Organic silicon defoaming composition and preparation method thereof

Abstract

The invention relates to an organic silicon defoaming composition and a preparation method thereof.The preparation method comprises the steps that high-hydrogen-content polysiloxane and high-vinyl-content vinyl polysiloxane react under the action of a catalyst, and solid organic silicon powder is formed; the preparation method comprises the following steps: reacting hydrogen-terminated polysiloxane with alpha-olefin under the action of a catalyst to form alkyl-terminated hydrogen-containing polysiloxane; the preparation method comprises the following steps: reacting side hydrogen-containing polyorganosiloxane with alpha-olefin under the action of a catalyst to form side alkyl hydrogen-containing polyorganosiloxane; the preparation method comprises the following steps: mixing solid organic silicon powder, side alkyl hydrogen-containing polysiloxane and end alkyl polysiloxane, putting the mixture into a reactor, carrying out crosslinking reaction on the solid organic silicon powder and residual hydrogen in the side alkyl hydrogen-containing polysiloxane and the end alkyl hydrogen-containing polysiloxane to form a polymer with a SiOSi space structure, and then adding organic silicon resin to prepare the organic silicon defoaming composition. The cross-linking density of the organic silicon defoaming composition is improved, and the defoaming and foam inhibition performance of the defoaming agent is greatly improved.

Description

Technical Field

[0001] The invention relates to an organosilicon defoaming composition and a preparation method thereof. The organosilicon defoaming composition belongs to fine chemicals, so the invention belongs to the technical field of fine chemical preparations. Background Art

[0002] In the process of industrial production, the generation of a large amount of foam seriously affects the production process, such as reducing the working efficiency of production equipment, delaying the working time of production personnel, and affecting the quality of production products. The methods of eliminating harmful foam can be divided into physical methods and chemical methods. Using defoaming agents to eliminate foam is one of the chemical methods. In recent years, defoaming agents have been widely promoted and applied. At present, defoaming agents on the market are classified by active ingredients, mainly polyethers, silicones, mineral oils, fatty alcohols and other polymers. Among them, silicone defoaming agents are widely favored by consumers due to their stable chemical properties, small side effects, and strong defoaming and suppression properties.

[0003] The organosilicon defoaming composition is the core component of the organosilicon defoamer. Its defoaming speed and antifoaming performance directly affect the performance of the final product. For organosilicon defoamers, the improvement of the defoaming and antifoaming performance of its active ingredients is the main optimization direction of the organosilicon defoamer. The original organosilicon defoaming composition was prepared by polydimethylsiloxane and silicon dioxide through a specific processing technology. For example, the defoamer composition introduced in GB1051687A was prepared by heating polydimethylsiloxane and hydrophilic silicon dioxide, but its antifoaming performance was poor. Later, DE-OS2925722 replaced hydrophilic silicon dioxide with hydrophobic silicon dioxide; US-A4145308 introduced (CH3)3SiO 1 / 2and SiO2 units; US4395352 describes an antifoaming agent composition containing a high-viscosity polydimethylsiloxane fluid and finely dispersed hydrophobic particles, which can be used as a defoaming agent itself or in the form of an emulsion; US3691091 discloses an organosilicon emulsion of an aqueous liquid defoaming agent, wherein the organosilicon consists of a polydimethylsiloxane fluid, silicon dioxide, and an organosilicon compound or oligomer containing an alkoxy group and / or a silanol group; EP0163541 discloses a method for preparing an organosilicon defoaming agent by reacting a mixture of components including a preformed polyorganosiloxane polymer with one or more hydroxyl groups and / or hydrocarbon oxygen groups, an organosilicon resin, a filler, and a catalyst for promoting the reaction; EP-A-578424 prepares a foam control agent using a polydiorganosiloxane having a part of its side chains as a long-chain alkyl group, each of which contains 9-35 carbon atoms. The above patents all mention non-crosslinked silicone polymers, and all introduce hydrophobic particles to improve the foam breaking performance of the composition. The degree of crosslinking of these compositions is not enough, and the foam suppression performance is poor in the later stage. At the same time, although the hydrophobic particles can improve the foam performance in the short term, with continuous application, the hydrophobic particles in the later stage of the composition may precipitate or agglomerate, the compatibility of the composition will deteriorate, and the performance is easy to decay.

[0004] Next, EP163541B1, CN102698475A, and CN104274998A introduce the use of terminal hydroxyl-containing polysiloxanes to react with polyorganosiloxanes containing other active functional groups under the action of a catalyst to form branched polyorganosiloxanes, and use this to replace ordinary polysiloxanes and hydrophilic silica for mixed treatment. The prepared organosilicon defoaming composition has improved crosslinking degree, but the viscosity is too high and it is difficult to emulsify and disperse it in water. US5153258 introduces the introduction of slightly crosslinked polyorganosiloxanes into the system to improve the defoaming and defoaming performance of the composition, for example, vinyl polyorganosiloxane and hydrogen-containing polyorganosiloxane, hydroxyl-containing polyorganosiloxane and alkyl silicate undergo crosslinking reaction under the action of a catalyst, but the degree of crosslinking is difficult to control. US5486306 introduces a defoamer synthesized directly by reacting hydrogen-containing polyorganosiloxane with α-olefins. This process is simple to synthesize, but the defoamer obtained has poor defoaming performance and is only used in washing powder. Silicon spots are easily generated when it comes into contact with fabrics. WO2007137948A1 introduces that after the reaction of hydrogen-containing polyorganosiloxane and vinyl polyorganosiloxane, trimethylsiloxy-terminated polydimethylsiloxane is added for dilution, but the contribution of the diluent to the defoaming performance is small, and when the hydrogen-containing polyorganosiloxane and vinyl polyorganosiloxane react, the viscosity is large and difficult to control, and the obtained defoamer composition has poor defoaming and antifoaming performance. CN105107237A synthesizes terminal alkyl polysiloxane and side alkyl polysiloxane with terminal hydrogen-containing polysiloxane and side hydrogen-containing polysiloxane respectively, and finally introduces silanol polymer as a crosslinking agent to improve the crosslinking degree of the composition. The above patents all improve the defoaming and antifoaming performance by improving the crosslinking degree of the composition, but the aggregation and precipitation problems of hydrophobic particles still exist. Summary of the invention

[0005] The invention relates to an organosilicon defoaming composition and a preparation method thereof. The invention comprises the following steps: reacting a high hydrogen-containing polyorganosiloxane and a high vinyl-content vinyl polysiloxane under the action of a catalyst to form a solid organosilicon powder; reacting a terminal hydrogen-containing polyorganosiloxane with an alpha-olefin under the action of a catalyst to form a terminal alkyl hydrogen-containing polyorganosiloxane; reacting a side hydrogen-containing polyorganosiloxane with an alpha-olefin under the action of a catalyst to form a side alkyl hydrogen-containing polyorganosiloxane; mixing the solid organosilicon powder, the side alkyl hydrogen-containing polyorganosiloxane and the terminal alkyl polyorganosiloxane into a reactor, so that the solid organosilicon powder reacts with the remaining hydrogen in the terminal and side alkyl hydrogen-containing polyorganosiloxanes to form a SiOSi defoaming composition. A polymer with an intermediate structure is then added to a silicone resin to obtain an organosilicon defoaming composition. The organosilicon solid powder can be completely compatible with the organosilicon system during the reaction process, which solves the defoaming and antifoaming performance attenuation and compatibility problems caused by the aggregation of hydrophobic particles. At the same time, it is obtained by the reaction of hydrogen-containing polysiloxane and vinyl polysiloxane containing high-active groups, and the molecular structure has high density, which can greatly improve the cross-linking density of the organosilicon defoaming composition and greatly improve the defoaming and antifoaming performance of the defoaming agent. This organosilicon defoaming composition can be prepared into a solid defoaming agent and a liquid defoaming agent, and has good defoaming and antifoaming performance in the papermaking and pulping, textile printing and dyeing, petroleum extraction, daily chemical washing and industrial cleaning industries.

[0006] The organosilicon defoaming composition of the present invention is composed of the following substances: A. Hydrogen-terminated polysiloxane At least one of the general structural formulas is as follows: R 0 2HSiO ( Me 2SiO) a SiH 0 2 In the formula, the substituent R 0 are the same or different, and are hydrocarbon groups with 1 to 12 carbon atoms, selected from alkyl, cycloalkyl, and aryl, wherein the alkyl group is selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, and n-dodecyl; the cycloalkyl group is selected from cyclopentyl and cyclohexylethyl; the aryl group is selected from phenyl, benzyl, phenethyl, and 2-phenylpropyl; preferably R 0 is methyl; subscript a It is an integer of 10 to 200; its usage is 20-40% of the total mass of the defoaming composition.

[0007] B. Side-containing hydrogen polysiloxane At least one of the general structural formulas is as follows: Me 3SiO(R 1 HSiO) b (R 12SiO) c Si Me 3 In the formula, the substituent R 1 are the same or different, and are hydrocarbon groups having 1 to 18 carbon atoms, selected from alkyl, cycloalkyl, and aryl, wherein the alkyl group is selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-dodecyl, and n-octadecyl; the cycloalkyl group is selected from cyclopentyl and cyclohexylethyl; the aryl group is selected from phenyl, benzyl, phenethyl, and 2-phenylpropyl; preferably R 1 is methyl; subscript b is an integer between 10 and 100; subscript c is an integer of 10 to 400; its amount is 20-40% of the total mass of the defoaming composition.

[0008] C. α-olefins The α-olefin is a mixture of any one or more of linear α-olefins, α-aromatic olefins or branched α-olefins, including α-octene, α-decene, α-dodecene, α-tetradecene, α-hexadecene, α-octadecene, α-eicosene, a C20-C24 linear α-olefin mixture, a C24-C28 linear α-olefin mixture, α-triacontene, α-methylstyrene, and α-styrene. The α-olefin can be used alone or mixed in any proportion. The α-olefin is added in two parts, the first part is used in an amount of 1-5% of the total mass of the defoaming composition, and the second part is used in an amount of 10-30% of the total mass of the defoaming composition.

[0009] D. Solid silicone powder The solid organosilicon powder is formed by reacting a high hydrogen-containing polyorganosiloxane D1 and a high vinyl-content vinyl polysiloxane D2 under the action of a platinum catalyst D3, and finally ground to obtain a solid organosilicon powder, the amount of which is 10-20% of the total mass of the defoaming composition; The general structural formula of high hydrogen-containing polyorganosiloxane D1 is as follows: H c R 3 3-c SiO(SiR 3 HO) d (SiR 3 2O) b S i 3 3-c H c R 3is an alkyl group having 1 to 5 carbon atoms, which may be the same or different; subscript c is 0, 1 or 2, subscript d is an integer of 100 to 300; subscript b is an integer of 50 to 1600; the hydrogen content of the high hydrogen polysiloxane is ≥ 0.1%; the amount used accounts for 10 to 30% of the total mass of the solid organosilicon powder; The general structure of high vinyl content vinyl polysiloxane D2 is as follows: Vi e R 4 3-e SiO(SiR 4 ViO) f (SiR 4 2O) g S i 4 3-e Vi e R 4 The value range is similar to R 3 The same; Vi is vinyl, subscript e is 0 or 1, subscript f is 30-80; subscript g is 20-80; the molecular weight of high vinyl content vinyl polysiloxane D2 is less than 10000; the amount is 70-90% of the total mass of solid silicone powder The platinum catalyst D3 is selected from platinum-alcohol complexes, platinum-olefin complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-ketone complexes, chloroplatinic acid isopropanol solution, and platinum-vinyl complexes; the amount used is 0.01%-0.05% of the total mass of the high hydrogen-containing polysiloxane and the high vinyl content vinyl polysiloxane.

[0010] E. Catalyst The catalyst is selected from platinum-alcohol complexes, platinum-olefin complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-ketone complexes, chloroplatinic acid isopropanol solution, and platinum-vinyl complexes, preferably chloroplatinic acid isopropanol solution; the amount of the catalyst is 3-20 ppm (in terms of platinum) of the total mass of the terminal hydrogen-containing polyorganosiloxane A, the side hydrogen-containing polyorganosiloxane B, the α-olefin C and the solid organosilicon powder D, and is used in three parts.

[0011] F. MQ Silicone Resin The MQ silicone resin is an MQ resin composed of chain segments (CH3)3SiOl / 2 (M unit) and chain segments SiO4 / 2 (Q unit), the molar ratio between the two is (0.4-1.2):1.0, and the dosage is 2-8% of the total mass of the defoaming composition.

[0012] The preparation method of the organosilicon defoaming composition of the present invention is as follows: (1) Adding terminal hydrogen-containing polyorganosiloxane A and the first part of α-olefin into a reaction vessel, adding a catalyst when the temperature rises to 50-80° C., and keeping the temperature for 0.5-1.5 hours to obtain terminal alkyl hydrogen-containing polyorganosiloxane X; (2) Add the side hydrogen-containing polyorganosiloxane B and the second part of α-olefin into another reaction container, add the catalyst when the temperature rises to 50-80°C, raise the temperature to 120-200°C, and keep the temperature for 0.5-1.5h to obtain the side alkyl hydrogen-containing polyorganosiloxane Y; (3) Add the catalyst to the solid organosilicon powder D, the side alkyl hydrogen-containing polyorganosiloxane Y, and the terminal alkyl hydrogen-containing polyorganosiloxane X at a temperature of 50-80°C, raise the temperature to 110-180°C, and keep the temperature for 0.5-1.5 hours; (4) Add MQ silicone resin to the mixture in (3), keep the mixture at 100-160°C for 1-5 hours, and cool it to room temperature to obtain an organosilicon defoaming composition.

[0013] For certain applications, the organosilicon defoaming composition of the present invention can be prepared into an emulsion defoaming agent or a solid defoaming agent for use.

[0014] If the silicone defoaming composition of the present invention is prepared into an emulsion defoaming agent, it can be prepared using the techniques for preparing silicone emulsions that are well known to those skilled in the art. Generally speaking, silicone emulsions contain the silicone defoaming composition as an oil phase, one or more surfactants, water and standard additives (such as preservatives, viscosity improvers, anti-gelling agents and / or thickeners); the surfactant can be selected from anionic, cationic, nonionic or amphoteric materials, or one or more mixtures thereof can be used.

[0015] The organosilicon defoaming composition of the present invention is prepared into a solid powder or granular defoaming agent. The preparation of the solid powder or granular defoaming agent can be carried out using methods well known to those skilled in the art, such as spray drying or agglomeration granulation, and additives well known to those skilled in the art. DETAILED DESCRIPTION

[0016] Solid organosilicon powder examples and comparative examples Example 1

[0017] 100g high hydrogen polysiloxane 100gH2MeSiO(SiMeHO) 130 (SiMe2O) 1600 SiMeH2, 900g high vinyl content vinyl polysiloxane Me3SiO (SiMeViO) 30 (SiMe2O) 80SiMe3 was mixed, 0.1 g of chloroplatinic acid isopropanol solution 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 organosilicon powder solid D1 Example 2

[0018] 200g of high hydrogen-containing polyorganosiloxane H3SiO[Si(C2H5)HO)] 150 [(SiMe(C2H5)O)] 1000 SiH3, 800g high vinyl content vinyl polysiloxane ViMe2SiO (SiMeViO) 80 (SiMe2O) 20 SiViMe2 was mixed, 0.2 g of platinum-alcohol complex was added at 50°C, then the temperature was raised to 80°C for reaction for 5 h, and the temperature was lowered to room temperature to obtain organosilicon powder solid D2 Example 3

[0019] 300 g of high hydrogen-containing polyorganosiloxane H (Me)(C3H7)SiO[Si(C3H7)HO)] 200 [(SiMe(C3H7)O)] 800 Si(Me)2H, 700g high vinyl content vinyl polysiloxane (C2H5)2(C3H7)SiO[Si(C2H5)ViO] 40 [Si(C2H5)2(C3H7)O] 40 Si(C2H5)2(C3H7) was mixed, 0.3 g of platinum-olefin complex was added at 60°C, then the temperature was raised to 110°C for reaction for 4 hours, and the temperature was lowered to room temperature to obtain organosilicon powder solid D3; Example 4

[0020] 150g of high hydrogen-containing polysiloxane (C4H9)2(C3H7)SiO[Si(C3H7)HO)] 300 [(SiMe(C3H7)O)] 500 Si(C4H9)(C3H7)2, 850g high vinyl content vinyl polysiloxane Vi(C4H9)2SiO[Si(C4H9)ViO] 20 [Si(C2H5)2(C4H9)O] 15 Si(C4H9)2Vi were mixed, 0.4 g of platinum-alkoxide complex was added at 70°C, then the temperature was raised to 150°C for reaction for 3 h, and the temperature was lowered to room temperature to obtain organosilicon powder solid D4 Example 5

[0021] 250g high hydrogen polysiloxane 450gH2(C5H 11 )SiO[Si(CH3)HO)]250 [(SiMe2O)] 200 Si(C5H 11 )H2, 750g high vinyl content vinyl polysiloxane (C5H 11 )3SiO[Si(Me)ViO] 15 [Si(C5H 11 )(Me)O] 10 Si(C5H 11 )3, add 0.5g of platinum-ether complex at 80℃, then heat to 180℃ for 2h, cool to room temperature to obtain organosilicon powder solid D5 Example 6

[0022] 180g high hydrogen-containing polysiloxane H3SiO[Si(CH3)HO)] 300 [(SiMe2O)] 50 SiH3, 820 g high vinyl content vinyl polysiloxane ViMe2SiO[Si(Me)ViO] 60 [Si(Me)2O] 60 SiMe2Vi was mixed, 0.25 g of platinum-ketone complex 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 organosilicon powder solid D6 Comparative Example 1

[0023] 100g hydrogen-containing polyorganosiloxane 100gH2MeSiO (SiMeHO) 100 (SiMe2O) 1600 SiMeH2, 900g high vinyl content vinyl polysiloxane Me3SiO (SiMeViO) 30 (SiMe2O) 80 SiMe3 was mixed, 0.1 g of chloroplatinic acid isopropanol solution 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 organosilicon powder solid D7 Comparative Example 2

[0024] 200g hydrogen-containing polyorganosiloxane 200gH3SiO[Si(C2H5)HO)] 50 [(SiMe(C2H5)O)] 1000 SiH3, 800g high vinyl content vinyl polysiloxane ViMe2SiO (SiMeViO) 80 (SiMe2O) 20 SiViMe2 was mixed, 0.2 g of platinum-alcohol complex was added at 50°C, then the temperature was raised to 80°C for reaction for 5 h, and the temperature was lowered to room temperature to obtain organosilicon powder solid D8; Comparative Example 3

[0025] 300 g of high hydrogen-containing polyorganosiloxane H (Me)(C3H7)SiO[Si(C3H7)HO)] 200 [(SiMe(C3H7)O)] 800 Si(Me)2H, 700g high vinyl content vinyl polysiloxane (C2H5)2(C3H7)SiO[Si(C2H5)ViO] 80 [Si(C2H5)2(C3H7)O] 40 Si(C2H5)2(C3H7) was mixed, 0.3 g of platinum-olefin complex was added at 60°C, then the temperature was raised to 110°C for reaction for 4 hours, and the temperature was lowered to room temperature to obtain organosilicon powder solid D9. Comparative Example 4

[0026] 400g of high hydrogen-containing polyorganosiloxane (C4H9)2(C3H7)SiO[Si(C3H7)HO)] 300 [(SiMe(C3H7)O)] 500 Si(C4H9)(C3H7)2, 600g high vinyl content vinyl polysiloxane Vi(C4H9)2SiO[Si(C4H9)ViO] 70 [Si(C2H5)2(C4H9)O] 15 Si(C4H9)2Vi were mixed, 0.4 g of platinum-alkoxide complex was added at 70°C, then the temperature was raised to 150°C for reaction for 3 h, and the temperature was lowered to room temperature to obtain organosilicon powder solid D10; Silicone defoaming composition example Example 7

[0027] (1) 200 g of hydrogen-terminated polyorganosiloxane Me2HSiO(Me2SiO) 200 SiHMe2 and 50 g of α-octene were added to a reaction vessel, and when the temperature was raised to 50-80°C, 1 ppm of chloroplatinic acid isopropanol solution was added, and the temperature was kept for 0.5-1.5 h to obtain terminal alkyl hydrogen-containing polyorganosiloxane X1; (2) 400 g of hydrogen-containing polyorganosiloxane Me2(C3H7)SiO(MeHSiO) 70 (Me2SiO) 50 SiMe2(C8H 17 ) and 100g of α-octene are added to another reaction container, and when the temperature is raised to 50-80°C, 1ppm of chloroplatinic acid isopropanol solution is added, and the temperature is raised to 120-200°C and kept warm for 0.5-1.5h to obtain a pendant alkyl hydrogen-containing polyorganosiloxane Y1; (3) Add 1 ppm chloroplatinic acid isopropanol solution to 200 g of solid organosilicon powder D1, side alkyl hydrogen-containing polyorganosiloxane Y1, and terminal alkyl hydrogen-containing polyorganosiloxane X1 at a temperature of 50-80 °C, raise the temperature to 110-180 °C, and keep the temperature for 0.5-1.5 h; (4) Add 50 g MQ silicone resin (M:Q=0.4:1.0) to the mixture in (3), keep the mixture at 100-160°C for 1-5 h, and cool it to room temperature to obtain an organosilicon defoaming composition. Example 8

[0028] (1) 300 g of hydrogen-terminated polyorganosiloxane Me2HSiO(Me2SiO) 32 SiHMe2 and 40g α-decene are added to a reaction vessel, and 2ppm of platinum-alcohol complex is added when the temperature rises to 50-80°C, and the temperature is kept for 0.5-1.5h to obtain terminal alkyl hydrogen-containing polyorganosiloxane X2; (2) 300 g of hydrogen-containing polyorganosiloxane Me2(C6H5)SiO(MeHSiO) 100 (Me2SiO) 400 SiMe2(C 12 H 25 ) and 180g of α-dodecene are added to another reaction container, and when the temperature is raised to 50-80°C, 2pp of platinum-alcohol complex is added, and the temperature is raised to 120-200°C and kept warm for 0.5-1.5h to obtain a side alkyl hydrogen-containing polyorganosiloxane Y2; (3) Add 3 ppm of platinum-alcohol complex to 100 g of solid organosilicon powder D2, side alkyl hydrogen-containing polyorganosiloxane Y2, and terminal alkyl hydrogen-containing polyorganosiloxane X2 at a temperature of 50-80 °C, raise the temperature to 110-180 °C, and keep the temperature for 0.5-1.5 h; (4) Add 80 g of MQ silicone resin (M:Q=0.6:1.0) to the mixture in (3), keep the mixture at 100-160°C for 1-5 hours, and cool it to room temperature to obtain an organosilicon defoaming composition. Example 9

[0029] (1) 400 g of hydrogen-terminated polyorganosiloxane Me2HSiO(Me2SiO) 80 SiHMe2 and 30 g of α-tetradecene are added to a reaction vessel, and when the temperature is raised to 50-80°C, 3 ppm of platinum-olefin complex is added, and the temperature is kept for 0.5-1.5 h to obtain terminal alkyl hydrogen-containing polyorganosiloxane X3; (2) 200 g of hydrogen-containing polyorganosiloxane Me2 (C6H 13 )SiO(MeHSiO) 17 (Me2SiO) 10SiMe3 and 170 g of α-hexadecene are added to another reaction container, and 3 ppm of platinum-olefin complex is added when the temperature is raised to 50-80°C, and the temperature is raised to 120-200°C and kept for 0.5-1.5 h to obtain a pendant alkyl hydrogen-containing polyorganosiloxane Y3; (3) Add 4 ppm of platinum-olefin complex to 180 g of solid organosilicon powder D3, side alkyl hydrogen-containing polyorganosiloxane Y3, and terminal alkyl hydrogen-containing polyorganosiloxane X3 at a temperature of 50-80 °C, raise the temperature to 110-180 °C, and keep the temperature for 0.5-1.5 h; (4) Add 20 g MQ silicone resin (M:Q=0.8:1.0) to the mixture in (3), keep the mixture at 100-160°C for 1-5 h, and cool it to room temperature to obtain an organosilicon defoaming composition. Example 10

[0030] (1) 280 g of terminal hydrogen-containing polyorganosiloxane Me (C5H 11 )HSiO(Me2SiO) 10 SiHMe2 and 20 g of α-octadecene are added to a reaction vessel, and when the temperature rises to 50-80°C, 5 ppm of platinum-alkoxide complex is added, and the temperature is kept for 0.5-1.5 h to obtain terminal alkyl hydrogen-containing polyorganosiloxane X4; (2) 230 g of hydrogen-containing polyorganosiloxane Me3SiO (MeHSiO) 50 (Me2SiO) 100 SiMe2(C 18 H 37 ) and 300g of α-eicosene are added to another reaction container, 5ppm of platinum-alkoxide complex is added when the temperature is raised to 50-80°C, the temperature is raised to 120-200°C, and the temperature is kept for 0.5-1.5h to obtain a pendant alkyl hydrogen-containing polyorganosiloxane Y4; (3) Add 5 ppm of platinum-alkoxide complex to 100 g of solid organosilicon powder D4, side alkyl hydrogen-containing polyorganosiloxane Y4, and terminal alkyl hydrogen-containing polyorganosiloxane X4 at a temperature of 50-80 °C, raise the temperature to 110-180 °C, and keep the temperature for 0.5-1.5 h; (4) Add 70 g of MQ silicone resin (M:Q=1.0:1.0) to the mixture in (3), keep the mixture at 100-160°C for 1-5 hours, and cool it to room temperature to obtain an organosilicon defoaming composition. Embodiment 11

[0031] (1) 330 g of hydrogen-terminated polyorganosiloxane Me2HSiO(Me2SiO) 100SiHMe (C6H5) and 10 g of a C20-C24 linear α-olefin mixture are added to a reaction vessel, and when the temperature rises to 50-80°C, 6 ppm of a platinum-ether complex is added, and the temperature is kept for 0.5-1.5 h to obtain an alkyl-terminated hydrogen-containing polyorganosiloxane X5; (2) 350 g of hydrogen-containing polyorganosiloxane Me3SiO(C3H7HSiO) 10 (Me2SiO) 200 SiMe3 and 130 g of α-eicosene are added to another reaction container, and when the temperature is raised to 50-80°C, 6 ppm of platinum-ether complex is added, and the temperature is raised to 120-200°C and kept for 0.5-1.5 h to obtain a pendant alkyl hydrogen-containing polyorganosiloxane Y5; (3) Add 8 ppm of platinum-ether complex to 150 g of solid organosilicon powder D5, side alkyl hydrogen-containing polyorganosiloxane Y5, and terminal alkyl hydrogen-containing polyorganosiloxane X5 at a temperature of 50-80 °C, raise the temperature to 110-180 °C, and keep the temperature for 0.5-1.5 h; (4) Add 30 g MQ silicone resin (M:Q=1.2:1.0) to the mixture in (3), keep the mixture at 100-160°C for 1-5 h, and cool it to room temperature to obtain an organosilicon defoaming composition. Example 12

[0032] (1) 350 g of terminal hydrogen-containing polyorganosiloxane Me (C8H 17 )HSiO(Me2SiO) 140 SiHMe2 and 20 g of α-styrene are added to a reaction vessel, and when the temperature rises to 50-80°C, 6 ppm of platinum-ketone complex is added, and the temperature is kept for 0.5-1.5 h to obtain terminal alkyl hydrogen-containing polyorganosiloxane X6; (2) 200 g of side hydrogen-containing polyorganosiloxane Me2 (C 11 H 23 )SiO(MeHSiO) 85 (Me2SiO) 290 SiMe3 and 250 g of α-triacontene are added to another reaction container, and 6 ppm of platinum-ketone complex is added when the temperature is raised to 50-80°C, and the temperature is raised to 120-200°C and kept for 0.5-1.5 h to obtain pendant alkyl hydrogen-containing polyorganosiloxane Y6; (3) Add 6 ppm of platinum-ketone complex to 120 g of solid organosilicon powder D6, side alkyl hydrogen-containing polyorganosiloxane Y6, and terminal alkyl hydrogen-containing polyorganosiloxane X6 at 50-80 °C, raise the temperature to 110-180 °C, and keep the temperature for 0.5-1.5 h; (4) Add 60 g of MQ silicone resin (M:Q=0.5:1.0) to the mixture in (3), keep the mixture at 100-160°C for 1-5 h, and cool it to room temperature to obtain an organosilicon defoaming composition. Embodiment 13

[0033] (1) 310 g of hydrogen-terminated polyorganosiloxane Me2HSiO(Me2SiO) 110 SiHMe(C 10 H 21 ) and 50 g of α-octadecene are added to a reaction container, and when the temperature rises to 50-80° C., 5 ppm of platinum-vinyl complex is added and the temperature is kept for 0.5-1.5 h to obtain terminal alkyl hydrogen-containing polyorganosiloxane X7; (2) 300 g of hydrogen-containing polyorganosiloxane Me3SiO (MeHSiO) 35 (Me2SiO) 70 SiMe2(C 15 H 31 ) and 150g of α-octadecene are added to another reaction container, and when the temperature is raised to 50-80°C, 5ppm of platinum-vinyl complex is added, and the temperature is raised to 120-200°C and kept warm for 0.5-1.5h to obtain a pendant alkyl hydrogen-containing polyorganosiloxane Y7; (3) Add 6 ppm of platinum-vinyl complex to 160 g of solid organosilicon powder D7, side alkyl hydrogen-containing polyorganosiloxane Y7, and terminal alkyl hydrogen-containing polyorganosiloxane X7 at a temperature of 50-80 °C, raise the temperature to 110-180 °C, and keep the temperature for 0.5-1.5 h; (4) Add 30 g MQ silicone resin (M:Q=1.1:1.0) to the mixture in (3), keep the mixture at 100-160°C for 1-5 h, and cool it to room temperature to obtain an organosilicon defoaming composition.

[0034] Comparative Example 5 (1) 200 g of hydrogen-terminated polyorganosiloxane Me2HSiO(Me2SiO) 200 SiHMe2 and 50 g of α-octene were added to a reaction vessel, and when the temperature was raised to 50-80°C, 1 ppm of chloroplatinic acid isopropanol solution was added, and the temperature was kept for 0.5-1.5 h to obtain terminal alkyl hydrogen-containing polyorganosiloxane X1; (2) 400 g of hydrogen-containing polyorganosiloxane Me2(C3H7)SiO(MeHSiO) 70 (Me2SiO) 50 SiMe2(C8H 17) and 100g of α-octene are added to another reaction container, and when the temperature is raised to 50-80°C, 1ppm of chloroplatinic acid isopropanol solution is added, and the temperature is raised to 120-200°C and kept warm for 0.5-1.5h to obtain a pendant alkyl hydrogen-containing polyorganosiloxane Y1; (3) Add 1 ppm chloroplatinic acid isopropanol solution to 200 g of solid organosilicon powder D7, side alkyl hydrogen-containing polyorganosiloxane Y1, and terminal alkyl hydrogen-containing polyorganosiloxane X1 at a temperature of 50-80 °C, raise the temperature to 110-180 °C, and keep the temperature for 0.5-1.5 h; (4) Add 50 g MQ silicone resin (M:Q=0.4:1.0) to the mixture in (3), keep the mixture at 100-160°C for 1-5 h, and cool it to room temperature to obtain an organosilicon defoaming composition.

[0035] Comparative Example 6 (1) 300 g of hydrogen-terminated polyorganosiloxane Me2HSiO(Me2SiO) 32 SiHMe2 and 40g α-decene are added to a reaction vessel, and 2ppm of platinum-alcohol complex is added when the temperature rises to 50-80°C, and the temperature is kept for 0.5-1.5h to obtain terminal alkyl hydrogen-containing polyorganosiloxane X2; (2) 300 g of hydrogen-containing polyorganosiloxane Me2(C6H5)SiO(MeHSiO) 100 (Me2SiO) 400 SiMe2(C 12 H 25 ) and 180g of α-dodecene are added to another reaction container, and when the temperature is raised to 50-80°C, 2pp of platinum-alcohol complex is added, and the temperature is raised to 120-200°C and kept warm for 0.5-1.5h to obtain a side alkyl hydrogen-containing polyorganosiloxane Y2; (3) Add 3 ppm of platinum-alcohol complex to 100 g of solid organosilicon powder D8, side alkyl hydrogen-containing polyorganosiloxane Y2, and terminal alkyl hydrogen-containing polyorganosiloxane X2 at a temperature of 50-80 °C, raise the temperature to 110-180 °C, and keep the temperature for 0.5-1.5 h; (4) Add 80 g of MQ silicone resin (M:Q=0.6:1.0) to the mixture in (3), keep the mixture at 100-160°C for 1-5 hours, and cool it to room temperature to obtain an organosilicon defoaming composition.

[0036] Comparative Example 7 (1) 400 g of hydrogen-terminated polyorganosiloxane Me2HSiO(Me2SiO) 80 SiHMe2 and 30 g of α-tetradecene are added to a reaction vessel, and when the temperature is raised to 50-80°C, 3 ppm of platinum-olefin complex is added, and the temperature is kept for 0.5-1.5 h to obtain terminal alkyl hydrogen-containing polyorganosiloxane X3; (2) 200 g of hydrogen-containing polyorganosiloxane Me2 (C6H 13 )SiO(MeHSiO) 17 (Me2SiO) 10 SiMe3 and 170 g of α-hexadecene are added to another reaction container, and 3 ppm of platinum-olefin complex is added when the temperature is raised to 50-80°C, and the temperature is raised to 120-200°C and kept for 0.5-1.5 h to obtain a pendant alkyl hydrogen-containing polyorganosiloxane Y3; (3) Add 4 ppm of platinum-olefin complex to 180 g of solid organosilicon powder D9, side alkyl hydrogen-containing polyorganosiloxane Y3, and terminal alkyl hydrogen-containing polyorganosiloxane X3 at a temperature of 50-80 °C, raise the temperature to 110-180 °C, and keep the temperature for 0.5-1.5 h; (4) Add 20 g MQ silicone resin (M:Q=0.8:1.0) to the mixture in (3), keep the mixture at 100-160°C for 1-5 h, and cool it to room temperature to obtain an organosilicon defoaming composition.

[0037] Comparative Example 8 (1) 280 g of terminal hydrogen-containing polyorganosiloxane Me (C5H 11 )HSiO(Me2SiO) 10 SiHMe2 and 20 g of α-octadecene are added to a reaction vessel, and when the temperature rises to 50-80°C, 5 ppm of platinum-alkoxide complex is added, and the temperature is kept for 0.5-1.5 h to obtain terminal alkyl hydrogen-containing polyorganosiloxane X4; (2) 230 g of hydrogen-containing polyorganosiloxane Me3SiO (MeHSiO) 50 (Me2SiO) 100 SiMe2(C 18 H 37 ) and 300g of α-eicosene are added to another reaction container, 5ppm of platinum-alkoxide complex is added when the temperature is raised to 50-80°C, the temperature is raised to 120-200°C, and the temperature is kept for 0.5-1.5h to obtain a pendant alkyl hydrogen-containing polyorganosiloxane Y4; (3) Add 5 ppm of platinum-alkoxide complex to 100 g of solid organosilicon powder D10, side alkyl hydrogen-containing polyorganosiloxane Y4, and terminal alkyl hydrogen-containing polyorganosiloxane X4 at a temperature of 50-80 °C, raise the temperature to 110-180 °C, and keep the temperature for 0.5-1.5 h; (4) Add 70 g of MQ silicone resin (M:Q=1.0:1.0) to the mixture in (3), keep the mixture at 100-160°C for 1-5 hours, and cool it to room temperature to obtain an organosilicon defoaming composition.

[0038] Comparative Example 9 (1) 330 g of hydrogen-terminated polyorganosiloxane Me2HSiO(Me2SiO) 100 SiHMe (C6H5) and 10 g of a C20-C24 linear α-olefin mixture are added to a reaction vessel, and when the temperature rises to 50-80°C, 6 ppm of a platinum-ether complex is added, and the temperature is kept for 0.5-1.5 h to obtain an alkyl-terminated hydrogen-containing polyorganosiloxane X5; (2) 350 g of hydrogen-containing polyorganosiloxane Me3SiO(C3H7HSiO) 10 (Me2SiO) 200 SiMe3 and 130 g of α-eicosene are added to another reaction container, and when the temperature is raised to 50-80°C, 6 ppm of platinum-ether complex is added, and the temperature is raised to 120-200°C and kept for 0.5-1.5 h to obtain a pendant alkyl hydrogen-containing polyorganosiloxane Y5; (3) 150 g of hydrophobic white carbon black (specific surface area: 200 m 2 / g), side alkyl hydrogen-containing polyorganosiloxane Y5, terminal alkyl hydrogen-containing polyorganosiloxane X5, add 8ppm of platinum-ether complex when the temperature is raised to 50-80°C, raise the temperature to 110-180°C, and keep warm for 0.5-1.5h; (4) Add 30 g MQ silicone resin (M:Q=1.2:1.0) to the mixture in (3), keep the mixture at 100-160°C for 1-5 h, and cool it to room temperature to obtain an organosilicon defoaming composition.

[0039] Example 14-Example 25 According to the solid defoamer preparation technology known in the technical field, the organosilicon defoamer compositions prepared in Examples 7 to 13 and the organosilicon defoamer compositions prepared in Comparative Examples 5 to 9 were used to prepare solid defoamers G1 to G7 and DG1 to DG5, respectively. The preparation methods are as follows: 20 g of the organosilicon defoaming composition, 12 g of polyacrylic acid polymer and 10 g of dodecylbenzene sulfonic acid were mixed evenly, and then 158 g of modified starch and 20 g of water were added, mixed evenly, granulated, and dried at 120° C. for 0.5 h to obtain a solid defoaming agent.

[0040] Embodiment 26 to Embodiment 37 According to the well-known emulsion defoamer preparation technology in the technical field, the organosilicon defoamer compositions prepared in Examples 7 to 13 and the organosilicon defoamer compositions prepared in Comparative Examples 5 to 9 were used to prepare liquid defoamers Y1 to Y7 and DY1 to DY5, respectively. The preparation methods are as follows: 100 g of an organosilicon defoaming composition, 30 g of sorbitan monostearate (span 60) and 20 g of polyoxyethylene (20) sorbitan monostearate were mixed at 70° C. for 10 minutes, and 500 g of water was added in batches; then 2 g of polyacrylic acid was added to the mixture, and the pH was adjusted to 6-7 with 10% NaOH, followed by adding 345 g of water; finally, the emulsion was homogenized with a high-pressure homogenizer, and the pH was adjusted to 6-7 with 10% NaOH again, and then 3 g of an isothiazolinone-based preservative was added to obtain an emulsion defoaming agent.

[0041] Solid defoamer performance test This test uses a Jinzhang drum washing machine, model: ZWH6125, with a capacity of 7kg.

[0042] Test method: Add 150g of commercially available laundry detergent, 0.75g of solid defoaming agent and 20kg of water into the washing machine. The test procedure is the cotton and linen procedure. There are 5 measurement marks on the window of the washing machine, which are 0, 25%, 50%, 75%, and 100% of the window height. "0" is the starting point, indicating no foam, and "100%" indicates full foam. Record the foam height every 5 minutes and record when the machine is stopped. The larger the value, the higher the foam scale value in the washing machine, and the worse the anti-foaming performance; the lower the foam scale value in the same time, the better the anti-foaming performance of the product. The test results are shown in Table 1: Table 1 Washing machine test results

[0043] As can be seen from Table 1, the solid defoamers G1 to G7 prepared using the organosilicon defoaming compositions prepared in Examples 7 to 13 have better defoaming and anti-foaming performance in machine washing in a washing powder solution than the solid defoamers YG1 to YG5 prepared using the organosilicon defoaming compositions of Comparative Examples 5 to 9, and have good anti-attenuation performance in the later stage.

[0044] Emulsion defoamer performance test Test 1: Papermaking black liquor system tested at 85°C Test method: First, add 600mL of black liquor (from pine wood) into the circulating bubbler, set the temperature to 85℃ and the flow rate to 6L / min, then turn on the temperature control switch, heat the foaming liquid to the set temperature, turn on the circulation pump, start impact foaming, and wait until the foam rises to 300mL, add 0.1% defoamer, and record the change of foam height over time. The better the defoaming performance of the defoamer, the lower the minimum scale reached by the foam; the better the anti-foaming performance of the defoamer, the longer it takes for the foam to reach 300mL again.

[0045] Table 2 Test results of black liquor system at 85°C

[0046] As can be seen from Table 2, the liquid defoamers G1 to G7 prepared using the organosilicon defoaming compositions prepared in Examples 7 to 13 have better defoaming and anti-foaming performance in black liquor than the liquid defoamers YG1 to YG5 prepared using the organosilicon defoaming compositions of Comparative Examples 5 to 9, and have good anti-attenuation performance in the later stage.

[0047] Test 2: Textile Slurry Test Test method: Take a 250ml stoppered measuring cylinder and add 160ml of prepared textile pulp, then add 0.05g of emulsion defoamer, shake the bottle up and down at a speed of 2s / time, shake each group of bottles 10 times, and record the defoaming time of each group. The shorter the defoaming time in each group of shaking bottles, the better the defoaming and defoaming performance of the defoamer sample.

[0048] Table 3 Slurry system test

[0049] As can be seen from Table 3, the liquid defoamers G1 to G7 prepared using the organosilicon defoaming compositions prepared in Examples 7 to 13 have better defoaming and anti-foaming performance in textile slurry than the liquid defoamers YG1 to YG5 prepared using the organosilicon defoaming compositions of Comparative Examples 5 to 9, and have good anti-attenuation performance in the later stage.

Claims

1. An organosilicon defoaming composition, characterized in that It is composed of the following substances: A. Hydrogen-terminated polysiloxane At least one of the general structural formulas is as follows: R 0 2HSiO ( Me 2SiO) a SiHR 0 2 In the formula, the substituent R 0 are the same or different, and are hydrocarbon groups with 1 to 12 carbon atoms, selected from alkyl, cycloalkyl, and aryl, wherein the alkyl group is selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, and n-dodecyl; the cycloalkyl group is selected from cyclopentyl and cyclohexylethyl; the aryl group is selected from phenyl, benzyl, phenethyl, and 2-phenylpropyl; the subscript a is an integer of 10 to 200; its usage is 20-40% of the total mass of the defoaming composition; B. Side-containing hydrogen polysiloxane At least one of the general structural formulas is as follows: Me 3SiO(R 1 HSiO) b (R 1 2SiO) c Si Me 3 In the formula, the substituent R 1 are the same or different and are hydrocarbon groups with 1 to 18 carbon atoms, selected from alkyl, cycloalkyl, and aryl groups, wherein the alkyl group is selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-dodecyl, and n-octadecyl; the cycloalkyl group is selected from cyclopentyl and cyclohexylethyl; the aryl group is selected from phenyl, benzyl, phenethyl, and 2-phenylpropyl; the subscript b is an integer between 10 and 100; subscript c is an integer of 10 to 400; its amount is 20-40% of the total mass of the defoaming composition; C. α-olefins The α-olefin is any one or more mixtures of linear α-olefins, α-aromatic olefins or branched α-olefins, including α-octene, α-decene, α-dodecene, α-tetradecene, α-hexadecene, α-octadecene, α-eicosene, a C20-C24 linear α-olefin mixture, a C24-C28 linear α-olefin mixture, α-triacontene, α-methylstyrene, and α-styrene, which can be used alone or mixed in any proportion; the α-olefin is added in two parts, the first part is used in an amount of 1-5% of the total mass of the defoaming composition, and the second part is used in an amount of 10-30% of the total mass of the defoaming composition; D. Solid silicone powder The solid organosilicon powder is formed by reacting a high hydrogen-containing polyorganosiloxane D1 and a high vinyl content vinyl polysiloxane D2 under the action of a platinum catalyst D3, and finally ground to obtain a solid organosilicon powder, the amount of which is 10-20% of the total mass of the defoaming composition; the hydrogen content of the high hydrogen-containing polyorganosiloxane is ≥0.1%; the molecular weight of the high vinyl content vinyl polysiloxane D2 is <10000; E. Catalyst 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 3-20 ppm (in terms of platinum) of the total mass of the terminal hydrogen-containing polyorganosiloxane A, the side hydrogen-containing polyorganosiloxane B, the α-olefin C and the solid organosilicon powder D, and is used in three parts; F. MQ Silicone Resin The MQ silicone resin is composed of chain segments (CH3)3SiO l / 2 (M unit) and chain SiO 4 / 2 The MQ resin composed of (Q units) has a molar ratio of (0.4-1.2):1.0, and the amount used is 2-8% of the total mass of the defoaming composition.

2. The organosilicon defoaming composition according to claim 1, characterized in that: The hydrogen-terminated polyorganosiloxane R 0 It is methyl.

3. The organosilicon defoaming composition according to claim 1, characterized in that: The side hydrogen-containing polyorganosiloxane is selected from R 1 It is methyl.

4. The organosilicon defoaming composition according to claim 1, characterized in that: The general structural formula of the high hydrogen-containing polyorganosiloxane D1 in the solid organosilicon powder is as follows: H c R 3 3-c SiO(SiR 3 HO) d (SiR 3 2O) b SiR 3 3-c H c R 3 are alkyl groups having 1 to 5 carbon atoms, which are the same or different; subscript c is 0, 1 or 2, subscript d is an integer of 100 to 300; subscript b is an integer of 50 to 1600; and the amount used accounts for 10 to 30% of the total mass of the solid organosilicon powder.

5. The organosilicon defoaming composition according to claim 1, characterized in that: The general structural formula of the high vinyl content vinyl polysiloxane D2 in the solid organosilicon powder is as follows: Vi e R 4 3-e SiO(SiR 4 ViO) f (SiR 4 2O) g SiR 4 3-e Vi e R 4 The value range is similar to R 3 The same; Vi is vinyl, subscript e is 0 or 1, subscript f is 30-80; subscript g is 20-80; the amount is 70-90% of the total mass of the solid organosilicon powder.

6. The organosilicon defoaming composition according to claim 1, characterized in that: The platinum catalyst D3 in the solid organosilicon powder is selected from platinum-alcohol complexes, platinum-olefin complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-ketone complexes, chloroplatinic acid isopropanol solution, and platinum-vinyl complexes; the amount used accounts for 0.01%-0.05% of the total mass of the high hydrogen-containing polysiloxane and the high vinyl content vinyl polysiloxane.

7. The organosilicon defoaming composition according to any one of claims 1 to 6, wherein the preparation method thereof is as follows: (1) Adding terminal hydrogen-containing polyorganosiloxane A and the first part of α-olefin into a reaction vessel, adding a catalyst when the temperature rises to 50-80° C., and keeping the temperature for 0.5-1.5 hours to obtain terminal alkyl hydrogen-containing polyorganosiloxane X; (2) Add the side hydrogen-containing polyorganosiloxane B and the second part of α-olefin into another reaction container, add the catalyst when the temperature rises to 50-80°C, raise the temperature to 120-200°C, and keep the temperature for 0.5-1.5h to obtain the side alkyl hydrogen-containing polyorganosiloxane Y; (3) Add the catalyst to the solid organosilicon powder D, the side alkyl hydrogen-containing polyorganosiloxane Y, and the terminal alkyl hydrogen-containing polyorganosiloxane X at a temperature of 50-80°C, raise the temperature to 110-180°C, and keep the temperature for 0.5-1.5 hours; (4) Add MQ silicone resin to the mixture in (3), keep the mixture at 100-160°C for 1-5 hours, and cool it to room temperature to obtain an organosilicon defoaming composition.

Images