific structure for secondary wrapping and emulsifying. And finally adding the dispersing agent and silicon dioxide and uniformly stirring. In the preparation process, an anacardol group is introduced into modified organic silicon, a benzene ring is taken as a parent body, and the benzene ring is provided with hydroxyl, so that the modified organic silicon shows flexibility of long alkane in performance characteristics and rigidity of the benzene ring, organic silicon active matters can be efficiently emulsified and wrapped, the stability and compatibility of the defoaming agent are improved, and silicone grease is prevented from being separated out; polyether modified organic silicon with a specific structure is introduced in the later stage for secondary wrapping, so that the dispersity of the defoaming agent is improved while the compatibility is further improved; finally, the dispersing agent and silicon dioxide are introduced, so that the defoaming and foam-inhibiting performance of the defoaming agent is improved.

Description

Technical Field

[0001] The invention relates to an organosilicon defoaming composition and belongs to the technical field of fine chemical preparations. Background Art

[0002] As a chemical additive, defoamer is widely used in industries including metalworking fluids, textile printing and dyeing, construction cement, daily chemical detergents, etc. With the continuous development of industrial technology, defoamer is used more and more widely as an internal additive. In addition to the basic requirements of defoaming and defoaming performance, internal defoamer also needs to meet compatibility and self-stability. This is more difficult for defoamers. Because a substance must have two basic conditions to have defoaming function: first, low surface tension; second, slightly soluble or incompatible with the foaming medium. On the other hand, as a defoamer product, it may be composed of multiple components. Due to the dissimilar structures of these components, they will form unstable conditions such as stratification and precipitation after being left for a long time. People have been committed to studying organic silicon defoaming compositions with good self-stability, good compatibility and good application performance. CN200710135025.2 and CN200810177184.3 introduce the synthesis method of organosilicon polyether, which has good compatibility, but the defoaming and antifoaming performance cannot meet the requirements. EP-A341952 introduces the use of a combination of polysiloxane defoamer and organosilicon polyether as a defoamer for use in pulp production, but the stability of the defoamer itself needs to be improved. US5523019 introduces a combination of mineral oil and organosilicon polyether as a defoamer, which is said to have a positive effect, but stratification occurs when the organosilicon polyether and silicone oil are mixed.

[0003] Patent CN101885916A utilizes the reaction of polyorganohydrogen siloxane and polyether, and then adds polyorganosiloxane to prepare a stable silicone composition, which solves the compatibility problem of the silicone composition, but the defoaming performance needs to be improved; Patent CN107115694A utilizes silicone active material, silicon polyether, two different saturated polyethers, silicon dioxide, and a catalyst to prepare a silicone composition, and the compatibility of the silicone composition needs to be improved; Patent CN111054100A utilizes a silicone composition composed of silicone active material, polyether-modified polysiloxane, silicon dioxide, ester compounds and surfactants, which well solves the disadvantage of incompatibility of the various components; Patent CN114728215A utilizes polyether-modified silicone with a specific HLB value, triethylene glycol mono-n-butyl ether or triethylene glycol butyl methyl ether, and water to compound to obtain a stable mutually soluble silicone defoamer composition.

[0004] Natural biophenol cardanol belongs to green environmentally friendly renewable resources and is the main component of cashew nut shell oil. Cardanol and its derivatives are widely used in various industries and fields, which has positive significance for solving the current excessive dependence of industrial chemicals on fossil raw materials. CN109734588A provides an ether- and ester-bonded allyl cardanol monomer and a preparation method thereof. Under the action of a catalyst, cardanol is reacted with allyl glycidyl ether to generate allyl ether cardanol, which is then reacted with methacrylic anhydride to prepare an ether- and ester-bonded allyl cardanol monomer, which has dual curing properties of ultraviolet light and oxygen. CN110628028B provides an organosilicon-modified cardanol polyglycidyl ether resin, which introduces cardanol into the main chain of the organosilicon resin, so that it has the heat resistance, weather resistance and flexibility of the organosilicon resin, and retains the properties of convenient construction brought by curing at room temperature and high crosslinking, as well as the unique mechanical properties and chemical resistance. CN115724872A combines organosilicon with natural biological resource cardanol, introduces organosilicon molecules through carbon-carbon unsaturated double bonds, and provides a bio-based cardanol defoamer. Summary of the invention

[0005] The present invention provides a silicone defoaming composition, wherein unsaturated polyether and cardanol are used to co-modify hydrogen-containing polyorganosiloxane to prepare modified silicone, and the modified silicone is used to disperse and encapsulate the emulsified silicone active substance at a high speed, and then polyether-modified silicone with a specific structure is added for secondary encapsulation and emulsification, and finally a dispersant and silicon dioxide are added to stir evenly. During the preparation process, the modified silicone introduces a cardanol group, with a benzene ring as the matrix, and a hydroxyl group on the benzene ring. In terms of performance characteristics, it shows the flexibility of long alkanes and the rigidity of benzene rings. It can efficiently emulsify and encapsulate silicone active substances, improve the stability and compatibility of the defoamer, and avoid the precipitation of silicone grease; the polyether-modified silicone with a specific structure is introduced for secondary encapsulation in the later stage, which further improves the compatibility and improves the dispersibility of the defoamer; the dispersant and silicon dioxide introduced at the end improve the defoaming and anti-foaming performance of the defoamer. Technical Solution

[0006] An organosilicon defoaming composition, consisting of the following substances: A Modified silicone A1. Polyorganohydrogensiloxane At least one polyorganohydrogensiloxane having the following general structural formula: H c R 2 3-c SiO(SiR 2 HO) d (SiR 2 2O) e S i 2 3-c Hc Substituent R 2 is a hydrocarbon group having 1 to 20 carbon atoms, selected from an alkyl group and an aryl group; wherein the alkyl group is selected from a methyl group, an ethyl group, a propyl group, a n-propyl group, a butyl group and an isobutyl group; and the aryl group is selected from a phenyl group and a benzyl group; R 2 Preferably methyl; c is 0, 1, or 2, subscript d is 0 or an integer from 1 to 65, and c+d≥1, the subscript e is an integer from 16 to 290, each molecule having at least 1 silicon-bonded hydrogen atom, preferably at least 2 silicon-bonded hydrogen atoms; A2. Unsaturated polyether At least one unsaturated polyether having the following general structural formula: MO(EO) m (PO) n R 1 In the molecular structure: R 1 Can be the same or different, R 1 is selected from a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R 1 Preferably a hydrogen atom; M is a polyether initiator, which is an unsaturated hydrocarbon group having 3 to 10 carbon atoms, selected from propenyl, α-butenyl, α-pentenyl, α-hexenyl, α-heptenyl, α-octenyl, α-nonenyl, α-decenyl, and M is preferably propenyl; wherein m , n is the degree of polymerization, m An integer between 0 and 50; n is an integer of 10 to 60, and the molecular weight of the EO unit accounts for less than 20% of the total molecular weight of the polyether; A3. Cardanol The structural formula of cardanol is as follows:

[0007] wherein the R group is an unsaturated olefin having 15 carbon atoms and containing at least one olefin group; A4. Catalyst The catalyst is used to catalyze the polymerization reaction of the components of polyorganohydrogen siloxane, unsaturated polyether and cardanol; the catalyst is selected from platinum-alcohol complex, platinum-olefin complex, platinum-alkoxide complex, platinum-ether complex, platinum-ketone complex, chloroplatinic acid isopropanol solution, platinum-vinyl complex. Chloroplatinic acid isopropanol solution is preferred, and the amount of the catalyst is 0.12-0.25% of the total mass of polyorganohydrogen siloxane, unsaturated polyether and cardanol.

[0008] During the synthesis of modified silicone, the ratio of the molar amount of hydrogen atoms in the polyorganohydrogensiloxane to the total molar amount of vinyl groups in the unsaturated polyether and cardanol is 1:1 to 1:1.2; the molar amount of vinyl groups in cardanol accounts for 50-90% of the total molar amount of vinyl groups in the unsaturated polyether and cardanol; and the amount of modified silicone accounts for 30 to 50% of the total mass of the silicone defoaming composition.

[0009] B Polyether modified silicone B1. Polyorganohydrogensiloxane At least one polyorganohydrogensiloxane having the following general structural formula: H c R 2 3-c SiO(SiR 2 HO) d (SiR 2 2O) e S i 2 3-c H c Substituent R 2 is a hydrocarbon group having 1 to 20 carbon atoms, selected from an alkyl group and an aryl group; wherein the alkyl group is selected from a methyl group, an ethyl group, a propyl group, a n-propyl group, a butyl group and an isobutyl group; and the aryl group is selected from a phenyl group and a benzyl group; R 2 Preferably methyl; c is 0, 1, or 2, subscript d is 0 or an integer from 1 to 65, and c+d≥1, the subscript e is an integer from 16 to 290, each molecule having at least 1 silicon-bonded hydrogen atom, preferably at least 2 silicon-bonded hydrogen atoms; B2. Unsaturated polyether At least one unsaturated polyether having the following general structural formula: MO(EO) q (PO) z R 1 In the molecular structure: R 1 Can be the same or different, R 1 is selected from a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R 1 Preferably a hydrogen atom; M is a polyether initiator, which is an unsaturated hydrocarbon group having 3 to 10 carbon atoms, selected from propenyl, α-butenyl, α-pentenyl, α-hexenyl, α-heptenyl, α-octenyl, α-nonenyl, α-decenyl, and M is preferably propenyl; wherein q , z is the degree of polymerization, q An integer from 5 to 40; zis an integer of 0 to 20, and the molecular weight of the EO unit accounts for more than 40% of the total molecular weight of the polyether; B3. Catalyst The catalyst is used to catalyze the polymerization reaction of the components of polyorganohydrogen-containing siloxane and unsaturated polyether; the catalyst is selected from platinum-alcohol complex, platinum-olefin complex, platinum-alkoxide complex, platinum-ether complex, platinum-ketone complex, chloroplatinic acid isopropanol solution, platinum-vinyl complex; preferably chloroplatinic acid isopropanol solution; the amount of the catalyst is 0.12-0.25% of the total mass of the polyorganohydrogen-containing siloxane and the unsaturated polyether.

[0010] During the synthesis of the polyether-modified silicone, the molar ratio of hydrogen atoms in the polyorganohydrogensiloxane to vinyl groups in the unsaturated polyether is 1:1 to 1:1.2, and the amount of the polyether-modified silicone accounts for 20-40% of the total mass of the silicone defoaming composition.

[0011] C Silicone Actives The organosilicon active material is prepared by technicians according to known techniques, and is prepared from polyorganohydrogen siloxane, coupling agent, unsaturated hydrocarbon, catalyst, organosilicon resin and silicon dioxide. The amount of the organosilicon active material accounts for 10-30% of the total mass of the organosilicon defoaming composition.

[0012] D Silica The silicon dioxide is hydrophobic silicon dioxide, selected from gas phase hydrophobic silicon dioxide and precipitated hydrophobic silicon dioxide, and has a specific surface area of ​​50 to 500 m 2 / g; the amount of silicon dioxide accounts for 5-10% of the total mass of the organosilicon defoaming composition.

[0013] E Dispersant The dispersant is selected from nonionic surfactants, selected from fatty alcohol polyoxyethylene ether, oleic acid polyoxyethylene ether, castor oil polyoxyethylene ether, polyoxyethylene fatty amine compounds, polyoxyethylene sorbitan monolaurate (Tween-20), polyoxyethylene sorbitan monopalmitate (Tween-40), polyoxyethylene sorbitan monostearate (Tween-60), polyoxyethylene sorbitan monooleate (Tween-80), polyoxyethylene sorbitan trioleate (Tween-85), sorbitan monolaurate Span-20), sorbitan monopalmitate (Span-40), sorbitan monostearate (Span-60), sorbitan monooleate (Span-80), sorbitan trioleate (Span-85), and can be used alone or in combination; the amount used accounts for 5-10% of the total mass of the silicone defoaming composition.

[0014] The mass sum of the above components is 100%.

[0015] The above components are used to prepare the organosilicon composition, and the method for preparing the organosilicon composition is as follows: (1) Mixing polyorganohydrogen siloxane A1, unsaturated polyether A2 and cardanol A3, adding a catalyst at 40°C to 90°C, then heating to 50°C to 200°C for reaction for 1 to 6 hours, and cooling to room temperature to obtain modified organosilicon; (2) Mixing polyorganohydrogen siloxane B1 and unsaturated polyether B2, adding a catalyst at 40°C to 90°C, then heating to 80°C to 180°C for reaction for 1 to 6 hours, and cooling to room temperature to obtain polyether-modified silicone; (3) Mixing the modified silicone and silicone active material C, using a high shear device, at a rotation speed of 1000 to 3000 rpm for 0.5 to 3 hours; then adding the polyether modified silicone, and continuing to mix for 0.5 to 3 hours to obtain a mixture I; (4) Add silicon dioxide to mixture I and pass through a high shear device with a rotation speed of 15,000 to 25,000 rpm to obtain mixture II; finally, add a dispersant and mix evenly to obtain the organosilicon defoaming composition. Implementation Example 1

[0017] (1) 1406 g of polyorganohydrogen siloxane (CH3)3SiO(SiCH3HO)(SiCH3CH3O) 16 Si(CH3)3, 333g unsaturated polyether C4H7O(PO) 10 CH3, 208g cardanol (in the structural formula, R is -C 15 H 29 ) were mixed, 2.34 g of platinum-vinyl complex was added at 40° C., then the temperature was raised to 50° C. for reaction for 6 h, and the temperature was lowered to room temperature to obtain modified organosilicon; (2) 1406 g of polyorganohydrogen siloxane (CH3)3SiO(SiCH3HO)(SiCH3CH3O) 16 Si(CH3)3 and 306g of unsaturated polyether C4H7O(EO)5CH3 were mixed, 2.05g of platinum-vinyl complex was added at 40℃, then the temperature was raised to 80℃ for reaction for 6h, and the temperature was lowered to room temperature to obtain polyether-modified silicone; (3) 30 g of modified silicone and 10 g of silicone active material (prepared according to Example 1 of patent CN104274998A) were mixed, and mixed for 3 h at a speed of 1000 rpm using a high shear device; then 40 g of polyether modified silicone was added, and the mixture was mixed for another 3 h to obtain mixture I-1; (4) Add 10 g of fumed silica (with a specific surface area of ​​50 m 2 / g) was passed through a high shear device at a rotation speed of 15000 rpm to obtain a mixture II-1; finally, 10 g of fatty alcohol polyoxyethylene ether was added and mixed evenly to obtain the organosilicon defoaming composition. Example 2

[0018] (1) 29962 g of polyorganohydrogen siloxane H(C6H5)2SiO[Si(C2H5)2O] 290 Si(C6H5)2H, 829g unsaturated polyether C3H5O(EO) 10 (PO) 20 H, 124.2g cardanol (where R is -C 15 H 27 ) were mixed, 46.37 g of chloroplatinic acid isopropanol solution was added at 90° C., then the temperature was raised to 200° C. for reaction for 1 h, and the temperature was lowered to room temperature to obtain modified organosilicon; (2) 29962 g of polyorganohydrogen siloxane H(C6H5)2SiO[Si(C2H5)2O] 290 Si(C6H5)2H, 3275.8g unsaturated polyether C3H5O(EO) 40 (PO) 20 H, add 49.86g of chloroplatinic acid isopropanol solution at 90°C, then heat to 180°C for reaction for 1h, and cool to room temperature to obtain polyether modified silicone; (3) 50 g of modified silicone and 20 g of silicone active material (prepared according to Example 2 of patent CN104274998A) were mixed, and mixed at a speed of 3000 rpm for 0.5 h using a high shear device; then 20 g of polyether modified silicone was added, and the mixture was mixed for another 0.5 h to obtain mixture I-2; (4) Add 5 g of precipitated silica (with a specific surface area of ​​100 m 2 / g) was passed through a high shear device at a rotation speed of 25000 rpm to obtain a mixture II-2; finally, 5 g of a mixture of oleic acid polyoxyethylene ether and castor oil polyoxyethylene ether was added and mixed evenly to obtain the organosilicon defoaming composition. Example 3

[0019] (1) 5076 g of polyorganohydrogen siloxane H2C4H9SiO[Si(CH3)HO] 20 [Si(CH3)2O] 50 SiC3H7H2, 362.88g unsaturated polyether C5H9O (EO) 20 (PO) 35 C2H5, 444.96g cardanol (where R is -C 15 H 25) were mixed, 11.77 g of platinum-ketone complex was added at 50° C., then the temperature was raised to 80° C. for reaction for 3 h, and the temperature was lowered to room temperature to obtain modified organosilicon; (2) 5076 g of polyorganohydrogen siloxane H2C4H9SiO[Si(CH3)HO] 20 [Si(CH3)2O] 50 SiC3H7H2, 1540.8g unsaturated polyether C5H9O (EO) 20 (PO)5C2H5 was mixed, 13.32 g of platinum-ketone complex was added at 50°C, then the temperature was raised to 120°C for reaction for 2 h, and the temperature was lowered to room temperature to obtain polyether-modified silicone; (3) 40 g of modified silicone and 15 g of silicone active material (prepared according to Example 3 of patent CN104274998A) were mixed, and mixed at a speed of 2000 rpm for 3 h using a high shear device; then 30 g of polyether modified silicone was added, and mixing was continued for 1.5 h to obtain mixture I-3; (4) Add 8 g of fumed silica (with a specific surface area of ​​200 m 2 / g) through a high shear device at a rotation speed of 20000 rpm to obtain a mixture II-3; finally, 7 g of a mixture of a polyoxyethylene fatty amine compound and polyoxyethylene sorbitan monolaurate was added and mixed evenly to obtain the organosilicon defoaming composition. Example 4

[0020] (1) 10422 g of polyorganohydrogen siloxane (CH3)3SiO[Si(CH3)HO] 65 [Si(CH3)2O] 100 Si(CH3)3, 930.4g unsaturated polyether C6H 11 O(EO) 30 (PO) 55 C3H7, 165.6g cardanol (where R is -C 15 H 27 ) were mixed, 28.8 g of platinum-ether complex was added at 460° C., then the temperature was raised to 120° C. for reaction for 2 h, and the temperature was lowered to room temperature to obtain modified organosilicon; (2) 10422 g of polyorganohydrogen siloxane (CH3)3SiO[Si(CH3)HO] 65 [Si(CH3)2O] 100 Si(CH3)3, 2042g unsaturated polyether C6H 11 O(EO) 30 (PO) 10C3H7 was mixed, 31.16 g of platinum-ether complex was added at 50°C, then the temperature was raised to 130°C for reaction for 4 h, and the temperature was lowered to room temperature to obtain polyether-modified silicone; (3) 38 g of modified silicone and 12 g of silicone active material (prepared according to Example 4 of patent CN104274998A) were mixed, and mixed for 2 h at a speed of 1500 rpm using a high shear device; then 35 g of polyether modified silicone was added, and the mixture was mixed for another 2 h to obtain mixture I-4; (4) Add 7 g of precipitated silica (with a specific surface area of ​​300 m 2 / g) passed through a high shear device at a rotation speed of 22000 rpm to obtain a mixture II-4; finally, 8 g of a mixture of polyoxyethylene sorbitan trioleate (Tween-85) and sorbitan monopalmitate (Span-40) was added and mixed evenly to obtain the silicone defoaming composition. Example 5

[0021] (1) 17420 g of polyorganohydrogen siloxane H(C2H5)2SiO[Si(CH3)HO] 40 [Si(CH3)2O] 200 Si(CH3)2H, 1084.8g unsaturated polyether C8H 15 O(EO) 40 (PO) 60 C4H9, 123.6g cardanol (where R is -C 15 H 25 ) were mixed, 37.26 g of platinum-ether complex was added at 70° C., then the temperature was raised to 150° C. for reaction for 4 h, and the temperature was lowered to room temperature to obtain modified organosilicon; (2) 17420 g of polyorganohydrogen siloxane H(C2H5)2SiO[Si(CH3)HO] 40 [Si(CH3)2O] 200 Si(CH3)2H, 2853.4g unsaturated polyether C8H 15 O(EO) 35 (PO) 15 C4H9 was mixed, 40.55 g of platinum-ether complex was added at 70°C, then the temperature was raised to 150°C for reaction for 1.5 h, and the temperature was lowered to room temperature to obtain polyether-modified silicone; (3) 45 g of modified silicone and 18 g of silicone active material (prepared according to Example 5 of patent CN104274998A) were mixed, and mixed at a speed of 2500 rpm using a high shear device for 0.5 to 3 h; then 23 g of polyether modified silicone was added, and the mixture was mixed for 1.5 h to obtain mixture I-5; (4) Add 9 g of precipitated silica (with a specific surface area of ​​400 m 2 / g) was passed through a high shear device at a rotation speed of 18000 rpm to obtain a mixture II-5; finally, 5 g of a mixture of sorbitan trioleate (Span-85) and polyoxyethylene sorbitan monostearate (Tween-60) was added and mixed evenly to obtain the silicone defoaming composition. Example 6

[0022] (1) 20490 g of polyorganohydrogen siloxane H(C3H7)2SiO[Si(CH3)HO] 30 [Si(CH3)2O] 250 Si(CH3)2H, 1782.6g unsaturated polyether C 10 H 19 O(EO) 50 (PO) 60 C4H9, 374.4g cardanol (where R is -C 15 H 29 ) were mixed, 45.29 g of chloroplatinic acid isopropanol solution was added at 80° C., then the temperature was raised to 180° C. for reaction for 1 h, and the temperature was lowered to room temperature to obtain modified organosilicon; (2) 20490 g of polyorganohydrogen siloxane H(C3H7)2SiO[Si(CH3)HO] 30 [Si(CH3)2O] 250 Si(CH3)2H, 2395.2g unsaturated polyether C 10 H 19 O(EO) 30 (PO)8C4H9 was mixed, 45.77 g of chloroplatinic acid isopropanol solution was added at 80°C, then the temperature was raised to 160°C for reaction for 2 hours, and the temperature was lowered to room temperature to obtain polyether-modified silicone; (3) 35 g of modified silicone and 25 g of silicone active material (prepared according to Example 6 of patent CN104274998A) were mixed, and mixed for 0.5 h at a speed of 2800 rpm using a high shear device; then 28 g of polyether modified silicone was added, and the mixture was mixed for another 0.5 h to obtain mixture I-6; (4) Add 6 g of precipitated silica (with a specific surface area of ​​500 m 2 / g) was passed through a high shear device at a rotation speed of 16000 rpm to obtain a mixture II-6; finally, 6 g of castor oil polyoxyethylene ether was added and mixed evenly to obtain the organosilicon defoaming composition. Example 7

[0023] (1) 9054 g of polyorganohydrogen siloxane H(CH3)2SiO[Si(CH3)HO] 50 [Si(CH3)2O] 80 Si(CH3)2H, 1547g unsaturated polyether C5H9O(EO) 15 (PO) 40 C2H5, 208g cardanol (where R is -C 15 H 29 ) were mixed, 21.62 g of chloroplatinic acid isopropanol solution was added at 60° C., then the temperature was raised to 100° C. for reaction for 5 h, and the temperature was lowered to room temperature to obtain modified organosilicon; (2) 9054 g of polyorganohydrogen siloxane H(CH3)2SiO[Si(CH3)HO] 50 [Si(CH3)2O] 80 Si(CH3)2H, 2699.4g unsaturated polyether C5H9O(EO) 40 (PO) 10 C2H5 was mixed, 23.51 g of chloroplatinic acid isopropanol solution was added at 45°C, then the temperature was raised to 140°C for reaction for 4 hours, and the temperature was lowered to room temperature to obtain polyether-modified silicone; (3) 31 g of modified silicone and 30 g of silicone active material (prepared according to Example 7 of patent CN104274998A) were mixed, and mixed for 0.5 h at a speed of 2800 rpm using a high shear device; then 22 g of polyether modified silicone was added, and the mixture was mixed for 1 h to obtain mixture I-7; (4) Add 8 g of fumed silica (with a specific surface area of ​​450 m 2 / g) passed through a high shear device at a rotation speed of 23000 rpm to obtain a mixture II-7; finally, 9 g of a mixture of anhydrous sorbitan monolaurate (Span-20) and polyoxyethylene anhydrous sorbitan monolaurate (Tween-20) were added and mixed evenly to obtain the silicone defoaming composition. Comparative Example 1

[0024] (1) 1406 g of polyorganohydrogen siloxane (CH3)3SiO(SiCH3HO)(SiCH3CH3O) 16 Si(CH3)3, 541g unsaturated polyether C4H7O(PO) 10 CH3, add 2.34 g of platinum-vinyl complex at 40°C, then heat to 50°C for reaction for 6 h, and cool to room temperature to obtain modified silicone; (2) 1406 g of polyorganohydrogen siloxane (CH3)3SiO(SiCH3HO)(SiCH3CH3O) 16Si(CH3)3 and 306g of unsaturated polyether C4H7O(EO)5CH3 were mixed, 2.05g of platinum-vinyl complex was added at 40℃, then the temperature was raised to 80℃ for reaction for 6h, and the temperature was lowered to room temperature to obtain polyether-modified silicone; (3) 30 g of modified silicone and 10 g of silicone active material (prepared according to Example 1 of patent CN104274998A) were mixed, and mixed for 3 h at a speed of 1000 rpm using a high shear device; then 40 g of polyether modified silicone was added, and the mixture was mixed for another 3 h to obtain mixture I-8; (4) Add 10 g of fumed silica (with a specific surface area of ​​50 m 2 / g) was passed through a high shear device at a rotation speed of 15000 rpm to obtain a mixture II-8; finally, 10 g of fatty alcohol polyoxyethylene ether was added and mixed evenly to obtain the organosilicon defoaming composition. Comparative Example 2

[0025] (1) 29962 g of polyorganohydrogen siloxane H(C6H5)2SiO[Si(C2H5)2O] 290 Si(C6H5)2H, 829g unsaturated polyether C3H5O(EO) 10 (PO) 20 H, 124.2g cardanol (where R is -C 15 H 27 ) were mixed, 46.37 g of chloroplatinic acid isopropanol solution was added at 90° C., then the temperature was raised to 200° C. for reaction for 1 h, and the temperature was lowered to room temperature to obtain modified organosilicon; (2) 70 g of modified silicone and 20 g of silicone active material (prepared according to Example 2 of patent CN104274998A) were mixed, and mixed at a speed of 3000 rpm for 0.5 h using a high shear device to obtain mixture I-9; (3) Add 5 g of precipitated silica (with a specific surface area of ​​100 m 2 / g) was passed through a high shear device at a rotation speed of 25000 rpm to obtain a mixture II-9; finally, 5 g of a mixture of oleic acid polyoxyethylene ether and castor oil polyoxyethylene ether was added and mixed evenly to obtain the silicone defoaming composition. Comparative Example 3

[0026] (1) 5076 g of polyorganohydrogen siloxane H2C4H9SiO[Si(CH3)HO] 20 [Si(CH3)2O] 50 SiC3H7H2, 1540.8g unsaturated polyether C5H9O (EO) 20(PO)5C2H5 was mixed, 13.32 g of platinum-ketone complex was added at 50°C, then the temperature was raised to 120°C for reaction for 2 h, and the temperature was lowered to room temperature to obtain polyether-modified silicone; (2) 70 g of polyether-modified silicone and 15 g of silicone active material (prepared according to Example 3 of patent CN104274998A) were mixed and mixed at a speed of 2000 rpm for 3 h using a high shear device; mixture I-10; (3) Add 8 g of fumed silica (with a specific surface area of ​​200 m 2 / g) through a high shear device at a rotation speed of 20000 rpm to obtain a mixture II-10; finally, 7 g of a mixture of a polyoxyethylene fatty amine compound and polyoxyethylene sorbitan monolaurate was added and mixed evenly to obtain the organosilicon defoaming composition.

[0027] Performance Testing 1. Stability test: Use Formulaction / Turbiscan Tower / Multiple Light Scattering Stability Analyzer to test the stability of the sample. The test temperature is 40°C and the sample amount is 20g. The smaller the TSI index in the test result, the better the sample stability. 2. Anti-foaming performance test: Add 0.5% anti-foaming agent to 0.2% sodium dodecylbenzene sulfonate solution, take 100g and add it to a 250ml sample bottle. Place the sample bottle on a vertical oscillator for testing (set the oscillation frequency to 450Hz and the amplitude to 30mm). The shorter the anti-foaming time, the better the anti-foaming performance. 3. Compatibility test: Put the sodium dodecylbenzene sulfonate solution that has been tested for its defoaming and antifoaming properties into a beaker, let it stand and visually observe the state of the silicone defoaming composition. The higher the level, the worse the compatibility.

[0028] Visual inspection according to the following scale: 1# = no precipitation or stratification.

[0029] 2#=Small siloxane precipitates on the surface or wall.

[0030] 3#=Large siloxane precipitates on the surface or wall.

[0031] 4#=Siloxane precipitates in clusters on the surface or wall.

[0032] One week Two weeks Four weeks Eight weeks Example 1 1# 1# 1# 1# Example 2 1# 1# 1# 1# Example 3 1# 1# 1# 1# Example 4 1# 1# 1# 1# Example 5 1# 1# 1# 1# Example 6 1# 1# 1# 1# Example 7 1# 1# 1# 2# Comparative Example 1 2# 2# 3# 3# Comparative Example 2 2# 3# 3# 4# Comparative Example 3 4# 4# 4# 4#

Claims

1. An organosilicon defoaming composition, characterized in that It is composed of the following substances: A. Modified silicone, which is obtained by reacting polyorganohydrogen siloxane A1, unsaturated polyether A2 and cardanol A3 under the action of a platinum catalyst, and the amount of the modified silicone accounts for 30-50% of the total mass of the silicone defoaming composition; B. polyether-modified silicone, which is obtained by reacting polyorganohydrogensiloxane B1 and unsaturated polyether B2 under the action of a platinum catalyst, and the amount of polyether-modified silicone accounts for 20-40% of the total mass of the silicone defoaming composition; C. Organic silicon active material, which is prepared by technicians according to known techniques, and is prepared from polyorganohydrogen siloxane, coupling agent, unsaturated hydrocarbon, catalyst, organic silicon resin and silicon dioxide, and the amount of organic silicon active material accounts for 10-30% of the total mass of the organic silicon defoaming composition; D. Silica, wherein the silica is hydrophobic silica selected from gas phase hydrophobic silica and precipitated hydrophobic silica, and has a specific surface area of ​​50 to 500 m 2 / g; the amount of silicon dioxide accounts for 5-10% of the total mass of the organosilicon defoaming composition; E. Dispersant. The dispersant is a nonionic surfactant selected from fatty alcohol polyoxyethylene ether, oleic acid polyoxyethylene ether, castor oil polyoxyethylene ether, polyoxyethylene fatty amine compound, polyoxyethylene sorbitan monolaurate (Tween-20), polyoxyethylene sorbitan monopalmitate (Tween-40), polyoxyethylene sorbitan monostearate (Tween-60), polyoxyethylene sorbitan monooleate (Tween-80), polyoxyethylene sorbitan trioleate (Tween-85), sorbitan monolaurate Span-20), sorbitan monopalmitate (Span-40), sorbitan monostearate (Span-60), sorbitan monooleate (Span-80), sorbitan trioleate (Span-85), and can be used alone or in combination. The amount used accounts for 5-10% of the total mass of the silicone defoaming composition.

2. The organosilicon defoaming composition according to claim 1, characterized in that: The general structural formula of the polyorganohydrogensiloxane A1 is as follows: H c R 2 3-c SiO(SiR 2 HO) d (SiR 2 2O) e SiR 2 3-c H c Substituent R 2 is a hydrocarbon group having 1 to 20 carbon atoms, selected from alkyl and aryl groups; wherein the alkyl group is selected from methyl, ethyl, propyl, n-propyl, butyl and isobutyl; the aryl group is selected from phenyl and benzyl; R 2 Preferably methyl; c is 0, 1, or 2, subscript d is 0 or an integer from 1 to 65, and c+d≥1, the subscript e is an integer from 16 to 290, and each molecule has at least one silicon-bonded hydrogen atom.

3. The organosilicon defoaming composition according to claim 1, characterized in that: The polyorganohydrogensiloxane A1 preferably has at least 2 silicon-bonded hydrogen atoms.

4. The organosilicon defoaming composition according to claim 1, characterized in that: The general structural formula of the unsaturated polyether A2 is as follows: IN(EO) m (NIGHT) n R 1 In the molecular structure: R 1 Can be the same or different, R 1 is selected from a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R 1 Preferably a hydrogen atom; M is a polyether initiator, which is an unsaturated hydrocarbon group having 3 to 10 carbon atoms, selected from propenyl, α-butenyl, α-pentenyl, α-hexenyl, α-heptenyl, α-octenyl, α-nonenyl, α-decenyl; wherein m , n is the degree of polymerization, m An integer between 0 and 50; n is an integer of 10 to 60, and the molecular weight of the EO unit accounts for less than 20% of the total molecular weight of the polyether.

5. The organosilicon defoaming composition according to claim 1, characterized in that: In the unsaturated polyether A2, the M group is preferably a propenyl group.

6. The organosilicon defoaming composition according to claim 1, characterized in that: The general structural formula of the cardanol A3 is as follows: The R group is an unsaturated olefin having 15 carbon atoms and contains at least one olefin group.

7. The organosilicon defoaming composition according to claim 1, characterized in that: The catalyst A4 is used to catalyze the polymerization reaction of components such as polyorganohydrogensiloxane, unsaturated polyether and cardanol; the catalyst is selected from platinum-alcohol complex, platinum-olefin complex, platinum-alkoxide complex, platinum-ether complex, platinum-ketone complex, chloroplatinic acid isopropanol solution, platinum-vinyl complex, preferably chloroplatinic acid isopropanol solution.

8. The organosilicon defoaming composition according to claim 1, characterized in that: The ratio of the molar amount of hydrogen atoms in the polyorganohydrogensiloxane to the total molar amount of vinyl groups in the unsaturated polyether and cardanol is 1:1 to 1:1.2; the molar amount of vinyl groups in the cardanol accounts for 50-90% of the total molar amount of vinyl groups in the unsaturated polyether and cardanol; and the amount of the catalyst used is 0.12 to 0.25% of the total mass of the polyorganohydrogensiloxane, the unsaturated polyether and cardanol.

9. The organosilicon defoaming composition according to claim 1, characterized in that: The general structural formula of polyorganohydrogensiloxane B1 is as follows: H c R 2 3-c SiO(SiR 2 HO) d (SiR 2 2O) e SiR 2 3-c H c Substituent R 2 is a hydrocarbon group having 1 to 20 carbon atoms, selected from alkyl and aryl groups; wherein the alkyl group is selected from methyl, ethyl, propyl, n-propyl, butyl and isobutyl; the aryl group is selected from phenyl and benzyl; R 2 Preferably methyl; c is 0, 1, or 2, subscript d is 0 or an integer from 1 to 65, and c+d≥1, the subscript e is an integer from 16 to 290, and each molecule has at least one silicon-bonded hydrogen atom.

10. The organosilicon defoaming composition according to claim 1, characterized in that: The polyorganohydrogensiloxane B1 preferably has at least 2 silicon-bonded hydrogen atoms.

11. The organosilicon defoaming composition according to claim 1, characterized in that: The unsaturated polyether B2 has the structural formula: IN(EO) q (NIGHT) z R 1 R 1 Can be the same or different, R 1 is selected from a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R 1 Preferably a hydrogen atom; M is a polyether initiator, which is an unsaturated hydrocarbon group having 3 to 10 carbon atoms, selected from propenyl, α-butenyl, α-pentenyl, α-hexenyl, α-heptenyl, α-octenyl, α-nonenyl, α-decenyl; wherein q , z is the degree of polymerization, q An integer from 5 to 40; z is an integer of 0 to 20, and the molecular weight of the EO unit accounts for more than 40% of the total molecular weight of the polyether.

12. The organosilicon defoaming composition according to claim 1, characterized in that: The M group in the unsaturated polyether B2 is preferably a propenyl group.

13. The organosilicon defoaming composition according to claim 1, characterized in that: The catalyst B3 is used to catalyze the polymerization reaction of the components of polyorganohydrogen-containing siloxane and unsaturated polyether; the catalyst is selected from platinum-alcohol complex, platinum-olefin complex, platinum-alkoxide complex, platinum-ether complex, platinum-ketone complex, chloroplatinic acid isopropanol solution, and platinum-vinyl complex.

14. The organosilicon defoaming composition according to claim 1, characterized in that: The catalyst B3 is preferably chloroplatinic acid isopropanol solution.

15. The organosilicon defoaming composition according to claim 1, characterized in that: In the preparation process of the polyether-modified silicone, the molar ratio of hydrogen atoms in the polyorganohydrogensiloxane to vinyl groups in the unsaturated polyether is 1:1 to 1:1.2; and the amount of the catalyst used is 0.12 to 0.25% of the total mass of the polyorganohydrogensiloxane and the unsaturated polyether.

16. The organosilicon defoamer composition according to any one of claims 1 to 15, wherein the preparation method thereof is as follows: (1) Mixing polyorganohydrogen siloxane A1, unsaturated polyether A2 and cardanol A3, adding a catalyst at 40°C to 90°C, then heating to 50°C to 200°C for reaction for 1 to 6 hours, and cooling to room temperature to obtain modified organosilicon; (2) Mixing polyorganohydrogen siloxane B1 and unsaturated polyether B2, adding a catalyst at 40°C to 90°C, then heating to 80°C to 180°C for reaction for 1 to 6 hours, and cooling to room temperature to obtain polyether-modified silicone; (3) Mixing the modified silicone and silicone active material C, using a high shear device, at a rotation speed of 1000 to 3000 rpm for 0.5 to 3 hours; then adding the polyether modified silicone, and continuing to mix for 0.5 to 3 hours to obtain a mixture I; (4) Add silicon dioxide to mixture I and pass through a high shear device with a rotation speed of 15,000 to 25,000 rpm to obtain mixture II; finally, add a dispersant and mix evenly to obtain the organosilicon defoaming composition.

Images