CN109289255B - Foam control composition and preparation method thereof - Google Patents
Foam control composition and preparation method thereof Download PDFInfo
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- CN109289255B CN109289255B CN201811506022.XA CN201811506022A CN109289255B CN 109289255 B CN109289255 B CN 109289255B CN 201811506022 A CN201811506022 A CN 201811506022A CN 109289255 B CN109289255 B CN 109289255B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
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Abstract
The invention relates to a foam control composition and a preparation method thereof, wherein the foam control composition is prepared by mixing and adding inert polysiloxane, vinyl-containing polysiloxane, hydrogen-containing polysiloxane, a structure control agent, a catalyst, silicon dioxide, inert organic silicon resin and water. The addition of the structure control agent of alkynol and water solves the problem of sudden polymerization in the implementation process and also effectively solves the problem of viscosity increase in the storage period. The organic silicon foam control agent prepared by the method can be used in industries such as papermaking black liquor, textile printing and dyeing, sewage treatment, industrial cleaning and the like.
Description
Technical Field
The present invention relates to a polyorganosiloxane-based foam control composition having excellent foam control properties in surfactant-rich industrial systems. The invention belongs to the technical field of fine chemical preparations.
Background
Foam is a common phenomenon in daily life and industrial production processes, and has advantages and disadvantages, such as people often utilize foam to fight fires, utilize formed foam to make polyurethane, and utilize foam to make food cakes; in many industrial systems, foam is a major hazard to productive life because it affects yield, quality, environmental and economic benefits. The method for eliminating foam is generally divided into a mechanical method and a chemical method, wherein the mechanical method is to eliminate harmful foam by utilizing methods such as high-pressure impact, temperature rise, negative pressure and the like, but the overall effect is poor; the so-called "chemical method" is to eliminate foam by using chemical agents, such as foam control, whose basic principle is by surface tension variation; rather than eliminating foam by reducing the concentration of foaming material through a true chemical reaction. One typically chooses to eliminate, reduce or control the deleterious foam with foam control agents. Currently, foam control agents have been widely used in paper making, coatings, chemical industry, printing and dyeing, medicine, water treatment, food processing, oil extraction and other processes.
It is known that, from the viewpoint of active materials, silicone type foam control agents have the widest application range as compared with polyether type, fatty alcohol type, and mineral oil type foam control agents, and are commercially favored because of their advantages such as small amount, high defoaming ability, low volatility, no toxicity, and no side effects. The foam control agent of organosilicon class mainly comprises several basic components such as polysiloxane, hydrophobic particle, silicone resin and catalyst, etc., US4639489 is the original foam control agent, it introduces and processes and obtains by polydimethylsiloxane and silica for a long time at high temperature, but this kind of foam control composite structure is single, the foam-inhibiting performance is bad, still is applied by some trades so far. The structure of polysiloxane, the kind and amount of hydrophobic particles, the kind of silicone resin, the process, etc. have been widely studied since the 80's in the 20 th century. US4338217A1 is prepared by mixing alkoxy polysiloxane and white carbon black particles to prepare an organic silicon active substance; US5824739 directly mixing amino or carboxyl containing polysiloxane with white carbon black to obtain an organosilicon composition; US2008064806a1 investigated the difference between the viscosity and the foam suppressing effect of silicone compositions; CN201010213081.5 is prepared by mixing polydimethylsiloxane and modified polydimethylsiloxane with white carbon black and silicon resin; EP0163398A1 researches the preparation of silicon paste by mixing high-low viscosity polysiloxane and white carbon black. The preparation of these silicon pastes was studied around how the structure of the polysiloxanes was. In EP2794760, hydrophilic white carbon black and hydrophobic white carbon black are introduced simultaneously, and the viscosity of the composition is reduced to 50% of the viscosity measured by the mixture before heating through equipment such as a colloid mill, so that the defoaming composition is finally emulsified at a proper viscosity, but a crosslinking structure formed by hydroxyl condensation is weak, and the defoaming composition cannot play a good foam inhibition role in an anion system with strong foaming power.
It has been generally accepted in the industry that silicone compositions having a steric structure are required to provide silicone foam control agents with excellent performance through recent 40 years of research. US5153258 describes the incorporation of a lightly crosslinked polysiloxane and white carbon black into a system to improve the defoaming and foam suppressing properties of the composition. US8053480B2 also describes a high viscosity vinyl siloxane and a low viscosity hydrogen polysiloxane crosslinked in the presence of hydrophobic white carbon black until partially gelled, and then applying high shear to this partially gelled mixture until a suitable viscosity range, which composition has relatively good foam suppressing properties in strong alkaline systems, but still lacks foam suppressing ability, and the gelling produced when preparing the composition is not easily controlled. Both US3455839 and CA2074060 describe a polysiloxane defoaming composition with a cross-linked structure formed by reacting vinyl polysiloxane and hydrogen-containing polysiloxane under the condition of a transition metal catalyst such as chloroplatinic acid, which improves the late-stage foam inhibition capability, but how to control the difference between batches is not solved well.
The most significant problem with the compositions described in the above patents is that they are susceptible to implosion, which results in unstable properties or difficulty in emulsifying dispersion.
The inventors of the present invention have studied the reaction between a vinyl-containing polysiloxane and a hydrogen-containing polysiloxane and found that the degree of crosslinking can be controlled by the addition of a control agent, and the problem of implosion, that is, the difference in product properties, can be solved.
The foam control composition prepared by the method can be used in industries such as papermaking black liquor, textile printing and dyeing, sewage treatment, industrial cleaning and the like.
Disclosure of Invention
The invention relates to a foam control composition and a preparation method thereof. The foam composition is characterized by comprising inert polysiloxane, vinyl-containing polysiloxane, hydrogen-containing polysiloxane, a structure control agent, a catalyst, silicon dioxide, inert organic silicon resin and water:
A. inert polysiloxanes
The inert polysiloxane has the following structural general formula:
R a SiO a(4-)/2
（Ⅰ）
in the formula (I), the compound is shown in the specification,athe value of (a) is 1.9-2.2, and the polysiloxane comprises a straight chain, a branched chain and a spatial structure; the substituent R is univalent substituted or unsubstituted alkyl with 1-30 carbon atoms, the values are the same or different, and the substituent R specifically comprises the following components:
alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, hexacosyl, octacosyl, triacontyl;
aromatic hydrocarbons, e.g. phenyl,α-a methylphenylethyl group;
polyethers are predominantly polymerized from allyl alcohol with Ethylene Oxide (EO) and Propylene Oxide (PO).
From the viewpoint of availability of raw materials and cost, 80% of the substituents R in the inert polysiloxane are methyl groups.
The inert polysiloxane has a dynamic viscosity of 100-10,000 mPa & s at 25 ℃. The amount of the inert polysiloxane is 60-90% of the total mass of the organic silicon composition.
B. Hydrogenpolysiloxanes
The structural general formula of the vinyl-containing polysiloxane is as follows:
in the formula (II), R1Is an alkyl or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, pentyl, hexyl, octyl, phenyl, styrene, preferably R1Is methyl; subscriptbAndcis the degree of polymerization,b0 or an integer of 1 to 5, and the dynamic viscosity of the vinyl-containing polysiloxane at 25 ℃ is 200 to 80,000mPa.s, preferably 1000 to 40,000 mPa.s. The amount of the vinyl-containing polysiloxane is 5-35% of the total mass of the foam control composition.
C. Hydrogenpolysiloxanes
The general structural formula of the hydrogenpolysiloxane is as follows:
in the formula (III), R2Is alkyl or aryl of 1-8 carbon atoms, such as methyl, ethyl, propyl, pentyl, hexyl, octyl, phenyl, styrene, preferably R2Is methyl; r3Is a hydrogen atom or a methyl group; subscriptdIs 0 or an integer of 1 to 10, and at least two silicon-bonded hydrogen atoms are present in each molecule; subscripteRepresents an integer of a value such that the hydrogen-containing polyorganosiloxane has a dynamic viscosity at 25 ℃ in the range of 2 to 60 mPa.s. The dosage of the hydrogenpolysiloxane is 0.05-8% of the total mass of the foam control composition.
D. Structure control agent
The structure control agent is mainly alkynol substances selected from octynol, decylenol, 2-methyl-3-butyn-2-ol, methylbutylenol, methylpentylenol, 1-alkynylcyclohexanol, 1, 4-butynediol, 3,7, 11-trimethyldodecyn-3-ol, 4-pentyn-1-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3-pentyn-1-ol, 3, 5-dimethyl-1-hexyn-3-ol and 3, 6-dimethyl-4-octyne-3, 6-diol.
The dosage of the structure control agent is 0.01-2% of the total mass of the foam control composition.
E. Catalyst and process for preparing same
The catalyst is a noble metal catalyst for promoting hydrosilylation, and is selected from platinum-alcohol complex, platinum-olefin complex, platinum-alkoxide complex, platinum-ether complex, platinum-ketone complex, chloroplatinic acid isopropanol solution with chloroplatinic acid concentration of 1%, rhodium-alcohol complex and rhodium-alkoxide complex, and preferably chloroplatinic acid isopropanol solution with mass concentration of 1%. The amount of the catalyst is 3 to 30ppm, preferably 5 to 15ppm (in terms of platinum) based on the total mass of the foam control composition.
F. Silicon dioxide
Silica is classified into precipitated silica and vapor-phase silica according to the manufacturing method, and hydrophilic silica and hydrophobic silica according to the surface properties. The invention selects hydrophobic silicon dioxide, comprises a gas phase method and a precipitation method, and has a specific surface area of 50-500 m2Per g, preferably 80 to 400m2And/g, the precipitates with different specific surface areas and the fumed silica are used independently or in a mixed manner, and the using amount of the precipitates and the fumed silica is 3-10% of the total mass of the foam control composition.
G. Inert silicone resins
The inert organic silicon resin generally refers to a silicon resin which does not substantially react with other substances, and generally refers to MQ resin consisting of M chain links and Q chain links, wherein the molar ratio of the M chain links to the Q chain links is (0.5-1.2): 1.0. the usage amount of the inert organic silicon resin is 1-8% of the total mass of the foam control composition.
H. Water (W)
The water comprises tap water, process water and purified water, and the appearance forms of the water comprise liquid water and solid ice.
The using amount of the water is 0.1-2% of the total mass of the foam control composition.
The preparation method of the foam control composition of the invention is as follows:
(1) adding inert polysiloxane, silicon dioxide and inert silicone resin into a container, heating to 40-120 ℃, controlling the rotating speed to be 1000-3000 rpm, completely dispersing solid particles in the inert polysiloxane, enabling the final solid dispersed particle size to be less than 5 micrometers through grinding equipment, cooling to room temperature for later use, and marking as a dispersoid I;
(2) adding vinyl-containing polysiloxane, hydrogen-containing polysiloxane and a structure control agent into another container, raising the temperature to 30-140 ℃, and stirring to ensure that the mixture is transparent and is marked as a mixture II;
(3) adding the dispersoid I into the mixture II, controlling the temperature to be 50-100 ℃, adding a catalyst, then heating to 100-150 ℃, preserving the heat for 0.5-4 h to obtain viscous liquid, adding water when the temperature is reduced to be below 90 ℃, stirring and mixing uniformly, and further cooling to room temperature to obtain the foam control composition.
The foam control composition prepared by the invention can be directly provided for use according to the requirements of actual use, or can be diluted by a solvent, or prepared into an emulsion, or prepared into a solid type foam control product.
Methods for preparing foam control agents in the form of oil-in-water emulsions are well known to those skilled in the art and can be looked up on general technical information, such emulsions generally consisting of a foam control composition, an emulsifier, water, a thickener and a preservative.
The nonionic surfactant comprises nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, lauric acid polyoxyethylene ether, oleic acid polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, octanol polyoxyethylene ether, isooctanol polyoxyethylene ether, heterogeneous decanol polyoxyethylene ether, heterogeneous tridecanol polyoxyethylene ether, cetyl alcohol polyoxyethylene ether, stearyl alcohol polyoxyethylene ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan tristearate, And one or more of castor oil polyoxyethylene ether, preferably a mixture of more.
The thickening agent is selected from polyacrylamide, polyvinyl alcohol, carbomer, xanthan gum, polyacrylate, cellulose ether, preferably xanthan gum and polyacrylate, and the addition amount is adjusted according to the requirement of emulsion viscosity.
Detailed Description
Example 1
85.13 parts of trimethylsilyl-terminated polydimethylsiloxane having a viscosity of 1000 mPas and 3 parts of a specific surface area of 200m were charged in a vessel2Hydrophobic fumed silica R974 per gram and 1.3 parts of inert silicone resin (molar ratio of M units to Q units is 0.7: 1.0, heated to 45 ℃ C., controlled at 3000rpm, so that the solid particles are completely dispersed in the inert polysiloxane, and the final solid dispersion particle size is less than 5 μ M by a grinding device, and cooled to room temperature for later use, and is marked as dispersion I;
in another container, 10 parts of a vinyl-containing polysiloxane (R)1Is a methyl group, and the compound is,b= 0, viscosity 20,000mPa · s), 0.06 parts of hydrogenpolysiloxane (R)2Is methyl, R3Is a methyl group, and the compound is,d= 0, viscosity 25mPa · s) and 0.01 part of 1, 4-butynediol, the temperature being kept at 35 ℃ and stirring being carried out so that the mixture is transparent and is designated as mixture ii;
adding the dispersion I into the mixture II, controlling the temperature at 50 ℃, adding 10ppm chloroplatinic acid/isopropanol solution (calculated by platinum), heating to 100 ℃, preserving the temperature for 4 hours to obtain viscous liquid, adding 0.5 part of water when the temperature is reduced to 88 ℃, stirring and mixing uniformly, and further reducing to room temperature to obtain the foam control composition FC-1, wherein the dynamic viscosity at 25 ℃ is 93,000 mPas.
Example 2
60.8 parts of trimethylsilyl-terminated hexadecyl-modified polydimethylsiloxane having a viscosity of 100 mPas and 5 parts of a specific surface area of 380m were charged in a vessel2830/g of hydrophobic fumed silica and 3 parts of powdered inert silicone resin (molar ratio of M units to Q units is 0.5: 1.0, heated to 120 ℃ and controlled at 1000rpm so that the solid particles are in the inert siliconeCompletely dispersing in alkane, reducing the particle size of the final solid dispersion to be below 5 mu m by grinding equipment, and recording as a dispersion I;
in another vessel, 30 parts of a vinyl-containing polysiloxane (R)1Is a methyl group, and the compound is,b=1, viscosity 40,000mPa · s), 0.2 parts of hydrogenpolysiloxane (R)2Is methyl, R3Is a hydrogen atom, and is a hydrogen atom,d=10, viscosity 58mPa · s) and 0.5 part of methylpentylenol, the temperature being maintained at 135 ℃, stirring until the mixture is clear, denoted as mixture ii;
adding the dispersion I into the mixture II, controlling the temperature at 100 ℃, adding 11ppm chloroplatinic acid/isopropanol solution (calculated by platinum), heating to 150 ℃, preserving the temperature for 0.5h to obtain viscous liquid, adding 0.5 part of crushed ice when the temperature is reduced to 80 ℃, stirring and mixing uniformly, and further cooling to room temperature to obtain the foam control composition FC-2, wherein the dynamic viscosity at the temperature of 25 ℃ is 157,000mPa & s.
Example 3
76.2 parts of a trimethylsilyl-terminated product having a viscosity of 2000 mPas were added to the vesselα-methylstyrene-modified polydimethylsiloxane, 5 parts of a specific surface area of 80m2Precipitated hydrophobic silica D10 per g and 7 parts of an inert silicone resin (molar ratio of M units to Q units 1.2: 1, heated to 100 ℃ C., controlled at 2500rpm, so that the solid particles are completely dispersed in the inert polysiloxane, and the final solid dispersion particle size is below 5 μ M by a grinding device, cooled to room temperature for use as dispersion I;
in another container, 5 parts of a vinyl-containing polysiloxane (R)1Is composed ofα-a methyl-styrene-based monomer,b=5, viscosity 1,000 mPas), 8 parts of hydrogenpolysiloxane (R)2Is composed ofα-methylstyrene, R3Is a hydrogen atom, and is a hydrogen atom,d=1, viscosity 20mPa · s) and 2 parts of 1-alkynylcyclohexanol, the temperature being kept at 115 ℃, stirring until the mixture is transparent, denoted as mixture ii;
adding the dispersion I into the mixture II, controlling the temperature at 80 ℃, adding 9ppm chloroplatinic acid/isopropanol solution (calculated by platinum), heating to 120 ℃, preserving the temperature for 2 hours to obtain viscous liquid, adding 0.9 part crushed ice and 0.9 part water when the temperature is reduced to 75 ℃, stirring and mixing uniformly, and further reducing the temperature to room temperature to obtain the foam control composition FC-3, wherein the dynamic viscosity at 25 ℃ is 33,000 mPas.
Example 4
74.1 parts of a trimethylsilyl-terminated hexadecyl-modified polydimethylsiloxane having a viscosity of 1400 mPas and 6 parts of a specific surface area of 80m were charged in a vessel2Precipitated hydrophobic silica D10 in a proportion of 3 parts by weight and a specific surface area of 380m2830/g of hydrophobic fumed silica and 2 parts of inert organic silicon resin (the molar ratio of M chain link to Q chain link is 0.66: 1, the mixture is heated to 80 ℃, the rotating speed is controlled to be 1500rpm, so that solid particles are completely dispersed in the inert polysiloxane, the final solid dispersed particle size is less than 5 mu M through grinding equipment, and the mixture is cooled to room temperature for standby and is marked as dispersion I;
in another vessel 4 parts of a vinyl-containing polysiloxane (R) were added1Is a hexadecyl group, and the alkyl is a hexadecyl group,b=3, viscosity of 30,000 mPas), 8 parts of hydrogenpolysiloxane (R)2Is hexadecyl, R3Is a methyl group, and the compound is,d=1, viscosity 38mPa · s) and 1.5 parts of 3, 5-dimethyl-1-hexyn-3-ol, the temperature being maintained at 105 ℃, stirring until the mixture is clear and is designated as mixture ii;
adding the dispersion I into the mixture II, controlling the temperature at 100 ℃, adding 8ppm chloroplatinic acid/isopropanol solution (calculated by platinum), heating to 130 ℃, preserving the temperature for 1.5h to obtain viscous liquid, adding 1.4 parts of water when the temperature is reduced to 85 ℃, stirring and mixing uniformly, and further reducing to room temperature to obtain the foam control composition FC-4, wherein the dynamic viscosity at 25 ℃ is 47,000 mPas.
Example 5
65.2 parts of a trimethylsilyl-terminated polyether-modified polydimethylsiloxane (CH) having a viscosity of 1400 mPas were charged in a vessel2CH2CH2O(EO)5(PO)18H) 5 parts of a specific surface area of 150m2Hydrophobic fumed silica R972/g and 3 parts of an inert silicone resin (molar ratio of M units to Q units 0.75: 1, heated to 100 ℃ C.) and controlledThe preparation rotating speed is 2000rpm, so that solid particles are completely dispersed in the inert polysiloxane, the final solid dispersion particle size is less than 5 microns through grinding equipment, and the temperature is reduced to room temperature for later use and is marked as a dispersoid I;
in another vessel 25 parts of a vinyl-containing polysiloxane (R) were charged1Is a methyl group, and the compound is,b=4, viscosity 23,000mPa · s), 0.8 parts of hydrogenpolysiloxane (R)2Is methyl, R3Is a methyl group, and the compound is,d=1, viscosity 48mPa · s) and 3, 5-dimethyl-1-hexyn-3-ol, maintaining the temperature at 115 ℃, stirring until the mixture is clear, denoted as mixture ii;
adding the dispersion I into the mixture II, controlling the temperature to be 85 ℃, adding 5ppm chloroplatinic acid/isopropanol solution (calculated by platinum), heating to 150 ℃, preserving the temperature for 3.5 hours to obtain viscous liquid, adding 1.0 part of water when the temperature is reduced to 85 ℃, stirring and mixing uniformly, and further reducing to room temperature to obtain the foam control composition FC-5, wherein the dynamic viscosity at 25 ℃ is 130,000 mPas.
Example 6
71.7 parts of a trimethylsilyl-terminated polydimethylsiloxane having a viscosity of 10,000 mPas and 3 parts of a specific surface area of 90m were charged in a vessel2Hydrophobic precipitated phase silica D10 per g and 6 parts of an inert silicone resin (molar ratio of M units to Q units is 0.7: 1.0, heated to 45 ℃ C., controlled at 3000rpm, so that the solid particles are completely dispersed in the inert polysiloxane, and the final solid dispersion particle size is less than 5 μ M by a grinding device, and the solution is cooled to room temperature for later use and is marked as dispersion I;
in another container 18 parts of a vinyl-containing polysiloxane (R) are added1Is a methyl group, and the compound is,b= 0, viscosity 20,000 mPas), 0.5 part of hydrogenpolysiloxane (R)2Is methyl, R3Is a methyl group, and the compound is,d= 0, viscosity 25mPa · s) and 1, 4-butynediol, maintaining the temperature at 35 ℃, stirring to make the mixture transparent, denoted as mixture ii;
adding the dispersion I into the mixture II, controlling the temperature at 50 ℃, adding 10ppm chloroplatinic acid/isopropanol solution (calculated by platinum), heating to 100 ℃, preserving the temperature for 4 hours to obtain viscous liquid, adding 0.8 part of water when the temperature is reduced to 88 ℃, stirring and mixing uniformly, and further reducing to room temperature to obtain the foam control composition FC-6, wherein the dynamic viscosity at 25 ℃ is tested to be 115,000 mPas.
Example 7
To the vessel were added 72.4 parts of trimethylsilyl-terminated polydimethylsiloxane having a viscosity of 5,000 mPas and 4 parts of a specific surface area of 200m2Hydrophobic fumed silica R202 per gram and 3 parts of inert organic silicon resin (the molar ratio of M chain link to Q chain link is 0.60: 1.0, the mixture is heated to 85 ℃, the rotating speed is controlled to be 2300rpm, so that solid particles are completely dispersed in the inert polysiloxane, the final solid dispersed particle size is less than 5 mu M through grinding equipment, and the mixture is cooled to room temperature for standby and is marked as dispersion I;
in another container, 15 parts of a vinyl-containing polysiloxane (R)1Is a methyl group, and the compound is,b= 2, viscosity 15,000 mPas), 2 parts of hydrogenpolysiloxane (R)2Is methyl, R3Is a hydrogen atom, and is a hydrogen atom,d=5, viscosity 58mPa · s) and 1.6 parts of 3, 6-dimethyl-4-octyne-3, 6-diol, the temperature being maintained at 105 ℃ and stirring being carried out such that the mixture is transparent and is designated as mixture ii;
adding the dispersion I into the mixture II, controlling the temperature at 75 ℃, adding 14ppm chloroplatinic acid/isopropanol solution (calculated by platinum), heating to 120 ℃, preserving the temperature for 3 hours to obtain viscous liquid, adding 2 parts of water when the temperature is reduced to 83 ℃, stirring and mixing uniformly, and further reducing to room temperature to obtain the foam control composition FC-7, wherein the dynamic viscosity at 25 ℃ is 146,000 mPas.
Examples 8 to 10
An amplification of 1kg, 10kg and 100kg was carried out in accordance with the formulation of example 7 to obtain FC-8, FC-9 and FC-10, and the dynamic viscosities at 25 ℃ were 128,000 mPas, 154,000 mPas and 145,000 mPas, respectively.
Comparative example 1
74.4 parts of trimethylsilyl-terminated polydimethylsiloxane having a viscosity of 5,000 mPas and 4 parts of a specific surface area of 200m were charged in a vessel2Per g of hydrophobic fumed silica R202 and 3 parts of inert silicone resin (M mer andthe molar ratio of Q units is 0.60: 1.0, heating to 85 ℃, controlling the rotating speed to be 2300rpm, completely dispersing solid particles in inert polysiloxane, enabling the final solid dispersed particle size to be less than 5 mu m through grinding equipment, and cooling to room temperature for later use, and marking as a dispersoid I;
in another container, 15 parts of a vinyl-containing polysiloxane (R)1Is a methyl group, and the compound is,b= 2, viscosity 15,000 mPas), 2 parts of hydrogenpolysiloxane (R)2Is methyl, R3Is a hydrogen atom, and is a hydrogen atom,d=5, viscosity 58mPa · s) and 1.6 parts of 3, 6-dimethyl-4-octyne-3, 6-diol, the temperature being maintained at 105 ℃ and stirring being carried out such that the mixture is transparent and is designated as mixture ii;
adding the dispersion I into the mixture II, controlling the temperature at 75 ℃, adding 14ppm chloroplatinic acid/isopropanol solution (calculated as platinum), then raising the temperature to 120 ℃, preserving the temperature for 3 hours to obtain viscous liquid, cooling to room temperature to obtain a foam control composition CFC-7A, and testing the dynamic viscosity at 25 ℃ to be 140,000 mPas.
Comparative example 2:
74 parts of trimethylsilyl-terminated polydimethylsiloxane having a viscosity of 5,000 mPas and 4 parts of a specific surface area of 200m were charged in a vessel2Hydrophobic fumed silica R202 per gram and 3 parts of inert organic silicon resin (the molar ratio of M chain link to Q chain link is 0.60: 1.0, the mixture is heated to 85 ℃, the rotating speed is controlled to be 2300rpm, so that solid particles are completely dispersed in the inert polysiloxane, the final solid dispersed particle size is less than 5 mu M through grinding equipment, and the mixture is cooled to room temperature for standby and is marked as dispersion I;
in another container, 15 parts of a vinyl-containing polysiloxane (R)1Is a methyl group, and the compound is,b= 2, viscosity 15,000 mPas), 2 parts of hydrogenpolysiloxane (R)2Is methyl, R3Is a hydrogen atom, and is a hydrogen atom,d=5, viscosity 58mPa · s), the temperature is maintained at 105 ℃, the mixture is stirred until it is transparent, and is denoted as mixture ii;
adding the dispersion I into the mixture II, controlling the temperature at 75 ℃, adding 14ppm chloroplatinic acid/isopropanol solution (calculated by platinum), heating to 120 ℃, preserving the temperature for 3 hours to obtain viscous liquid, adding 2 parts of water when the temperature is reduced to 83 ℃, stirring and mixing uniformly, and further reducing to room temperature to obtain a foam control composition CFC-7B, wherein the dynamic viscosity at 25 ℃ is 230,000mPa & s.
Comparative example 3:
prepared according to the method of example 2 of CN101454061A to give a foam control composition CFC-7B having a kinematic viscosity at 25 ℃ of 78,000 mPas.
Testing of foam control performance:
preparation of test samples: diluting foam control composition with cyclohexane as diluting medium
Test medium: 1% NP-10 aqueous solution
The test method comprises the following steps: testing by the Shake flask method
The test method comprises the following steps: 50mL of the foaming medium is added into a 100mL measuring cylinder with a plug, then 0.010g of a test sample is added, the test sample is shaken for 50 times at the amplitude of 30-40 cm at the frequency of 100-120 times/min in the vertical direction, then the test sample is kept stand, the time of foam elimination until the liquid level appears is recorded as defoaming time, the defoaming time is recorded by shaking for 50 times, and the shorter the time is until the total shaking times reach 400 times, the better the defoaming effect of the defoaming composition is.
The foam control performance test results for the silicone compositions are shown in table 1:
as can be seen from the data in table 2:
(1) the foam control ability of examples 1-10 was good;
(2) examples 8 to 10 are the amplification experiments carried out on the basis of example 7, and also show a good effect;
(3) comparative example CFC-7A was water-free and had no significant effect on foam control, but CFC-7B had poorer foam control than both FC-7 and CFC-7A because without the control agent, implosion occurred easily, resulting in a very high viscosity and poor dispersion in the bubble medium.
Comparing the results of CFC-7C and the remaining examples, it can be seen that a composition having more excellent properties than those of the prior patents can be obtained by adding a trace amount of water and a structure-controlling agent and controlling the process.
And (3) stability testing:
the initial viscosity was compared to the change in viscosity after one month at room temperature and the results are shown in table 2:
as can be seen from the data in table 2:
(1) the viscosity change of the compositions of examples 1-10 after being placed for one month is within 10%, and subsequent emulsification application is not influenced;
(2) compositions without structure control agents are capable of undergoing implosion during implementation; the implementation process without adding water has no sudden aggregation, but the viscosity change is large in the placing process, so that the later use is seriously influenced;
(3) in conclusion, the sudden polymerization problem of hydrogenpolysiloxane and vinyl polysiloxane can be solved through the addition of the structure control agent of alkynol and water, and the later-period viscosity increase can also be effectively controlled.
Claims (9)
1. A foam control composition comprising an inert polysiloxane, a vinyl-containing polysiloxane, a hydrogen-containing polysiloxane, a structure control agent, a catalyst, silica, an inert silicone resin, and water:
A. the dynamic viscosity of the inert polysiloxane at 25 ℃ is 100-10,000 mPa & s, and the using amount of the inert polysiloxane is 60-90% of the total mass of the organic silicon composition;
B. vinyl-containing polysiloxane, wherein the using amount of the vinyl-containing polysiloxane is 5-35% of the total mass of the foam control composition;
C. hydrogen-containing polysiloxane, wherein the using amount of the hydrogen-containing polysiloxane is 0.05-8% of the total mass of the foam control composition;
D. a structure control agent selected from the group consisting of octynol, decylenol, 2-methyl-3-butyn-2-ol, methylbutynol, methylpentylenol, 1-alkynylcyclohexanol, 1, 4-butynediol, 3,7, 11-trimethyldodecyn-3-ol, 4-pentyn-1-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3, 6-dimethyl-4-octyn-3, 6-diol; the using amount of the foam control composition is 0.01-2% of the total mass of the foam control composition;
E. a catalyst selected from the group consisting of platinum-alcohol complexes, platinum-olefin complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-ketone complexes, chloroplatinic acid isopropanol solution with a chloroplatinic acid concentration of 1%, rhodium-alcohol complexes, rhodium-alkoxide complexes; the dosage of the catalyst is 3-30 ppm of the total mass of the foam control composition;
F. the silicon dioxide comprises a gas phase method and a precipitation method, and the specific surface area of the silicon dioxide is 50-500 m2The precipitates with different specific surface areas and the fumed silica are used independently or in a mixed mode, and the using amount of the precipitates and the fumed silica is 3-10% of the total mass of the foam control composition;
G. the inert organic silicon resin is silicon resin which does not react with other substances and is MQ resin consisting of M chain links and Q chain links, and the molar ratio of the M chain links to the Q chain links is (0.5-1.2): 1.0; the using amount of the foam control composition is 1-8% of the total mass of the foam control composition;
H. the water comprises tap water and purified water, and the appearance forms of the water are liquid water and solid ice; the using amount of the foam control composition is 0.1-2% of the total mass of the foam control composition;
the preparation method of the foam control composition comprises the following steps:
(1) adding inert polysiloxane, silicon dioxide and inert silicone resin into a container, heating to 40-120 ℃, controlling the rotating speed to be 1000-3000 rpm, completely dispersing solid particles in the inert polysiloxane, enabling the final solid dispersed particle size to be less than 5 micrometers through grinding equipment, cooling to room temperature for later use, and marking as a dispersoid I;
(2) adding vinyl-containing polysiloxane, hydrogen-containing polysiloxane and a structure control agent into another container, raising the temperature to 30-140 ℃, and stirring to ensure that the mixture is transparent and is marked as a mixture II;
(3) adding the dispersoid I into the mixture II, controlling the temperature to be 50-100 ℃, adding a catalyst, then heating to 100-150 ℃, preserving the heat for 0.5-4 h to obtain viscous liquid, adding water when the temperature is reduced to be below 90 ℃, stirring and mixing uniformly, and further cooling to room temperature to obtain the foam control composition.
2. The foam control composition of claim 1, wherein said inert polysiloxane has the general structural formula:
R a SiO a(4-)/2
（Ⅰ）
in the formula (I), the compound is shown in the specification,athe value of (a) is 1.9-2.2, and the polysiloxane comprises a straight chain, a branched chain and a spatial structure; the substituent R is univalent substituted or unsubstituted hydrocarbon with 1-30 carbon atoms, is the same or different in value, and is selected from alkyl, aromatic hydrocarbon and allyl alcohol polyether formed by polymerizing allyl alcohol, Ethylene Oxide (EO) and Propylene Oxide (PO).
3. A foam control composition according to claim 2, wherein 80% of the substituents R in the inert polysiloxane structure are methyl groups.
4. The foam control composition of claim 1, wherein said vinyl-containing polysiloxane has the general structural formula:
（Ⅱ）
in the formula (II), R1Is an alkyl or aryl group having 1 to 8 carbon atoms; subscriptbAndcis the degree of polymerization,b0 or an integer of 1 to 5, and the dynamic viscosity of the vinyl-containing polysiloxane at 25 ℃ is 200 to 80,000mPa·s。
5. The foam control composition according to claim 4, wherein the vinyl-containing polysiloxane has a dynamic viscosity of 1000 to 40,000 mPa-s at 25 ℃.
6. The foam control composition of claim 1, wherein said hydrogenpolysiloxane has the general structural formula:
（Ⅲ）
in the formula (III), R2Is an alkyl or aryl group having 1 to 8 carbon atoms; r3Is a hydrogen atom or a methyl group; subscriptdIs 0 or an integer of 1 to 10, and at least two silicon-bonded hydrogen atoms are present in each molecule; subscripteIs an integer of a value such that the hydrogen-containing polyorganosiloxane has a dynamic viscosity of 2 to 60 mPas at 25 ℃.
7. The foam control composition as claimed in claim 1, wherein the catalyst is a 1% by weight solution of chloroplatinic acid in isopropanol.
8. The foam control composition according to claim 7, wherein the amount of the catalyst is 5 to 15ppm based on platinum based on the total mass of the foam control composition.
9. The foam control composition according to claim 1, wherein the silica has a specific surface area of 80 to 400m2/g。
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