Preparation and application of organic silicon composition

Abstract

The organic silicon composition provided by the invention can be prepared into organic silicon emulsion to be used in a papermaking pulping system, and has the characteristics of high defoaming speed, long foam inhibition time and good dispersity. The preparation method comprises the following steps: reacting polysiloxane with fluorine-containing hydrogen polysiloxane and vinyl polysiloxane, mixing with reactants obtained by reacting with organic silicon resin and polyether, and adding silicon dioxide to obtain the organic silicon composition. The large-molecular-weight fluorine-hydrogen-containing polysiloxane is grafted with vinyl silicone oil, so that the defoaming performance of the composition can be improved, and the low-viscosity vinyl silicone oil can enable the structure of a reactant to be tighter, so that the foam inhibition performance of the composition is improved; due to the characteristic that the end of the fluorine-containing hydrogen silicone oil contains hydrogen, the fluorine-containing hydrogen silicone oil is more applicable to water-based and oil-based systems, is easier to disperse and is not easy to separate out floating oil.

Description

Technical Field

[0001] The invention relates to an organosilicon composition which can be used for organosilicon emulsion, and belongs to the technical field of fine chemical preparations. Background Art

[0002] Foam is a common phenomenon in life and work. However, in industrial production, foam can sometimes bring great harm, such as reducing the working efficiency of the machine, delaying working time, affecting the quality of the product, etc. There are mainly physical and chemical methods to eliminate harmful foam, and defoaming agent defoaming is one of the chemical methods. With the substantial increase in the production scale and production efficiency of industrial enterprises, defoaming agent defoaming has been more widely used. At present, defoaming agents have been widely used in papermaking, textile printing and dyeing, oil extraction and refining, coatings, emulsion polymerization, sewage treatment, metal cleaning and other industries, and defoaming agents have become an indispensable functional additive in the production process.

[0003] The defoaming composition is the core of the silicone defoamer. Its defoaming speed and antifoaming performance directly affect the performance of the final product. The most primitive polysiloxane defoamer active substance is obtained by treating polydimethylsiloxane and silicon dioxide with a specific processing technology, such as the defoamer composition introduced in US3383327. However, since it cannot suppress foam for a long time, that is, the antifoaming performance is poor, researchers at home and abroad have conducted large-scale research on its performance. US4338217A1 uses alkoxy polysiloxane to replace ordinary polysiloxane and mixes it with silica particles to prepare a defoaming composition; US5824739 introduces amino polysiloxane or carboxyl polysiloxane as the main body of the defoaming composition, and mixes it with silica to obtain a defoaming composition; EP163541B1 introduces the use of polysiloxane containing terminal hydroxyl groups to react with polysiloxane containing other active functional groups under the action of a catalyst to form a branched polysiloxane, and uses this to replace ordinary polysiloxane and hydrophilic silica for mixing. The obtained defoaming agent has a very high viscosity and is difficult to emulsify and disperse in water.

[0004] CN1931417A discloses a high temperature and strong alkali resistant defoamer composition, which is obtained by crosslinking polysiloxane and silicone resin, and the performance is tested after the active substance is prepared into an emulsion. It has good antifoaming performance, but the defoaming speed needs to be further improved. Moreover, due to the large viscosity of the defoaming composition, it is quite difficult to disperse it in water. CN103275483B discloses a high temperature and strong alkali resistant defoamer composition, which is obtained by crosslinking polysiloxane and silicone resin and reacting hydroxy polysiloxane. The performance is tested after the active substance is prepared into an emulsion. It has good antifoaming performance, but the long-term persistence test defoaming performance needs to be further improved. CN103275493A discloses a silicone composition obtained by reacting hydrogen-containing polyorganosiloxane and silicone resin, adding hydroxy polyorganosiloxane, and mixing with hydrophobic particles. Its antifoaming performance and dispersibility need to be improved.

[0005] The defoamer compositions in the above patents all have the problems of poor defoaming and suppressing performance, difficulty in emulsification, and difficulty in dispersion. Summary of the invention

[0006] The present invention obtains an organosilicon composition by reacting polyorganosiloxane with fluorine hydrogen polyorganosiloxane and vinyl polyorganosiloxane, and then mixing the reactants with organosilicon resin and polyether, and then adding silicon dioxide. The high molecular weight fluorine hydrogen polyorganosiloxane grafted with vinyl silicone oil can improve the defoaming performance of the composition, and the low viscosity vinyl silicone oil can make the reactant structure more compact, thereby improving the anti-foaming performance of the composition; due to the terminal hydrogen-containing characteristic of fluorine hydrogen silicone oil, it is more suitable in aqueous and oily systems, easier to disperse, and not easy to precipitate floating oil. The organosilicon emulsion prepared by the organosilicon composition of the present invention can be used in papermaking and pulping systems, and has the characteristics of fast defoaming speed, long anti-foaming time, and good dispersibility.

[0007] The organosilicon composition described in the present invention is composed of the following substances:

[0008] A. Polyorganosiloxane

[0009] The general structural formula of polyorganosiloxane is as follows:

[0010] R a SiO (4-a) / 2

[0011] The value of a is 1.9 to 2.2, and R in the molecular structure is the same or different, and includes hydrogen atoms, monovalent substituted or unsubstituted branched or linear alkyl groups with 1 to 20 carbon atoms, specifically including methyl, ethyl, propyl, n-propyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl. From the perspective of the availability of raw materials, it is preferred that more than 80% of the substituents R are methyl. The dynamic viscosity of the polyorganosiloxane at 25°C is 1,000 to 300,000 mPa·s. The polyorganosiloxane used in the present invention is trimethylsiloxy-terminated polydimethylsiloxane. The amount of the polyorganosiloxane used accounts for 40 to 70% of the total mass of the silicone composition;

[0012] B. Fluorohydrogen-containing polysiloxane

[0013] The fluorine-containing hydrogen polyorganosiloxane of the present invention refers to a polyorganosiloxane containing at least three silicon-bonded hydrogen groups:

[0014]

[0015] Where Me is methyl, R 1 The same or different, selected from H and F atoms. The subscript m is an integer of 5 to 350, preferably an integer of 35 to 200; the subscript n is an integer of 15 to 30. The kinematic viscosity of the fluorine hydrogen polysiloxane at 25°C is between 10 and 30,000 mPa.s, preferably between 40 and 5000 mPa.s. The amount of the fluorine hydrogen polysiloxane is 0.01 to 30%, preferably 5 to 19%, of the total mass of the silicone composition.

[0016] C. Vinyl polysiloxane

[0017] The vinyl polyorganosiloxane described in the present invention refers to a polysiloxane containing at least two silicon-bonded vinyl groups, and has the following general structural formula:

[0018]

[0019] Where Me is methyl, R 2 is vinyl or methyl, and R 2 At least one is a vinyl group. The subscript p is an integer of 10 to 2000, preferably an integer of 50 to 1000; the subscript q is an integer of 2 to 500, preferably an integer of 40 to 300. The kinematic viscosity of the vinyl polyorganosiloxane at 25°C ranges from 1000 to 200,000 mPa.s, preferably from 3,000 to 100,000 mPa.s. The amount of the vinyl polyorganosiloxane is 5% to 40% of the total mass of the silicone composition, preferably 10% to 30%.

[0020] D. Silicon dioxide

[0021] The silicon dioxide described in the present invention is hydrophobic silicon dioxide, specifically selected from gas phase hydrophobic silicon dioxide and precipitated hydrophobic silicon dioxide, and its specific surface area is 50 to 500 m 2 / g. The amount of silicon dioxide accounts for 2% to 15% of the total mass of the organosilicon composition, preferably 4% to 8%.

[0022] E. Silicone resin

[0023] The organic silicon resin of the present invention is generally a non-linear siloxane resin having a formula R 3 m SiO 4-m / 2 Siloxane units, where R 3 represents a hydroxyl group, a hydrocarbon group or a hydrocarbonoxy group, and the average value of the subscript m is 0.5 to 2.4; specifically selected from a monovalent trihydrocarbylsiloxane (M) group R 4 3SiO 1 / 2 and tetrafunctional (Q) groups SiO 4 / 2 MQ resin composed of units, where R 4 It represents a monovalent hydrocarbon group, the molar ratio of M group to Q group is (0.5-0.8):1.0, and contains up to 10% by weight of free Si-bonded hydroxyl groups. The amount of the silicone resin is 1% to 15% of the total mass of the silicone composition, preferably 4% to 8%.

[0024] F. Polyether

[0025] At least one polyether having the general structural formula:

[0026] R 5 (EO) d (PO) e

[0027] In the molecular structure: R 5 The initiator of the polyether may be the same or different, and is an alcohol having 2 to 30 carbon atoms, including ethylene glycol, propylene glycol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, carbon dodecanol, carbon tetradecanol, carbon hexadecanol, carbon octadecanol, carbon eicosanol, carbon twentieth-one alcohol, carbon tetracosanol, and carbon hexacosanol. Wherein d and e are the degree of polymerization, d is an integer of 1 to 60, and e is an integer of 0 to 50. The amount of the polyether is 1 to 3% of the total mass of the organosilicon composition.

[0028] G. Catalyst-1

[0029] Catalyst-1 is a precious metal catalyst selected from platinum-alcohol complex, platinum-olefin complex, platinum-ether complex, platinum-ketone complex, 1% chloroplatinic acid isopropanol solution, rhodium-alcohol complex, rhodium-alkoxide complex, preferably 1% chloroplatinic acid isopropanol solution. Catalyst The dosage is 0.0001% to 0.001% of the total mass of the organosilicon composition, preferably 0.0005% to 0.001%.

[0030] H. Catalyst-2

[0031] Catalyst-2 is selected from potassium hydroxide-isopropanol solution, potassium hydroxide-methanol solution, potassium hydroxide-ethanol solution, potassium hydroxide-methylpolysiloxane mixture, preferably potassium hydroxide-isopropanol solution. The dosage is 0.1% to 5% of the total mass of the organosilicon composition, preferably 1% to 3%.

[0032] The preparation method of the organosilicon composition of the present invention is as follows:

[0033] (1) Adding silicone resin and polyether into a reaction vessel, adding catalyst-2 at 50-90°C, controlling the reaction temperature at 60-130°C, reacting for 3-8h, and obtaining reactant I;

[0034] (2) adding polyorganosiloxane, fluorine hydrogen polyorganosiloxane and vinyl polyorganosiloxane into a reaction vessel, adding catalyst-1 at 40-70° C., reacting at 40-90° C. for 3-8 hours, and obtaining reactant II;

[0035] (3) Add reactant I to reactant II, mix well, add silicon dioxide to the mixture of reactant I and reactant II, disperse at high speed at 90-150° C. for 3 h, and finally homogenize by a high-pressure homogenizer at 40-60 MPa to obtain an organosilicon composition. DETAILED DESCRIPTION

[0036] Example 1

[0037] (1) Add 10 parts of silicone resin (M:Q=0.65:1) and 1 part of polyether (the initiator is hexadecanol, d is 20, e is 30) into a reaction vessel, add 3 parts of potassium hydroxide-methanol solution at 60°C, control the reaction temperature at 70°C, and react for 8 hours to obtain reactant Ⅰ-1;

[0038] (2) 55 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 1,000 mPa·s and 19 parts of a polydimethylsiloxane with a viscosity of 12,000 mPa·s and a structural formula of H(Me)2SiO(MeFSiO) 135 [(Me)2SiO]15 Si(Me)2H containing fluorine hydrogen polysiloxane and 10 parts of a viscosity of 1000 mPa.s (unless otherwise specified, the viscosity described below is the kinematic viscosity value at 25°C), a structural formula of (Me)3SiO(MeViSiO) 10 [(Me)2SiO]4Si(Me)3 (Vi mentioned in the text is the abbreviation of vinyl functional group) vinyl polysiloxane is added to the reaction container, 0.0001 parts of platinum-alcohol complex is added at 60°C, and the reaction is carried out at 70°C for 8 hours to obtain reactant II-1;

[0039] (3) Add reactant I-1 to reactant II-1, mix well, and add 1.9999 parts of a 2 / g of fumed hydrophobic silica was added to the mixture of reactants Ⅰ-1 and Ⅱ-1, dispersed at high speed at 120°C for 3 hours, and finally homogenized by a high-pressure homogenizer at 40 MPa to obtain an organosilicon composition.

[0040] Example 2

[0041] (1) Add 15 parts of silicone resin (M:Q=0.5:1) and 3 parts of polyether (the initiator is octadecyl alcohol, d is 3, e is 0) into a reaction vessel, add 2 parts of potassium hydroxide-ethanol solution at 55°C, control the reaction temperature at 85°C, and react for 7 hours to obtain reactant Ⅰ-2;

[0042] (2) 60 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 10,000 mPa·s and 0.01 parts of a polysiloxane with a viscosity of 30,000 mPa·s and a structural formula of H(Me)2SiO(MeFSiO) 350 [(Me)2SiO] 30 Si(Me)2H containing fluorine hydrogen polysiloxane and 5 parts of a viscosity of 200000 mPa.s and a structural formula of Vi(Me)2SiO[(Me)2SiO] 2500 Si(Me)3 vinyl polyorganosiloxane was added to the reaction vessel, 0.0008 parts of rhodium-alkoxide complex was added at 55°C, and the reaction was carried out at 80°C for 3h to obtain reactant II-2;

[0043] (3) Add reactant I-2 to reactant II-2, mix well, and add 14.9892 parts of a specific surface area of ​​100 m 2 / g of fumed hydrophobic silica was added to the mixture of reactants Ⅰ-2 and Ⅱ-2, dispersed at high speed at 140°C for 3 hours, and finally homogenized by a high-pressure homogenizer at 50 MPa to obtain an organosilicon composition.

[0044] Example 3

[0045] (1) 8 parts of silicone resin (M:Q=0.8:1) and 2 parts of polyether (the initiator is ethylene glycol, d is 40, e is 50) are added to a reaction vessel, and 5 parts of potassium hydroxide-methyl polysiloxane mixture are added at 90°C. The reaction temperature is controlled at 120°C and the reaction is carried out for 4 hours to obtain reactant Ⅰ-3;

[0046] (2) 43.9998 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 200,000 mPa·s and 15 parts of a polydimethylsiloxane with a viscosity of 8000 mPa·s and a structural formula of H(Me)2SiO(MeFSiO) 80 [(Me)2SiO] 20 Si(Me)2H containing fluorine hydrogen polysiloxane and 22 parts of a viscosity of 50000 mPa.s and a structural formula of (Me)3SiO[(Me)2SiO] 675 Si(Me)2Vi vinyl polyorganosiloxane was added to the reaction vessel, and 0.0002 parts of 1% chloroplatinic acid isopropanol solution was added at 70°C, and the reaction was carried out at 90°C for 4 hours to obtain reactant II-3;

[0047] (3) Add reactant I-3 to reactant II-3, mix well, and add 4 portions of a specific surface area of ​​250m 2 / g of fumed hydrophobic silica was added to the mixture of reactants I-3 and II-3, dispersed at high speed at 130°C for 3 hours, and finally homogenized by a high-pressure homogenizer at 60 MPa to obtain an organosilicon composition.

[0048] Example 4

[0049] (1) 13 parts of silicone resin (M:Q=0.7:1) and 2 parts of polyether (the initiator is amyl alcohol, d is 40, e is 20) are added to a reaction vessel, and 2.6 parts of potassium hydroxide-isopropanol solution are added at 80°C. The reaction temperature is controlled at 130°C and the reaction is carried out for 3 hours to obtain reactant Ⅰ-4;

[0050] (2) 40 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 300,000 mPa·s and 5 parts of polydimethylsiloxane with a viscosity of 10000 mPa·s and a structural formula of H(Me)2SiO(MeFSiO) 105 [(Me)2SiO] 15 Si(Me)2H containing fluorine hydrogen polysiloxane and 30 parts of a viscosity of 3000 mPa.s and a structural formula of (Me)3SiO(MeViSiO) 15 [(Me)2SiO] 26Si(Me)3 vinyl polyorganosiloxane was added to the reaction vessel, 0.0005 parts of platinum-olefin complex was added at 40°C, and the reaction was carried out at 40°C for 5 hours to obtain reactant II-4;

[0051] (3) Add reactant I-4 to reactant II-4, mix well, and add 7.3995 parts of a specific surface area of ​​500 m 2 / g of fumed hydrophobic silica was added to the mixture of reactants I-4 and II-4, dispersed at high speed at 110°C for 3 hours, and finally homogenized by a high-pressure homogenizer at 45 MPa to obtain an organosilicon composition.

[0052] Example 5

[0053] (1) Add 1 part of silicone resin (M:Q=0.55:1) and 2 parts of polyether (the initiator is octanol, d is 30, e is 25) into a reaction vessel, add 4 parts of potassium hydroxide-methyl polysiloxane mixture at 85°C, control the reaction temperature at 120°C, and react for 5 hours to obtain reactant Ⅰ-5;

[0054] (2) 40 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 80,000 mPa·s and 12 parts of a polydimethylsiloxane with a viscosity of 15000 mPa·s and a structural formula of H(Me)2SiO(MeFSiO) 195 [(Me)2SiO] 25 Si(Me)2H containing fluorine hydrogen polysiloxane and 38.999 parts of a viscosity of 50000 mPa.s and a structural formula of Vi(Me)2SiO[(Me)2SiO] 675 Si(Me)2Vi vinyl polyorganosiloxane was added to the reaction vessel, 0.0001 parts of platinum-olefin complex was added at 45°C, and the reaction was carried out at 60°C for 6 hours to obtain reactant II-5;

[0055] (3) Add reactant I-5 to reactant II-5, mix well, and mix two portions with a specific surface area of ​​250m 2 / g of precipitated hydrophobic silica was added to the mixture of reactants I-5 and II-5, dispersed at high speed at 90°C for 3 hours, and finally homogenized by a high-pressure homogenizer at 55 MPa to obtain an organosilicon composition.

[0056] Example 6

[0057] (1) Add 3 parts of silicone resin (M:Q=0.75:1) and 3 parts of polyether (the initiator is carbon tetracosyl alcohol, d is 35, e is 50) into a reaction vessel, add 1 part of potassium hydroxide-isopropanol solution at 70°C, control the reaction temperature at 90°C, and react for 7 hours to obtain reactant Ⅰ-6;

[0058] (2) 52.9895 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 60,000 mPa·s and 0.01 parts of a polysiloxane with a viscosity of 1500 mPa·s and a structural formula of H(Me)2SiO(MeFSiO)5[(Me)2SiO] 15 Si(Me)2H containing fluorine hydrogen polysiloxane and 30 parts of a viscosity of 100000 mPa.s and a structural formula of Vi(Me)2SiO(MeViSiO) 62 [(Me)2SiO] 73 Si(Me)2Vi vinyl polyorganosiloxane was added to the reaction vessel, and 0.0005 parts of 1% chloroplatinic acid isopropanol solution was added at 70°C, and the reaction was carried out at 65°C for 7h to obtain reactant II-6;

[0059] (3) Add reactant I-6 to reactant II-6, mix well, and add 10 parts of a specific surface area of ​​300m 2 / g of fumed hydrophobic silica was added to the mixture of reactants I-6 and II-6, dispersed at high speed at 100°C for 3 hours, and finally homogenized by a high-pressure homogenizer at 50 MPa to obtain a silicone composition.

[0060] Example 7

[0061] (1) Add 4 parts of silicone resin (M:Q=0.5:1) and 2 parts of polyether (the initiator is carbonyl alcohol, d is 20, e is 10) into a reaction vessel, add 0.5 parts of potassium hydroxide-isopropanol solution at 65°C, control the reaction temperature at 100°C, and react for 3 hours to obtain reactant Ⅰ-7;

[0062] (2) 45 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 150,000 mPa·s and 16 parts of a polydimethylsiloxane with a viscosity of 2000 mPa·s and a structural formula of H(Me)2SiO(MeFSiO) 10 [(Me)2SiO] 15 Si(Me)2H containing fluorine hydrogen polysiloxane and 24.499 parts of a viscosity of 5000 mPa.s and a structural formula of Vi(Me)2SiO[(Me)2SiO] 66 Si(Me)2Vi vinyl polyorganosiloxane was added to the reaction vessel, and 0.0001 parts of 1% chloroplatinic acid isopropanol solution was added at 65°C, and the reaction was carried out at 50°C for 4 hours to obtain reactant II-7;

[0063] (3) Add reactant I-7 to reactant II-7, mix well, and add 8 portions of reactant I-7 with a specific surface area of ​​50 m 2 / g of precipitated hydrophobic silica was added to the mixture of reactants I-7 and II-7, dispersed at high speed at 120°C for 3 hours, and finally homogenized by a high-pressure homogenizer at 60 MPa to obtain a silicone composition.

[0064] Example 8

[0065] (1) Add 1 part of silicone resin (M:Q=0.8:1) and 1 part of polyether (the initiator is hexadecyl alcohol, d is 40, e is 10) into a reaction vessel, add 0.1 part of potassium hydroxide-methanol solution at 70°C, control the reaction temperature at 110°C, and react for 5 hours to obtain reactant Ⅰ-8;

[0066] (2) 41.899 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 5,000 mPa·s and 30 parts of a polydimethylsiloxane with a viscosity of 20,000 mPa·s and a structural formula of H(Me)2SiO(MeFSiO) 230 [(Me)2SiO] 20 Si(Me)2H containing fluorine hydrogen polysiloxane and 20 parts of a viscosity of 3000 mPa.s and a structural formula of (Me)3SiO(MeViSiO) 30 [(Me)2SiO] 11 Si(Me)2Vi vinyl polyorganosiloxane was added to the reaction vessel, 0.001 parts of platinum-ether complex was added at 70°C, and the reaction was carried out at 75°C for 8 hours to obtain reactant II-8;

[0067] (3) Add reactant I-8 to reactant II-8, mix well, and add 6 portions of reactant I-8 with a specific surface area of ​​500 m 2 / g of precipitated hydrophobic silica was added to the mixture of reactants I-8 and II-8, dispersed at high speed at 140°C for 3 hours, and finally homogenized by a high-pressure homogenizer at 50 MPa to obtain an organosilicon composition.

[0068] Comparative Example 1

[0069] (1) Add 1 part of silicone resin (M:Q=0.55:1) and 2 parts of polyether (the initiator is octanol, d is 30, e is 25) into a reaction vessel, add 4 parts of potassium hydroxide-methyl polysiloxane mixture at 85°C, control the reaction temperature at 120°C, and react for 5 hours to obtain reactant Ⅰ-9;

[0070] (2) 40 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 500 mPa·s and 12 parts of a polysiloxane with a viscosity of 15000 mPa·s and a structural formula of H(Me)2SiO(MeFSiO) 195 [(Me)2SiO] 25Si(Me)2H containing fluorine hydrogen polysiloxane and 38.999 parts of a viscosity of 50000 mPa.s and a structural formula of Vi(Me)2SiO[(Me)2SiO] 675 Si(Me)2Vi vinyl polyorganosiloxane was added to the reaction vessel, 0.0001 parts of platinum-olefin complex was added at 45°C, and the reaction was carried out at 60°C for 6 hours to obtain reactant II-9;

[0071] (3) Add reactant I-9 to reactant II-9, mix well, and mix two portions with a specific surface area of ​​250m 2 / g of precipitated hydrophobic silica was added to the mixture of reactants I-9 and II-9, dispersed at high speed at 90°C for 3 hours, and finally homogenized by a high-pressure homogenizer at 55 MPa to obtain an organosilicon composition.

[0072] Comparative Example 2

[0073] (1) Add 3 parts of silicone resin (M:Q=0.75:1) and 3 parts of polyether (the initiator is tetracosyl alcohol, d is 35, e is 50) into a reaction vessel, add 1 part of potassium hydroxide-isopropanol solution at 70°C, control the reaction temperature at 90°C, and react for 7 hours to obtain reactant Ⅰ-10;

[0074] (2) 52.9895 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 60,000 mPa·s and 0.01 parts of a polysiloxane with a viscosity of 1500 mPa·s and a structural formula of H(Me)2SiO(MeFSiO)5[(Me)2SiO] 15 Si(Me)2H containing fluorine hydrogen polysiloxane and 30 parts of a viscosity of 300000 mPa.s and a structural formula of Vi(Me)2SiO(MeViSiO) 62 [(Me)2SiO] 73 Si(Me)2Vi vinyl polyorganosiloxane was added to the reaction vessel, and 0.0005 parts of 1% chloroplatinic acid isopropanol solution was added at 70°C, and the reaction was carried out at 65°C for 7h to obtain reactant II-10;

[0075] (3) Add reactant I-10 to reactant II-10, mix well, and add 10 parts of a specific surface area of ​​300m 2 / g of fumed hydrophobic silica was added to the mixture of reactants I-10 and II-10, dispersed at high speed at 100°C for 3 hours, and finally homogenized by a high-pressure homogenizer at 50 MPa to obtain an organosilicon composition.

[0076] Comparative Example 3

[0077] (1) 4 parts of silicone resin (M:Q=0.5:1) and 2 parts of polyether (the initiator is carbonyl alcohol, d is 20, e is 10) are added to a reaction vessel, and 0.5 parts of potassium hydroxide-isopropanol solution are added at 65°C. The reaction temperature is controlled at 100°C and the reaction is carried out for 2 hours to obtain reactant Ⅰ-11;

[0078] (2) 45 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 150,000 mPa·s and 16 parts of a polydimethylsiloxane with a viscosity of 2000 mPa·s and a structural formula of H(Me)2SiO(MeFSiO) 10 [(Me)2SiO] 15 Si(Me)2H containing fluorine hydrogen polysiloxane and 24.499 parts of a viscosity of 5000 mPa.s and a structural formula of Vi(Me)2SiO[(Me)2SiO] 66 Si(Me)2Vi vinyl polyorganosiloxane was added to the reaction vessel, and 0.0001 parts of 1% chloroplatinic acid isopropanol solution was added at 65°C, and the reaction was carried out at 50°C for 4 hours to obtain reactant II-11;

[0079] (3) Add reactant I-11 to reactant II-11, mix well, and add 8 parts of reactant I-11 with a specific surface area of ​​50 m 2 / g of precipitated hydrophobic silica was added to the mixture of reactants Ⅰ-11 and Ⅱ-11, dispersed at high speed at 120°C for 3 hours, and finally homogenized by a high-pressure homogenizer at 60 MPa to obtain an organosilicon composition.

[0080] Comparative Example 4

[0081] (1) Add 1 part of silicone resin (M:Q=0.8:1) and 1 part of polyether (the initiator is hexadecyl alcohol, d is 40, e is 10) into a reaction vessel, add 0.1 part of potassium hydroxide-methanol solution at 70°C, control the reaction temperature at 110°C, and react for 5 hours to obtain reactant Ⅰ-12;

[0082] (2) 41.899 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 5,000 mPa·s and 30 parts of a polydimethylsiloxane with a viscosity of 20,000 mPa·s and a structural formula of H(Me)2SiO(MeFSiO) 230 [(Me)2SiO] 20 Si(Me)2H containing fluorine hydrogen polysiloxane and 20 parts of a viscosity of 3000 mPa.s and a structural formula of (Me)3SiO(MeViSiO) 30 [(Me)2SiO] 11Si(Me)2Vi vinyl polyorganosiloxane was added to the reaction vessel, 0.001 parts of platinum-ether complex was added at 70°C, and the reaction was carried out at 75°C for 9 hours to obtain reactant II-12;

[0083] (3) Add reactant I-12 to reactant II-12, mix well, and add 6 portions of reactant I-12 with a specific surface area of ​​500 m 2 / g of precipitated hydrophobic silica was added to the mixture of reactants I-8 and II-8, dispersed at high speed at 140°C for 3 hours, and finally homogenized by a high-pressure homogenizer at 50 MPa to obtain an organosilicon composition.

[0084] Comparative Example 5

[0085] (1) Add 15 parts of silicone resin (M:Q=0.5:1) and 3 parts of polyether (the initiator is octadecyl alcohol, d is 3, e is 0) into a reaction vessel, add 2 parts of potassium hydroxide-ethanol solution at 55°C, control the reaction temperature at 85°C, and react for 7 hours to obtain reactant Ⅰ-13;

[0086] (2) 60 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 10,000 mPa·s and 0.01 parts of H(Me)2SiO(MeHSiO) with a viscosity of 30,000 mPa·s were added. 350 [(Me)2SiO] 30 Si(Me)2H containing fluorine hydrogen polysiloxane and 5 parts of a viscosity of 200000 mPa.s and a structural formula of Vi(Me)2SiO[(Me)2SiO] 2500 Si(Me)3 vinyl polyorganosiloxane was added to the reaction vessel, 0.0008 parts of rhodium-alkoxide complex was added at 55°C, and the reaction was carried out at 80°C for 3h to obtain reactant II-13;

[0087] (3) Add reactant I-13 to reactant II-13, mix well, and add 14.9892 parts of a specific surface area of ​​100 m 2 / g of fumed hydrophobic silica was added to the mixture of reactants Ⅰ-13 and Ⅱ-13, dispersed at high speed at 140°C for 3 hours, and finally homogenized by a high-pressure homogenizer at 50 MPa to obtain a silicone composition.

[0088] Comparative Example 6

[0089] (1) 55 parts of trimethylsiloxy-terminated polydimethylsiloxane with a viscosity of 1,000 mPa·s and 19 parts of a polydimethylsiloxane with a viscosity of 12,000 mPa·s and a structural formula of H(Me)2SiO(MeFSiO) 135 [(Me)2SiO] 15Si(Me)2H containing fluorine hydrogen polysiloxane and 10 parts of a viscosity of 1000 mPa.s (unless otherwise specified, the viscosity described below is the kinematic viscosity value at 25°C), a structural formula of (Me)3SiO(MeViSiO) 10 [(Me)2SiO]4Si(Me)3 (Vi mentioned in the text is the abbreviation of vinyl functional group) vinyl polysiloxane is added to the reaction container, 0.0001 parts of platinum-alcohol complex is added at 60°C, and the reaction is carried out at 70°C for 8 hours to obtain reactant II-14;

[0090] (2) Add 10 parts of silicone resin (M:Q=0.65:1) and 1 part of polyether (the initiator is hexadecanol, d is 20, e is 30), 3 parts of potassium hydroxide-methanol solution, and 1.9999 parts of gas-phase hydrophobic silica with a specific surface area of ​​50m2 / g to reactant II-14, control the temperature at 120°C and disperse at high speed for 3 hours, and finally homogenize by a high-pressure homogenizer at 40MPa to obtain a silicone composition.

[0091] Performance testing of silicone compositions

[0092] The above-mentioned embodiments and comparative examples were prepared into silicone emulsions according to the prior art to carry out performance testing. The specific implementation method is: the silicone composition and the emulsifier are mixed, and water and a thickener are gradually added. After mixing evenly, mechanical equipment such as a colloid grinder and a homogenizer are used to prepare an oil-in-water silicone emulsion.

[0093] Emulsifiers include nonionic surfactants and anionic surfactants.

[0094] The nonionic surfactant is selected from one or more of nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, lauric acid polyoxyethylene ether, oleic acid polyoxyethylene ether, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, sorbitan trioleate, sorbitan monostearate polyoxyethylene ether ester, sorbitan monooleate polyoxyethylene ether ester, sorbitan tristearate polyoxyethylene ether ester, and castor oil polyoxyethylene ether.

[0095] The anionic surfactant is selected from one or more of sodium dodecyl polyoxyethylene ether sulfate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, sodium hexadecyl sulfonate, sodium hexadecylbenzene sulfonate, and sodium dodecyl diphenyl ether disulfonate.

[0096] The thickener is selected from one or more of xanthan gum, guar gum, polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, polyacrylamide and polyacrylate.

[0097] 1. Test method for foam removal and suppression performance of papermaking black liquor system

[0098] Add 600mL of papermaking pulping black liquor to a circulating bubbler with a glass tube with a scale of 0-500mL and an inner diameter of 5cm, so that the liquid level reaches the lowest scale "0mL", then set the temperature to 80℃, the flow rate to 6L / min, and the voltage to 220V, then turn on the temperature control switch, heat the papermaking pulping black liquor to the set temperature, turn on the circulation pump, start impact bubbling, wait for the foam to rise to 500mL, add 0.15ml of silicone emulsion, and record the change of foam height over time. The shorter the time for the foam to reach the lowest scale and the lower the scale reached, the better the instantaneous defoaming performance of the silicone emulsion; the longer the time it takes for the foam to reach 500mL again, the better the anti-foaming performance of the silicone emulsion.

[0099]

[0100] 2. Particle size test

[0101] Testing equipment: Laser particle size analyzer

[0102] Test method: dilute the silicone emulsion to an appropriate concentration, add the sample for test and analysis according to the particle size analyzer operating procedures, and retain the test results; D90 represents the equivalent diameter of the maximum particle size when the cumulative distribution is 90% in the particle size distribution curve, and D50 represents the equivalent diameter of the maximum particle size when the cumulative distribution is 50% in the particle size distribution curve; the smaller the D90 / D50 value, the more uniform the emulsification, the better its stability, and there is basically no oil floating or precipitation during use.

[0103] sample <![CDATA[D 90 / μm]]> <![CDATA[D 50 / μm]]> <![CDATA[D 90 / D 50 ]]> Example 1 13.13 6.41 2.05 Example 2 16.24 7.42 2.19 Example 3 15.02 6.81 2.21 Example 4 18.01 8.01 2.25 Example 5 14.14 6.67 2.12 Example 6 15.44 7.01 2.20 Example 7 14.02 6.1 2.30 Example 8 12.43 5.89 2.11 Comparative Example 1 56.01 21.1 2.65 Comparative Example 2 57.29 21.14 2.71 Comparative Example 3 58.14 22.09 2.63 Comparative Example 4 56.01 21.2 2.64 Comparative Example 5 57.01 21.2 2.69 Comparative Example 6 59.02 21.1 2.79

[0104] 3. Water dispersibility test

[0105] Add 0.5g of silicone emulsion into a beaker, then add 100g of water, shake, and observe its dispersion in water. If it disperses quickly and there is no oily matter on the liquid surface, the water dispersibility is excellent; if it disperses quickly and there is no oily matter on the liquid surface, the water dispersibility is good; if it disperses slowly and a small amount of floccules appear on the liquid surface, the water dispersibility is medium; if it is not easy to disperse and the floccules are difficult to disappear, the water dispersibility is poor.

[0106] sample Water dispersibility Example 1 excellent Example 2 excellent Example 3 excellent Example 4 excellent Example 5 excellent Example 6 excellent Example 7 excellent Example 8 excellent Comparative Example 1 Difference Comparative Example 2 middle Comparative Example 3 Difference Comparative Example 4 middle Comparative Example 5 middle Comparative Example 6 Difference

Claims

1. An organosilicon composition, characterized in that The organosilicon composition consists of the following components: A. Polyorganosiloxane: The amount accounts for 40-70% of the total mass of the organosilicon composition; B. Fluorine-hydrogen-containing polysiloxane: the amount is 0.01-30% of the total mass of the organosilicon composition; C. Vinyl polysiloxane: the amount is 5% to 40% of the total mass of the silicone composition; D. Silicon dioxide: The amount is 2% to 15% of the total mass of the organosilicon composition; E. Silicone resin: The amount is 1% to 15% of the total mass of the silicone composition; F. Polyether: The amount is 1-3% of the total mass of the silicone composition; G. Catalyst-1: The amount is 0.0001% to 0.001% of the total mass of the organosilicon composition; H. Catalyst-2: The dosage is 0.1% to 5% of the total mass of the organosilicon composition; The preparation method of the organosilicon composition is: (1) Adding silicone resin and polyether into a reaction vessel, adding catalyst-2 at 50-90°C, controlling the reaction temperature at 60-130°C, reacting for 3-8h, and obtaining reactant I; (2) adding polyorganosiloxane, fluorine hydrogen polyorganosiloxane and vinyl polyorganosiloxane into a reaction vessel, adding catalyst-1 at 40-70° C., reacting at 40-90° C. for 3-8 hours, and obtaining reactant II; (3) Add reactant I to reactant II, mix well, add silicon dioxide to the mixture of reactant I and reactant II, disperse at high speed at 90-150° C. for 3 h, and finally homogenize by a high-pressure homogenizer at 40-60 MPa to obtain an organosilicon composition.

2. The organosilicon composition according to claim 1, characterized in that: The general structural formula of the polyorganosiloxane is as follows: R a SiO (4-a) / 2 The value of a is 1.9 to 2.2, R in the molecular structure is the same or different, and includes hydrogen atoms, monovalent substituted or unsubstituted branched or linear alkyl groups with 1 to 20 carbon atoms, specifically including methyl, ethyl, propyl, n-propyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl groups; the dynamic viscosity of the polyorganosiloxane at 25° C. is 1,000 to 300,000 mPa·s.

3. The organosilicon composition according to claim 1, characterized in that: The fluorine-containing hydrogen polyorganosiloxane refers to a polyorganosiloxane containing at least three silicon-bonded hydrogen groups:

4. Where Me is methyl, R 1 The same or different atoms are selected from H and F atoms. The subscript m is an integer of 5 to 350; the subscript n is an integer of 15 to 30; the kinematic viscosity of the fluorine hydrogen-containing polyorganosiloxane at 25° C. is between 10 and 30,000 mPa.s.

5. The organosilicon composition according to claim 1, characterized in that: The vinyl polyorganosiloxane refers to a polysiloxane containing at least two silicon-bonded vinyl groups, and has the following general structural formula:

6. Where Me is methyl, R 2 is vinyl or methyl, and R 2 At least one is a vinyl group. The subscript p is an integer of 10 to 2000; the subscript q is an integer of 2 to 500. The kinematic viscosity of the vinyl polyorganosiloxane at 25° C. ranges from 1000 to 200,000 mPa.s.

7. The organosilicon composition according to claim 1, characterized in that: The silicon dioxide is hydrophobic silicon dioxide, specifically 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.

8. The organosilicon composition according to claim 1, characterized in that: The organic silicone resin is usually a non-linear siloxane resin, which is represented by the formula R 3 m SiO 4-m / 2 Siloxane units, where R 3 represents a hydroxyl group, a hydrocarbon group or a hydrocarbonoxy group, and the average value of the subscript m is 0.5 to 2.4; specifically selected from a monovalent trihydrocarbylsiloxane (M) group R 4 3SiO 1 / 2 and tetrafunctional (Q) groups SiO 4 / 2 MQ resin composed of units, where R 4 It represents a monovalent hydrocarbon group, the molar ratio of M group to Q group is (0.5-0.8):1.0, and contains up to 10% by weight of free Si-bonded hydroxyl groups.

9. The organosilicon composition according to claim 1, characterized in that: The polyether is at least one polyether having the following general structural formula: R 5 (IS) d (PO) e In the molecular structure: R 5 The initiator of the polyether may be the same or different and is an alcohol having 2 to 30 carbon atoms, including ethylene glycol, propylene glycol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, carbon dodecanol, carbon tetradecanol, carbon hexadecanol, carbon octadecanol, carbon eicosanol, carbon dodecanol, carbon tetradecanol, carbon hexadecanol, carbon hexadecanol, carbon eicosanol, carbon dodecanol, carbon tetradecanol, carbon hexadecanol. Wherein d and e are the degree of polymerization, d is an integer of 1 to 60, and e is an integer of 0 to 50.

10. The organosilicon composition according to claim 1, characterized in that: The catalyst-1 is a precious metal catalyst selected from platinum-alcohol complex, platinum-olefin complex, platinum-ether complex, platinum-ketone complex, 1% chloroplatinic acid isopropanol solution, rhodium-alcohol complex, rhodium-alkoxide complex.

11. The organosilicon composition according to claim 1, characterized in that: The catalyst-2 is selected from potassium hydroxide-isopropanol solution, potassium hydroxide-methanol solution, potassium hydroxide-ethanol solution, and potassium hydroxide-methylpolysiloxane mixture.

12. An organosilicon emulsion prepared by using the organosilicon composition according to any one of claims 1 to 9 and applied to a papermaking and pulping system.

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