CN115105868B - Organic silicon defoamer and preparation method thereof - Google Patents
Organic silicon defoamer and preparation method thereof Download PDFInfo
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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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- 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
Abstract
The invention provides an organosilicon defoamer, which comprises the following raw materials: hydroxyl-containing polysiloxane, a network structure agent, a condensation catalyst, a silicone resin, inorganic particles, an alkaline catalyst, water and an organic solvent. The preparation method of the organic silicon defoamer is also provided: adding water, an organic solvent, a reticular structure agent and a condensation catalyst into a reactor, stirring, and raising the temperature to react so that the reticular structure agent undergoes hydrolysis and condensation reaction to obtain condensation oligosiloxane; adding hydroxyl-containing polysiloxane for reaction, and evaporating volatile matters to obtain viscous oily matter, namely component XI; adding an organic solvent, inorganic particles and organic silicon resin into another reactor, stirring, heating and preserving heat until the solid is dissolved to obtain a component XII; finally, the components XI and XII are mixed in a reactor, an alkaline catalyst is added, the mixture is stirred and heated for reaction, and the solvent is distilled off, so that the organosilicon defoamer is obtained, and has good hydrophilicity and defoaming durability.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to an organosilicon defoamer and a preparation method thereof.
Background
The defoamer is one of the essential fine chemical auxiliary agents in the industrial production process, is mainly used for eliminating the harmful foam in the industrial production process, and can be classified into organic silicon, polyether, mineral oil, fatty alcohol and the like according to the different components of the defoamer. The products have the advantages of being suitable for fields of sewage treatment, petroleum exploitation, textile printing and dyeing, pulping and papermaking and the like, and have the functions of fast defoaming speed and long-time foam inhibition, but the simple organic silicon defoamer has the problem of compatibility in coatings, printing ink, metal processing liquid, is easy to separate out from a system, influences surface properties such as shrinkage cavity, fish eyes, floating, net blocking and the like, and the organic silicon needs to be modified at the moment, and modified groups comprise polyether, alkene, alkyne and the like. The polyether and fatty alcohol defoamer is generally used for defoaming and degassing papermaking white water in the wet end of papermaking, and the mineral oil defoamer is also generally used in paint, printing ink and adhesive, and has low defoaming speed, but generally does not influence the coating, and belongs to the favour of middle-low grade paint and printing ink.
In general, silicone defoamers are a major concern for numerous defoamer manufacturers and research institutions. 202011350420.4 describes a silicone landfill leachate defoamer which comprises polyether modified polydimethylsiloxane, nanoscale fumed silica, modified silicone oil, fatty acid polyoxyethylene ester, an emulsifier, a thickener and a biological inhibitor; US5271868A describes that the defoamer for high temperature dyeing is prepared from two polyether modified silicone oils + silicone pastes, low viscosity hydroxyl silicone oils and white carbon black; CN103814072a describes that methyl silicone oil, hydroxyl silicone oil, amino silicone oil and white carbon black prepare defoamer emulsion; US2014316015A1 describes the preparation of defoamer silicone pastes by treating polysiloxanes, hydrophilic white carbon black, hydrophobic white carbon black, silicone resins at 50-250 ℃ to obtain silicone grease with a viscosity half that of the original silicone grease, which greatly improves the defoaming performance; US2009234029A1 describes the preparation of silicone grease by treating a mixture of silicone oil, white carbon black, a small amount of a treating agent, water or ammonia in a kneader; EP0516109A1 describes the effect of silicone grease prepared with methyl silicone oil, hydrogen-containing silicone oil, vinyl silicone oil, catalysts under strong shear and strong alkaline conditions.
The information presented in these patents falls into two categories, one category being the preparation of silicone pastes and the other category being the preparation of compositions of silicone pastes, modified polysiloxanes and the like. The silicone paste is the core of the organic silicon defoamer, the viscosity of the silicone paste prepared by the prior patent technology is unstable in the treatment period, and the defoaming performance is still to be further improved.
The organic silicon defoamer has good defoaming speed and foam inhibition performance, and has the characteristic of water insolubility besides low surface tension. However, in the case of being insoluble in water, the defoaming particles aggregate, and small particles slowly become large particles, thereby losing the defoaming function. Therefore, in order for the silicone paste to function adequately in the foaming medium, the defoaming particulate units must remain fine for a long period of time without agglomerating the particles.
At present, the organosilicon defoamer is compounded by polydimethylsiloxane, polyether modified polysiloxane or olefin modified polysiloxane, hydroxyl-containing polysiloxane and hydrophobic particles, and the organosilicon active matter can be stably present in a polyether system for a long time through the synergistic winding and wrapping action of the polyether modified polysiloxane and the linear polyether modified polysiloxane with spatial structures. The defoaming effect is improved by a crosslinking and compounding technology, but the polyether system of the silicone grease has fewer hydrophilic groups and has the problem of poor hydrophilicity; and the defect of insufficient defoaming durability caused by insufficient embedding of hydrophobic particles in the system. Some of the anti-foam agent emulsion is prepared by adding a surfactant to increase hydrophilicity, and the emulsion occupies a large volume in the storage process, has a short effective period, is easy to aggregate and separate out precipitate particles, and causes unstable performance; however, the organic defoamer silicon paste has the advantages of small storage volume, good stability and good safety, and can be used for preparing defoamer emulsion with various content applications according to requirements, and has higher practical value than the emulsion.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide an organosilicon defoamer, in particular to a netlike structure agent, which is subjected to hydrolysis and condensation reaction to obtain a cage-type structure and then is combined with hydroxyl-containing polysiloxane to obtain a unique structure similar to an octopus structure, and the defoamer with the structure has the advantages of good hydrophilicity and good defoaming durability.
The second purpose of the invention is to provide a preparation method of the organosilicon defoamer, namely, adding water, an organic solvent, a network structure agent and a condensation catalyst into a reactor, stirring, and raising the temperature to react so that the network structure agent undergoes hydrolysis and condensation reaction to obtain semi-condensation oligosiloxane; adding hydroxyl-containing polysiloxane for reaction, and evaporating volatile matters to obtain viscous oily matter, namely component XI; adding an organic solvent, inorganic particles and organic silicon resin into another reactor, stirring, heating and preserving heat until the solid is dissolved to obtain a component XII; finally, the components XI and XII are mixed in a reactor, an alkaline catalyst is added, the mixture is stirred and heated for reaction, and the solvent is distilled off, so that the organosilicon defoamer provided by the invention has good hydrophilicity and defoaming durability.
One of the purposes of the invention is realized by adopting the following technical scheme:
the organic silicon defoamer comprises the following raw materials in parts by weight:
the network structure agent is silane which can react with the hydroxyl-containing polysiloxane to form a network structure after hydrolysis and condensation reaction.
(1) Hydroxyl-containing polysiloxanes:
the molecular formula of the hydroxyl-containing polysiloxane is shown as formula I:
[R 1 x (OH) y SiO 1/4 ] a [Me 2 SiO 2/4 ] b [Me(OH)SiO 2/4 ] c [MeSiO 3/4 ] d [SiO 4/4 ] e i
Wherein subscript x=2 or 3, y=0 or 1, and x+y=3; subscript a, b, c, d, e is the minimum of the four mer number and has at least one hydroxyl group on the side chain;
substituent R in formula I 1 The substituent R1 may be the same or different and is a hydrocarbon group having 1 to 12 carbon atoms and no functional group or a hydrocarbon group having a substituent having a functional group.
The hydroxyl-containing polysiloxane is one or more than two of compounds with the structure shown in the formula I.
Further, the viscosity of the hydroxyl-containing polysiloxane is 5 to 100000 mPa.s;
further, the R 1 The hydrocarbon group without functional group is one of alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl and aralkyl; the R is 1 The hydrocarbyl containing functional group substituent is one of halogen-substituted hydrocarbyl and cyano-substituted hydrocarbyl.
Further, the alkyl is one of methyl, ethyl, propyl, butyl, hexyl or octyl;
further, the cycloalkyl is one of cyclopentyl and cyclohexyl;
further, the alkenyl group is one of vinyl, allyl or propenyl;
further, the cycloalkenyl group is cyclohexenyl;
further, the aryl is one of phenyl and methylphenyl;
further, the aralkyl is one of benzyl and 2-phenethyl;
further, the halogen-substituted hydrocarbyl group is chloromethyl;
further, the cyano-substituted hydrocarbon group is one of 3, 3-trifluoropropyl and 2-cyanoethyl.
Preferably, said R 1 Methyl, vinyl, phenyl.
(2) The net-shaped structural agent comprises the following components:
the network structure agent is silane which can react with the hydroxyl-containing polysiloxane to form a network structure after hydrolysis and condensation reaction, and the molecular formula of the silane is shown as formula II:
(R 2 ) f —Si—(OR 3 ) g II type
Wherein R is 2 Is one of hydrocarbon groups with 1-18 carbon atoms and hydrocarbon groups substituted by hydrophilic groups; the hydrocarbyl is one of alkyl, alkenyl, alkynyl, aryl, alkylaryl, and aralkyl.
Further, the R 2 The hydrophilic group in (a) is one or more than two of hydroxyl, amino, oxygen heterocyclic group, nitrogen oxygen heterocyclic group and amide group.
Wherein R is 3 Is a hydrocarbon group having 1 to 10 carbon atoms; the hydrocarbon group is a straight-chain hydrocarbon group or a branched-chain hydrocarbon group.
Wherein, the subscript f takes the values of 0, 1, 2 and 3; g takes values of 1, 2, 3, 4 and satisfies f+g=4.
The network structure agent is a composition of one or more than two silanes shown in a formula II, and at least comprises a silane with a trialkoxy structure.
Further, the method comprises the steps of, the network structure agent is trimethylmethoxysilane, triethylmethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, trihexylmethoxysilane, trioctylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, tributylethoxysilane, trihexylethoxysilane, trioctylethoxysilane, trimethylbutoxysilane, triethylbutoxysilane, tripropbutoxysilane, tributylbutoxysilane, trihexylbutoxysilane, trioctylbutoxysilane, trivinylmethoxysilane, trivinylethoxysilane, trivinylbutoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylbutoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, dihexyldimethoxysilane, dioctyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dibutyldiethoxysilane, dihexyldiethoxysilane, dioctyldiethoxysilane, dimethyldibutoxysilane, diethyldibutoxysilane, dipropyldibutoxysilane, dibutyldibutoxysilane, dihexyldibutoxysilane, dioctyldibutoxysilane, divinyl dimethoxysilane, divinyl diethoxysilane, divinyl dibutoxysilane, diphenyldimethoxysilane, diphenyldibutoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, methyltriethoxysilane, ethyl triethoxysilane, butyl triethoxysilane, hexyl triethoxysilane, octyl triethoxysilane, methyl tributoxysilane, ethyl tributoxysilane, propyl tributoxysilane, butyl tributoxysilane, hexyl tributoxysilane, octyl tributoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tributoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, phenyl tributoxysilane, tetraethoxysilane, hydroxymethyl trimethoxysilane, hydroxymethyl triethoxysilane, trimethylaminomethoxysilane, dibutyl aminomethyl tributoxysilane, cyclohexyl aminomethyl trimethoxysilane, cyclohexyl aminomethyl triethoxysilane, aminoethylaminopropyl trimethoxysilane, aminoethylaminopropyl triethoxysilane, 3-dimethylaminopropyl aminomethyl trimethoxysilane, morpholinomethyl trialkoxysilane, dibutylaminomethyl triethoxysilane, morpholinomethyl triisopropoxy silane, morpholinomethyl triethoxysilane, and a combination of two or more thereof, and at least contains a silane of trialkoxy structure.
The network structure agent is not only a planar network structure, but also a network structure in a three-dimensional space, and because of the chemical bond between alkoxy groups and silicon atoms in silane, silanol hydroxyl groups are easy to hydrolyze in water, and the hydroxyl groups are dehydrated and condensed between intermolecular silanol hydroxyl groups to form a silicon ether bond under the conditions of acid base and heating, a huge three-dimensional space network structure is formed through intermolecular hydroxyl condensation, and part of silanol hydroxyl groups do not participate in the reaction because of the three-dimensional chemical factors, so that the silicon alcohol hydroxyl groups keep better hydrophilic performance. Unreacted silanol hydroxyl reacts with the hydroxyl-containing polysiloxane, and the obtained compound has more hydroxyl groups with good hydrophilicity, so that the hydrophilic performance of the hydroxyl-containing polysiloxane is increased, and the space structure is further extended and expanded.
(3) Condensation catalyst:
the condensation catalyst is one or more than two combinations which can act together from hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, cesium hydroxide, dibutyl tin dilaurate, stannous octoate, diethyl hydroxylamine, triethyl phosphate, cyclohexanone oxime and potassium acetate.
(4) Silicone resin:
the organic silicon resin is nonlinear siloxane resin, namely MQ silicon resin, and consists of organic silicon compound containing monofunctional siloxane chain units (M groups) and organic silicon compound containing tetrafunctional siloxane chain units (Q groups), wherein the molar ratio of the M groups to the Q groups is selected to be in the range of 0.4: 1-2.5:1.
Preferably, the molar ratio of the M groups to the Q groups in the organic silicon resin ranges from 0.4:1 to 1.1:1.
The MQ silicon resin has high thermal stability and chemical stability, low surface tension and strong foam breaking capability. The MQ silicone resin is composed of M units and Q units, wherein M groups are trimethyl chlorosilane, hexamethyldisiloxane and trimethyl methoxysilane, and Q groups are sodium silicate and tetraethoxysilane. The smaller the M/Q ratio, the greater the molecular weight of the silicone, and the final product is in powder form; the larger the M/Q ratio, the smaller the molecular weight of the silicone resin, even not the resinous structure at last, but only the low-viscosity branched silicone oil, which is of little significance for the defoamer.
(5) Inorganic particles:
the inorganic particles are one or a combination of more than two of silicon dioxide, aluminum oxide, zinc oxide and magnesium oxide. The specific surface area of these materials measured by BET method is 50m 2 And/g.
Further, the preferred inorganic particles are silica, which can be classified according to its standard manufacturing technique into fumed silica and precipitated silica.
The surface of the inorganic particles may be hydrophilic or hydrophobic in order to make the foam control composition sufficiently effective in an aqueous system. The average particle size of the hydrophobic silica is in the range of 0.1 to 20. Mu.m. The silicon dioxide has an important role in the defoamer, is adsorption, has a small particle size, large specific surface area and high demonstration energy, is of a three-dimensional network structure, can form a huge action force for adsorbing bubbles, and can attack the bubbles together with polysiloxane, namely the silicon dioxide adsorbs and impacts the weak points of the bubbles, so that the bubbles are broken under the action of low surface tension of the polysiloxane. Therefore, silica corresponds to "needlepoint" in the defoamer, and is used in small amounts but has a great effect. The active component of the efficient defoaming agent is taken together with polysiloxane, and the efficient defoaming agent has a composite efficient and synergistic defoaming effect. Meanwhile, because of the existence of the silicon dioxide particles, the polysiloxane can be rapidly dispersed in the foaming liquid, so that the dispersion efficiency of the polysiloxane is improved, and the defoaming effect is provided.
Preferably, the silica particles are one or a combination of more than two of hydrophilic silica 383DS, hydrophilic silica HL200, hydrophobic silica H2000, hydrophobic silica R974, hydrophobic silica R972 and hydrophobic silica D10.
If hydrophobic particles are desired for the inorganic particles, this can be achieved by treating the hydrophilic inorganic particles with a treatment agent comprising fatty acids, reactive silanes or siloxanes such as, in particular, stearic acid, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, hydroxyl-terminated and methyl-terminated polydimethylsiloxanes and silicone resins.
(6) Alkaline catalyst:
the alkaline catalyst is one or a combination of more than two of sodium hydroxide, potassium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate.
(7) Water and its preparation method
The water is deionized water.
(8) Organic solvents
The organic solvent is one or more of toluene, xylene and trimethylbenzene.
In order to achieve the second object, the present invention provides the following technical solutions:
the preparation method of the organic silicon defoamer comprises the following steps:
S1, adding water, an organic solvent, a netlike structure agent and a condensation catalyst in a formula amount into a reactor, stirring, raising the temperature and carrying out heat preservation reaction to enable the netlike structure agent to carry out hydrolysis and intermolecular condensation to form a condensation oligosiloxane core cage-type structure;
s2, adding hydroxyl-containing polysiloxane with the formula amount in the step S1, performing condensation reaction to form an octopus structure, and evaporating volatile matters to obtain a viscous oily substance, namely a component XI;
s3, adding the organic solvent, the inorganic particles and the organic silicon resin in the formula amount into the other reactor, stirring, heating and preserving heat until the solid is dissolved to obtain a solution, namely a component;
s4, mixing and stirring the component XI obtained in the step S2 and the component XII obtained in the step S3 in a reactor, adding the alkaline catalyst with the formula amount, stirring, raising the temperature, carrying out heat preservation reaction, and then evaporating the solvent to obtain the organosilicon defoamer.
In the reaction steps of the preparation method:
further, in the step S1, adding water, an organic solvent, a netlike structure agent and a condensation catalyst in a formula amount into a reactor, stirring, increasing the temperature to 40-100 ℃, and keeping the temperature for 0.5-3 h;
Further, in the step S2, the hydroxyl-containing polysiloxane with the formula amount is added, and the condensation reaction is carried out for 2-5 hours;
further, in the step S2, the evaporating temperature of evaporating volatile matters is 40-150 ℃ and the vacuum degree is 0-0.1 MPa;
further, in the step S3, adding the organic solvent, the inorganic particles and the organic silicon resin with the formula amount into another reactor, stirring, heating and preserving the temperature in the range of 60-130 ℃ for 10-60 min;
further, in the step S4, after adding the basic catalyst with the formula amount, stirring, raising the temperature to react at 50-200 ℃ for 3-8 hours, and then evaporating the solvent to obtain the organosilicon defoamer.
Further, in the step S4, the evaporating temperature of the evaporating solvent is 40-150 ℃ and the vacuum degree is 0-0.1 MPa.
The organic silicon defoamer obtained by the invention can be used for preparing internal-added defoamers and is used in systems such as metal processing liquid, laundry liquid, printing ink and the like.
The organic silicon defoamer has the beneficial effects that:
(1) The organic silicon defoamer of the invention is prepared by hydrolyzing silicon alkoxy into silanol hydroxyl in water by a netlike structure agent containing at least one silane with a trialkoxy structure, and condensing the silanol hydroxyl under the action of a condensation catalyst; in particular, the trialkoxysilane has three silanol hydroxyl structures after hydrolysis, the hydroxyl is unstable, under the action of a condensation catalyst and heating, intermolecular silanol hydroxyl is dehydrated and condensed, and a cage-shaped structure with a complicated three-dimensional net-shaped space structure can be formed, and the silanol hydroxyl which is not dehydrated and condensed exists in the polymers due to space effect, and the silanol hydroxyl has better hydrophilicity. The polymer with the cage structure is condensed with silanol hydroxyl on the hydroxyl-containing polysiloxane to connect the cage structure and the hydroxyl-containing polysiloxane together to form a more huge structure similar to octopus; the hydrophilic silanol hydroxyl groups in the molecules are staggered, so that the hydrophilicity of a polysiloxane structure formed by the hydroxyl-containing polysiloxane is enhanced, and the defoaming performance is improved.
(2) In the network structure agent, the alkyl substituent group is provided with hydrophilic groups such as hydroxyl, amino, oxygen heterocyclic group, nitrogen heterocyclic group and amide group, so that the hydrophilic property of the polysiloxane structure can be increased, and the defoaming performance can be improved.
(3) Inorganic particles, especially silicon dioxide, have an important role in the defoamer, namely adsorption, and because of the small particle size, large specific surface area and high demonstration energy and the three-dimensional network structure, the silicon dioxide can form a huge acting force for adsorbing bubbles, and the silicon dioxide and polysiloxane attack the bubbles together, namely the silicon dioxide adsorbs and impacts the weak points of the bubbles, so that the bubbles are broken under the action of low surface tension of the polysiloxane. Therefore, silica corresponds to "needlepoint" in the defoamer, and is used in small amounts but has a great effect. The active component of the efficient defoaming agent is taken together with polysiloxane, and the efficient defoaming agent has a composite efficient and synergistic defoaming effect. Meanwhile, because of the existence of the silicon dioxide particles, the polysiloxane can be rapidly dispersed in the foaming liquid, so that the dispersion efficiency of the polysiloxane is improved, and the defoaming effect is provided.
(4) The organic silicon defoamer provided by the invention has the advantages of high thermal stability and chemical stability of MQ silicon resin, low surface tension and strong foam breaking capability. The organic silicon resin and the inorganic particles are heated and dissolved in toluene, and the solid particles are fully dissolved, so that the inorganic particles can be well embedded into the organic silicon resin, and the inorganic particles can be well dispersed and uniformly mixed, so that the defoaming effect of the silicon resin and the inorganic particles is fully improved.
(5) In order to better utilize the defoaming performance of inorganic particles, the organic silicon defoaming agent combines a similar octopus structure with good hydrophilicity with organic silicon resin dissolved with inorganic particles, firmly embeds inorganic particle particles with defoaming effect into the similar octopus structure, and has good stability in the storage and use processes, wherein the inorganic particles are not easy to agglomerate.
(6) The preparation method of the organic silicon defoamer provided by the invention has the advantages that the organic silicon defoamer has good hydrophilicity, is not easy to agglomerate when sheared, and meanwhile, inorganic particles are not easy to separate out, so that the durability of the defoaming function is maintained.
According to the invention, the structure of the carrier polysiloxane is researched and designed, inorganic particles are embedded into the carrier polysiloxane through the cage structure of the polysiloxane, and different cage structures are connected through the polysiloxane, so that a polysiloxane composition similar to an octopus structure is formed, and the polysiloxane with the structure solves the problems of hydrophilicity and defoaming durability of common silicone paste.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Wherein, the specific molecular formula of the hydroxyl-containing polysiloxane represented by the abbreviation code in the examples is as follows:
A-1：[Me 2 (OH)SiO 1/4 ] 2 [Me 2 SiO 2/4 ] 80 [Me(OH)SiO 2/4 ] 3 the dynamic viscosity at 25℃is 157 mPas;
A-2：[Me 3 SiO 1/4 ] 3 [Me 2 SiO 2/4 ] 2000 [Me(OH)SiO 2/4 ] 35 [MeSiO 3/4 ] 1 [SiO 4/4 ] 2 the dynamic viscosity at 25℃was 15,000 mPas;
A-3：[(C 6 H 5 ) 2 (OH)SiO 1/4 ] 4 [Me 2 SiO 2/4 ] 25000 [Me(OH)SiO 2/4 ] 50 [SiO 4/4 ]the dynamic viscosity at 25℃was 65,800 mPa.s;
A-4：[(CH 2 ＝CH) 2 (OH)SiO 1/4 ] 2 [Me 2 SiO 2/4 ] 34000 [Me(OH)SiO 2/4 ] 50 [MeSiO 3/4 ]the dynamic viscosity at 25℃was 95,730 mPas;
A-5：[(C 8 H 17 ) 2 (OH)SiO 1/4 ] 3 [Me 2 SiO 2/4 ] 3 [Me(OH)SiO 2/4 ] 1 [MeSiO 3/4 ] 1 the dynamic viscosity at 25℃was 15 mPas.
Example 1:
5 parts of water, 50 parts of toluene, 12 parts of butyl triethoxysilane and 0.2 part of condensation catalyst potassium hydroxide are added into a reaction bottle, and the mixture is stirred, the temperature is raised to 40 ℃ and the temperature is kept for 3 hours, so that the butyl triethoxysilane undergoes hydrolysis and intermolecular condensation reaction to form a condensation oligomeric siloxane core 'cage' -shaped structure.
Then 67.3 parts of hydroxyl-containing polysiloxane A-1 is added into the structure, condensation reaction is further carried out for 3 hours, a structure with a similar core as octopus is formed, and volatile matters are distilled out, so that a viscous oily component XI is obtained;
50 parts of toluene, 5 parts of hydrophilic silica 383DS and 10 parts of methyl MQ silicone resin (M: Q molar ratio is 0.66:1) are added into another reaction bottle, and the temperature is raised to 100 ℃ and stirred until the solid is dissolved, so that a component XII is obtained;
component XI and component XII were added to a flask, stirring was started, and 0.5 part of cesium hydroxide as a basic catalyst was added, and after reacting at 55℃for 7.5 hours, the solvent was distilled off under reduced pressure to obtain silicone antifoaming agent CP1.
Example 2:
10 parts of water, 50 parts of dimethylbenzene, 10 parts of trimethylethoxysilane, 15 parts of dibutylaminomethyl tributoxy silane and 2 parts of condensation catalyst cyclohexanone oxime are added into a reaction bottle, and the mixture is stirred, heated to 75 ℃ and kept for 2 hours, so that the dimethyldiethoxy silane and the dibutylaminomethyl tributoxy silane undergo hydrolysis and intermolecular condensation reaction to form a condensation oligosiloxane core cage-type structure.
Then 48.5 parts of hydroxyl-containing polysiloxane A-2 is added into the structure, condensation reaction is further carried out for 2 hours, a core octopus structure is formed, and finally volatile matters are distilled out, so that a transparent viscous liquid component XI is obtained;
60 parts of dimethylbenzene, 10 parts of hydrophilic silicon dioxide HL200 and 4 parts of methyl MQ silicon resin (M: Q molar ratio is 0.45:1) are added into another reaction bottle, and the mixture is heated to 125 ℃ and stirred until solids are dissolved, so that a component XII is obtained;
component XI and component XII were added to a flask, stirring was started, and 1 part of potassium hydroxide as an alkaline catalyst was added, and after reacting at 135℃for 5 hours, the solvent was distilled off under reduced pressure to obtain silicone antifoaming agent CP2.
Example 3:
10 parts of water, 50 parts of dimethylbenzene, 10 parts of phenyl trimethoxysilane, 5 parts of dimethyl dimethoxy silane, 35 parts of amino ethyl amino propyl trimethoxysilane and 0.5 part of stannous octoate as a condensation catalyst are added into a reaction bottle, and the reaction bottle is stirred, heated to 95 ℃ and kept for 0.5h, so that the phenyl trimethoxysilane, the dimethyl dimethoxy silane and the amino ethyl amino propyl trimethoxysilane undergo hydrolysis and intermolecular condensation reaction to form a condensation oligosiloxane core cage-type structure.
Then adding 21 parts of hydroxyl-containing polysiloxane A-3 into the structure, further carrying out condensation reaction for 4.5 hours to form a core octopus structure, and finally evaporating volatile matters to obtain a transparent viscous liquid component XI;
60 parts of benzene, 10 parts of hydrophobic silicon dioxide H2000 and 8 parts of methyl MQ silicone resin (M: Q molar ratio is 0.8:1) are added into another reaction bottle, and the temperature is raised to 65 ℃ and stirred until the solid is dissolved, so that a component XII is obtained;
component XI and component XII were added to the flask, stirring was started, and 2 parts of sodium bicarbonate as a basic catalyst was added, and after 3 hours of reaction at 195℃the solvent was distilled off under reduced pressure to give silicone defoamer CP3.
Example 4:
adding 0.5 part of water, 80 parts of toluene, 10 parts of methyltrimethoxysilane, 15 parts of tetraethoxysilane and 1 part of condensing catalyst tetramethylammonium hydroxide into a reaction bottle, stirring, raising the temperature to 65 ℃ and preserving the heat for 1.5 hours, so that the methyltrimethoxysilane and the tetraethoxysilane undergo hydrolysis and intermolecular condensation reaction to form a condensation oligosiloxane core cage-type structure.
Then, 70 parts of hydroxyl-containing polysiloxane A-4 is added into the structure, condensation reaction is further carried out for 3.5 hours, a core octopus structure is formed, and finally volatile matters are distilled out, so that a transparent viscous liquid component XI is obtained;
60 parts of toluene, 3 parts of hydrophobic silica R974 and 0.5 part of methyl MQ silicone resin (M: Q molar ratio is 1.1:1) are added into another reaction bottle, and the mixture is heated to 85 ℃ and stirred until solid is dissolved, so that a component XII is obtained;
component XI and component XII were added to the flask, stirring was started, and 0.02 part of cesium hydroxide as a basic catalyst was added, and after reacting at 135℃for 4.5 hours, the solvent was distilled off under reduced pressure to obtain silicone antifoaming agent CP4.
Example 5:
5 parts of water, 100 parts of toluene, 3 parts of trivinylbutoxysilane, 10 parts of phenyltrimethoxysilane and 1 part of tetramethyl ammonium hydroxide as a condensation catalyst are added into a reaction bottle, and the mixture is stirred, heated to 80 ℃ and kept for 3 hours, so that the trivinylbutoxysilane and the phenyltrimethoxysilane undergo hydrolysis and intermolecular condensation reaction to form a condensation oligosiloxane core cage-type structure.
Then, adding 45 parts of hydroxyl-containing polysiloxane A-5 and 25 parts of hydroxyl-containing polysiloxane A-2 into the structure, and further carrying out condensation reaction for 4 hours to form a core octopus structure, and finally evaporating volatile matters to obtain a transparent viscous liquid component XI;
60 parts of dimethylbenzene, 5 parts of hydrophobic silicon dioxide R972 and 5 parts of methyl MQ silicon resin (M: Q molar ratio is 0.75:1) are added into another reaction bottle, and the mixture is heated to 120 ℃ and stirred until solids are dissolved, so that a component XII is obtained;
Component XI and component XII were added to the flask, stirring was started, and 1 part of cesium hydroxide as a basic catalyst was added, and after reacting at 155℃for 3 hours, the solvent was distilled off under reduced pressure to obtain silicone antifoaming agent CP5.
Example 6:
2 parts of water, 75 parts of toluene, 7 parts of methyltriethoxysilane, 10 parts of phenyltrimethoxysilane and 1 part of condensation catalyst triethyl phosphate are added into a reaction bottle, and the mixture is stirred, heated to 90 ℃ and kept for 3 hours, so that the methyltriethoxysilane and the phenyltrimethoxysilane undergo hydrolysis and intermolecular condensation reaction to form a condensation oligosiloxane core cage-type structure.
Then, adding 20 parts of hydroxyl-containing polysiloxane A-1 and 50 parts of hydroxyl-containing polysiloxane A-4 into the structure, further carrying out condensation reaction for 2.5 hours to form a core octopus structure, and finally evaporating volatile matters to obtain a transparent viscous liquid component XI;
30 parts of dimethylbenzene, 4 parts of hydrophobic silicon dioxide D10 and 4 parts of methyl MQ silicon resin (M: Q molar ratio is 0.65:1) are added into another reaction bottle, and the mixture is heated to 100 ℃ and stirred until solids are dissolved, so that a component XII is obtained;
component XI and component XII were added to the flask, stirring was started, and 2 parts of sodium carbonate as an alkaline catalyst was added, and after reacting at 65℃for 7 hours, the solvent was distilled off under reduced pressure to obtain silicone antifoaming agent CP6.
Example 7:
2 parts of water, 75 parts of toluene, 17 parts of hydroxymethyl triethoxysilane and 1 part of condensation catalyst triethyl phosphate are added into a reaction bottle, and the mixture is stirred, the temperature is increased to 90 ℃ and kept for 2.5 hours, so that the hydroxymethyl triethoxysilane undergoes hydrolysis and intermolecular condensation reaction to form a condensation oligomeric siloxane core cage-type structure.
Then adding 50 parts of hydroxyl-containing polysiloxane A-4 into the structure, further carrying out condensation reaction for 2 hours to form a core octopus structure, and finally evaporating volatile matters to obtain a transparent viscous liquid component XI;
30 parts of dimethylbenzene, 4 parts of hydrophobic silicon dioxide D10 and 5 parts of methyl MQ silicon resin (M: Q molar ratio is 0.65:1) are added into another reaction bottle, and the mixture is heated to 95 ℃ and stirred until solids are dissolved, so that a component XII is obtained;
component XI and component XII were added to a flask, stirring was started, and 0.3 part of sodium hydroxide as a basic catalyst was added, and after reacting at 50℃for 6 hours, the solvent was distilled off under reduced pressure to obtain silicone antifoaming agent CP7.
Example 8:
2 parts of water, 75 parts of toluene, 10 parts of hydroxymethyl triethoxysilane, 10 parts of methyl triethoxysilane and 0.1 part of condensation catalyst sulfuric acid are added into a reaction bottle, and the reaction bottle is stirred, heated to 90 ℃ and kept for 3 hours, so that the hydroxymethyl triethoxysilane and the phenyl trimethoxysilane undergo hydrolysis and intermolecular condensation reaction to form a condensation oligosiloxane core cage-type structure.
Then, adding 20 parts of hydroxyl-containing polysiloxane A-1 and 50 parts of hydroxyl-containing polysiloxane A-4 into the structure, further carrying out condensation reaction for 2.5 hours to form a core octopus structure, and finally evaporating volatile matters to obtain a transparent viscous liquid component XI;
30 parts of dimethylbenzene, 4 parts of hydrophobic silicon dioxide D10 and 4 parts of methyl MQ silicon resin (M: Q molar ratio is 0.65:1) are added into another reaction bottle, and the mixture is heated to 100 ℃ and stirred until solids are dissolved, so that a component XII is obtained;
component XI and component XII were added to the flask, stirring was started, and 2 parts of sodium carbonate as an alkaline catalyst was added, and after reacting at 65℃for 7 hours, the solvent was distilled off under reduced pressure to obtain silicone antifoaming agent CP8.
Example 9:
2 parts of water, 75 parts of toluene, 22 parts of morpholinomethyl triisopropoxy silane and 1 part of condensation catalyst triethyl phosphate are added into a reaction bottle, and the mixture is stirred, heated to 90 ℃ and kept for 3 hours, so that the morpholinomethyl triisopropoxy silane undergoes hydrolysis and intermolecular condensation reaction to form a condensation oligosiloxane core cage-type structure.
Then, adding 20 parts of hydroxyl-containing polysiloxane A-1 and 30 parts of hydroxyl-containing polysiloxane A-4 into the structure, further carrying out condensation reaction for 2.5 hours to form a core octopus structure, and finally evaporating volatile matters to obtain a transparent viscous liquid component XI;
Adding 30 parts of dimethylbenzene, 3 parts of hydrophilic silicon dioxide HL200 and 4 parts of methyl MQ silicon resin (M: Q molar ratio is 0.65:1) into another reaction bottle, heating to 100 ℃ and stirring until solid is dissolved to obtain a component XII;
component XI and component XII were added to the flask, stirring was started, and 2 parts of sodium carbonate as an alkaline catalyst was added, and after reacting at 65℃for 7 hours, the solvent was distilled off under reduced pressure to obtain silicone antifoaming agent CP9.
Comparative example 1:
5 parts of water, 75 parts of toluene, 5 parts of butyltriethoxysilane and 1 part of condensation catalyst triethyl phosphate are added into a reaction bottle, and the mixture is stirred, the temperature is increased to 90 ℃ and the mixture is kept for 3 hours, so that the butyltriethoxysilane undergoes hydrolysis and intermolecular condensation reaction to form a condensation oligomeric siloxane core cage-type structure.
Then, adding 20 parts of hydroxyl-containing polysiloxane A-1 and 50 parts of hydroxyl-containing polysiloxane A-4 into the structure, further carrying out condensation reaction for 2.5 hours to form a core octopus structure, and finally evaporating volatile matters to obtain a transparent viscous liquid component XI;
30 parts of dimethylbenzene, 8 parts of hydrophobic silicon dioxide D10 and 9 parts of methyl MQ silicon resin (M: Q molar ratio is 0.65:1) are added into another reaction bottle, and the mixture is heated to 100 ℃ and stirred until solids are dissolved, so that a component XII is obtained;
Component XI and component XII were added to a flask, stirring was started, and 2 parts of sodium carbonate as an alkaline catalyst was added, and after reacting at 65℃for 7 hours, the solvent was distilled off under reduced pressure to obtain silicone antifoaming agent CP6-1.
Comparative example 2:
adding 10 parts of water, 75 parts of toluene and 1 part of condensation catalyst triethyl phosphate into a reaction bottle, stirring, raising the temperature to 90 ℃ and preserving heat for reaction for 3 hours, then adding 20 parts of hydroxyl-containing polysiloxane A-1 and 50 parts of hydroxyl-containing polysiloxane A-4 into the reaction bottle, further reacting for 2.5 hours, and finally evaporating volatile matters to obtain a transparent viscous liquid component XI;
30 parts of dimethylbenzene, 8 parts of hydrophobic silicon dioxide D10 and 9 parts of methyl MQ silicon resin (M: Q molar ratio is 0.65:1) are added into another reaction bottle, and the mixture is heated to 100 ℃ and stirred until solids are dissolved, so that a component XII is obtained;
component XI and component XII were added to a flask, stirring was started, and 2 parts of sodium carbonate as an alkaline catalyst was added, and after reacting at 65℃for 7 hours, the solvent was distilled off under reduced pressure to obtain silicone antifoaming agent CP6-2.
Comparative example 3:
5 parts of water, 75 parts of toluene, 30 parts of methyltriethoxysilane, 30 parts of phenyltrimethoxysilane and 1 part of condensation catalyst triethyl phosphate are added into a reaction bottle, and the mixture is stirred, heated to 90 ℃ and kept for 3 hours, so that the methyltriethoxysilane and the phenyltrimethoxysilane undergo hydrolysis and intermolecular condensation reaction to form a condensation oligosiloxane core cage-type structure.
Then, adding 20 parts of hydroxyl-containing polysiloxane A-1 and 50 parts of hydroxyl-containing polysiloxane A-4 into the structure, further carrying out condensation reaction for 2.5 hours to form a core octopus structure, and finally evaporating volatile matters to obtain a transparent viscous liquid component XI;
30 parts of dimethylbenzene, 8 parts of hydrophobic silicon dioxide D10 and 9 parts of methyl MQ silicon resin (M: Q molar ratio is 0.65:1) are added into another reaction bottle, and the mixture is heated to 100 ℃ and stirred until solids are dissolved, so that a component XII is obtained;
component XI and component XII were added to a flask, stirring was started, and 2 parts of sodium carbonate as an alkaline catalyst was added, and after reacting at 65℃for 7 hours, the solvent was distilled off under reduced pressure to obtain silicone antifoaming agent CP6-3.
Comparative example 4:
5 parts of water, 75 parts of toluene, 15 parts of tributyl ethoxysilane, 15 parts of dimethyl dibutoxy silane, 15 parts of tetraethoxy silane and 1 part of triethyl phosphate serving as a condensation catalyst are added into a reaction bottle, and the mixture is stirred, the temperature is increased to 90 ℃ and kept for 3 hours, so that the tributyl ethoxysilane, the dimethyl dibutoxy silane and the tetraethoxy silane undergo hydrolysis and intermolecular condensation reactions to obtain a polymer.
Then, adding 20 parts of hydroxyl-containing polysiloxane A-1 and 50 parts of hydroxyl-containing polysiloxane A-4 into the structure, further carrying out condensation reaction for 2.5 hours to form a core octopus structure, and finally evaporating volatile matters to obtain a transparent viscous liquid component XI;
30 parts of dimethylbenzene, 8 parts of hydrophobic silicon dioxide D10 and 9 parts of methyl MQ silicon resin (M: Q molar ratio is 0.65:1) are added into another reaction bottle, and the mixture is heated to 100 ℃ and stirred until solids are dissolved, so that a component XII is obtained;
component XI and component XII were added to a flask, stirring was started, and 2 parts of sodium carbonate as an alkaline catalyst was added, and after reacting at 65℃for 7 hours, the solvent was distilled off under reduced pressure to obtain silicone antifoaming agent CP6-4.
Comparative example 5:
5 parts of water, 75 parts of toluene, 7 parts of methyltriethoxysilane, 10 parts of phenyltrimethoxysilane and 1 part of condensation catalyst triethyl phosphate are added into a reaction bottle, and the mixture is stirred, heated to 90 ℃ and kept for 3 hours, so that the methyltriethoxysilane undergoes hydrolysis and intermolecular condensation reaction to form a condensation oligosiloxane core cage-type structure.
Then, adding 20 parts of hydroxyl-containing polysiloxane A-1 and 50 parts of hydroxyl-containing polysiloxane A-4 into the structure, further condensing for 2.5 hours to form a core octopus structure, and finally evaporating volatile matters to obtain a transparent viscous liquid component XI;
30 parts of dimethylbenzene and 9 parts of methyl MQ silicone resin (molar ratio of M to Q is 0.65:1) are directly added into the component XI of the reaction bottle, and the mixture is stirred and heated to 100 ℃ to dissolve solids; obtaining a component XII;
And (3) stirring the component XII in the last step, adding 2 parts of alkaline catalyst sodium carbonate, reacting for 7 hours at 65 ℃, and then evaporating the solvent under reduced pressure to obtain the organosilicon defoamer CP6-5.
Comparative example 6:
5 parts of water, 75 parts of toluene, 7 parts of methyltriethoxysilane, 10 parts of phenyltrimethoxysilane and 1 part of condensation catalyst triethyl phosphate are added into a reaction bottle, and the mixture is stirred, heated to 90 ℃ and kept for 3 hours, so that the methyltriethoxysilane undergoes hydrolysis and intermolecular condensation reaction to form a condensation oligosiloxane core cage-type structure.
Then, adding 20 parts of hydroxyl-containing polysiloxane A-1 and 50 parts of hydroxyl-containing polysiloxane A-4 into the structure, further condensing for 2.5 hours to form a core octopus structure, and finally evaporating volatile matters to obtain a transparent viscous liquid component XI;
adding 30 parts of dimethylbenzene and 8 parts of hydrophobic silicon dioxide D10 into the component XI of the reaction bottle in the previous step, stirring and heating to 100 ℃ to dissolve solids; obtaining a component XII;
and adding 2 parts of alkaline catalyst sodium carbonate into the component XII, stirring, reacting at 65 ℃ for 7 hours, and then evaporating the solvent under reduced pressure to obtain the organosilicon defoamer CP6-6.
Comparative example 7:
silicone defoamers CP6-7 were prepared according to example 1 of patent US 4639489.
Comparative example 8:
silicone defoamers CP6-8 were prepared according to example 1 of patent WO2018024859A 1.
Performance test and comparative experiment of the defoamer
In order to verify the excellent performance of the silicone defoamer according to the present invention, the silicone defoamers in the above examples and comparative examples were prepared as emulsions by the following method:
30 parts of the silicone defoamer prepared in the examples or comparative examples (comparative examples CP1 to CP9, examples CP6-1 to 8), 10 parts of span 60 and 10 parts of tween were added to a vessel, stirring was started and mixed at a rotation speed of 500rpm for 20 minutes, then 60 parts of water was slowly added and ground into an emulsion of a target particle size by a colloid mill, finally an alkali-swellable thickener was added to adjust the viscosity, and silicone defoamer emulsions ECP (1 to 9) and ECP6- (1 to 8) were obtained, respectively.
Performance test experiment one:
the resulting emulsions ECP 1-ECP 9 and ECP 6-1-8 were each tested as follows:
in 2 wt% of sodium dodecylbenzenesulfonate+2 wt%NP10A +96 (wt)% water mixture was used as the test medium and was tested by shake flask. After 50ml of test medium was added to the shaking flask at room temperature, 30. Mu.L of defoamer emulsion was added, and vertical shaking was started up and down for 50 times, and the time for the foam to see the liquid surface was recorded. The shorter the time, the faster the defoaming speed. And the precipitation in the shake flask after shaking was recorded, and the more "+" indicated the less precipitation. The test results are shown in table 1:
Table 1 results of experiments comparing the foam eliminating and inhibiting properties and stability of the emulsion
| Sample name | Defoaming time/s | Precipitation in shake flask after shaking |
| ECP1 | 15 | ++++ |
| ECP2 | 20 | +++++ |
| ECP3 | 18 | +++++ |
| ECP4 | 23 | ++++ |
| ECP5 | 7 | ++++ |
| ECP6 | 10 | +++++ |
| ECP7 | 11 | ++++ |
| ECP8 | 13 | +++++ |
| ECP9 | 15 | ++++ |
| ECP6-1 | 55 | ++ |
| ECP6-2 | 40 | ++ |
| ECP6-3 | 160 | ++++ |
| ECP6-4 | 79 | + |
| ECP6-5 | 95 | ++ |
| ECP6-6 | 105 | + |
| ECP6-7 | 120 | + |
| ECP6-8 | 50 | + |
Performance test experiment II:
2 (wt)% of organosilicon defoamer emulsion ECP 1-ECP 9 and ECP 6-1-8 are added into the total synthesis cutting fluid, and then the total synthesis cutting fluid is put into a 50 ℃ oven for aging for 4 weeks, and the precipitation and floating conditions in the total synthesis cutting fluid are observed, and the results are shown in Table 2:
table 2 results of compatibility comparison experiments of emulsions with fully synthetic cutting fluids
| Sample name | Appearance of cutting fluid | Precipitation of cutting fluid level |
| ECP1 | Transparent and transparent | A little white oil spot |
| ECP2 | Transparent and transparent | A little white oil spot |
| ECP3 | Transparent and transparent | A little white oil spot |
| ECP4 | Semitransparent light | A little white oil spot |
| ECP5 | Transparent and transparent | A little white oil spot |
| ECP6 | Transparent and transparent | A little white oil spot |
| ECP7 | Transparent and transparent | A little white oil spot |
| ECP8 | Transparent and transparent | A little white oil spot |
| ECP9 | Transparent and transparent | A little white oil spot |
| ECP6-1 | Semitransparent light | White float |
| ECP6-2 | Semitransparent light | White float |
| ECP6-3 | Transparent and transparent | White float |
| ECP6-4 | Semitransparent light | White float |
| ECP6-5 | Semitransparent light | White float |
| ECP6-6 | Cloudiness | A little white oil spot |
| ECP6-7 | Cloudiness | White float |
| ECP6-8 | Cloudiness | White float |
Analysis and discussion of test experiment results:
as can be seen from the test experimental data in Table 1, the defoaming performance of the silicone defoamer prepared by the methods of examples 1 to 6 is obviously better, and when the network structure agent contains hydrophilic groups, namely the silicone defoamer prepared by the methods of examples 7 to 9 contains a certain amount of hydrophilic groups, the hydrophilic and hydrophobic properties of the defoamer are balanced, namely the silicone defoamer is extremely better in defoaming performance and excellent in compatibility. In the comprehensive view, the organic silicon defoamer prepared by the method has good defoaming performance and self stability, on one hand, the hydrophilic nature of cage-type structures brought by the netlike structure agent, and after condensation with hydroxyl-containing polysiloxane, the comprehensive performance of the polymer is more remarkable, so that the polymer is stable and the defoaming performance is increased; in addition, the foam breaking capability of the organic silicon resin and the firmly embedded foam puncturing effect of the inorganic particles enable the overall system to have better hydrophilicity and longer defoaming performance.
In contrast, the defoaming speed of the resulting silicone defoamer significantly decreased after less or no network agent was removed in comparative examples 1 and 2; in the comparative example 3, the reticular structure agent is too much, the hydrophilicity is particularly good, but inorganic particles are easy to separate out and aggregate, and the defoaming performance is affected; the network structure agent in comparative example 4 does not contain silane with trialkoxy structure, so that the defoaming performance is poor, and the important role of the network structure agent in the defoaming agent is fully illustrated; the defoamer prepared in comparative example 5, without the addition of inorganic particles, was also much inferior in performance; however, in comparative example 6, the effect of embedding inorganic particles in the polysiloxane composition was insufficient without adding the silicone resin, resulting in significant deterioration of defoaming property; the silicone defoamers prepared by the conventional methods in comparative examples 7 and 8 are also significantly insufficient in performance.
In summary, it can be shown that the polysiloxane structure composition containing the structure similar to the octopus, which is designed by the patent, has good hydrophilicity and good stability, and the stability of the whole system is also good, so that the defoaming is longer, and the improvement of the defoaming performance is particularly facilitated.
From the results of the compatibility experiments of the defoamer emulsion and the fully synthetic cutting fluid in table 2, it can be seen that the emulsions of the silicone defoamers ECP1 to ECP9 prepared by the method of the present invention all exhibit excellent compatibility, which is mainly attributed to the fact that the silicone composition with the octopus structure prepared by a series of reactions of the network structure agent has good hydrophilicity.
In the comparative examples, however, none of the comparative examples 1, 2 and 4 used a network structure agent or had little or no silane structure containing a trialkoxy structure, and did not give good performance; in comparative example 3, inorganic particles are easily precipitated due to excessive amount of the network structure agent, which affects the deterioration of the performance; comparative examples 5 and 6 also illustrate that the special structure of the octopus structure is provided with the organic silicon resin and the inorganic particles, and the special structure has better assistance effect to a certain extent; comparing the effect of the defoamers of comparative examples 7 and 8, the silicone defoamers of the present invention all have significant improvements.
Claims (7)
1. The preparation method of the organic silicon defoamer is characterized by comprising the following raw materials in parts by weight: hydroxyl-containing polysiloxanes: 20-70 parts; the net-shaped structural agent comprises the following components: 10-50 parts; condensation catalyst: 0.1 to 2 parts; silicone resin: 0.5 to 10 parts; inorganic particles: 3-10 parts; alkaline catalyst: 0.01 to 2 parts; water: 0.5 to 10 parts; organic solvent: 20-70 parts; the network structure agent is silane which can react with the hydroxyl-containing polysiloxane to form a network structure after hydrolysis and condensation reaction; the molecular formula of the hydroxyl-containing polysiloxane is shown as formula I:
[R 1 x (OH) y SiO 1/4 ] a [Me 2 SiO 2/4 ] b [Me(OH)SiO 2/4 ] c [MeSiO 3/4 ] d
[SiO 4/4 ] e I
Wherein subscript x=2 or 3, y=0 or 1, and x+y=3; subscript a, b, c, d, e is the minimum of the four mer number and has at least one hydroxyl group on the side chain;
substituent R in formula I 1 Is a hydrocarbon group containing no functional group or a hydrocarbon group containing a substituent of a functional group and having 1 to 12 carbon atoms, and the substituent R 1 May be the same or different;
the hydroxyl-containing polysiloxane is one or more than two of compounds with the structure shown in the formula I;
the preparation method of the organic silicon defoamer comprises the following steps:
s1, adding water, an organic solvent, a netlike structure agent and a condensation catalyst in a formula amount into a reactor, stirring, raising the temperature and carrying out heat preservation reaction to enable the netlike structure agent to carry out hydrolysis and intermolecular condensation to form a condensation oligosiloxane core cage-type structure;
s2, adding hydroxyl-containing polysiloxane with the formula amount in the step S1, performing condensation reaction to form an octopus structure, and evaporating volatile matters to obtain a viscous oily substance, namely a component XI;
s3, adding the organic solvent, the inorganic particles and the organic silicon resin in the formula amount into the other reactor, stirring, heating and preserving heat until the solid is dissolved to obtain a solution, namely a component;
S4, mixing and stirring the component XI obtained in the step S2 and the component XII obtained in the step S3 in a reactor, adding a formula amount of alkaline catalyst, stirring, raising the temperature, carrying out heat preservation reaction, and then evaporating out a solvent to obtain the organosilicon defoamer;
the molecular formula of the net-shaped structural agent is shown as formula II:
(R 2 ) f —Si—(OR 3 ) g II type
Wherein R is 2 Is one of hydrocarbon groups with 1-18 carbon atoms and hydrocarbon groups containing hydrophilic groups;
wherein R is 3 Is a hydrocarbon group having 1 to 10 carbon atoms;
wherein, the subscript f takes the values of 0, 1, 2 and 3; g takes values of 1, 2, 3 and 4, and satisfies f+g=4;
the network structure agent is a composition of one or more than two silanes shown in a formula II, and at least comprises a silane with a trialkoxy structure.
2. The method for producing an organosilicon defoamer according to claim 1, wherein the viscosity of the hydroxyl-containing polysiloxane is 5 to 100000 mPa-s; the R is 1 The hydrocarbon group without functional group is one of alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl and aralkyl; the R is 1 The hydrocarbyl containing functional group substituent is one of halogen substituted hydrocarbyl and cyano substituted hydrocarbyl.
3. The method for preparing the organic silicon defoamer according to claim 2, wherein,
The alkyl is one of methyl, ethyl, propyl, butyl, hexyl or octyl;
the cycloalkyl is one of cyclopentyl and cyclohexyl;
the alkenyl is one of vinyl, allyl or propenyl;
the cycloalkenyl is cyclohexenyl;
the aryl is one of phenyl and methylphenyl;
the aralkyl is one of benzyl and phenethyl;
the halogen substituted hydrocarbyl is chloromethyl;
the cyano-substituted hydrocarbon group is one of 3, 3-trifluoropropyl and 2-cyanoethyl.
4. The method for preparing the organic silicon defoamer according to claim 1, wherein, the network structure agent is trimethylmethoxysilane, triethylmethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, trihexylmethoxysilane, trioctylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, tributylethoxysilane, trihexylethoxysilane, trioctylethoxysilane, trimethylbutoxysilane, triethylbutoxysilane, tripropbutoxysilane, tributylbutoxysilane, trihexylbutoxysilane, trioctylbutoxysilane, trivinylmethoxysilane, trivinylethoxysilane, triethylbutoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylbutoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, dihexyldimethoxysilane, dioctyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dibutyldiethoxysilane, dihexyldiethoxysilane, dioctyldiethoxysilane, dimethyldibutoxysilane, diethyldibutoxysilane, dipropyldibutoxysilane, dibutyldibutoxysilane, dihexyldibutoxysilane, dioctyl, divinyldimethoxysilane, divinyl diethoxysilane, diethyldimethoxysilane, diethylethoxysilane, one or more of hexyltrimethoxysilane, octyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, methylttributoxysilane, ethyltributoxysilane, propyltributoxysilane, butyltributoxysilane, hexyltributoxysilane, octyltributoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, tetraethoxysilane, hydroxymethyl trimethoxysilane, hydroxymethyl triethoxysilane, trimethylaminomethoxysilane, dibutylaminomethyl tributoxysilane, cyclohexylaminomethyltrimethoxysilane, cyclohexylaminomethyltriethoxysilane, aminoethylaminopropyl trimethoxysilane, aminoethylaminopropyl triethoxysilane, 3-dimethylaminopropyl aminomethyltrimethoxysilane, morpholinomethyltrialkoxysilane, dibutylaminomethyltriethoxysilane, morpholinomethyl triisopropoxysilane, morpholinomethyl triethoxysilane, and silanes containing at least one trialkoxy structure.
5. The method for preparing the organic silicon defoamer according to claim 1, wherein the condensation catalyst is one of hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, cesium hydroxide, dibutyltin dilaurate, stannous octoate, diethylhydroxylamine, triethyl phosphate, cyclohexanone oxime, potassium acetate or a combination of two or more of them capable of acting together; the organic silicon resin is nonlinear siloxane resin, namely MQ silicon resin, and consists of an organic silicon compound containing a monofunctional siloxane chain unit M group and an organic silicon compound containing a tetrafunctional siloxane chain unit Q group, wherein the molar ratio of the M group to the Q group is selected to be 0.4:1-2.5:1;
the inorganic particles are one or a combination of more than two of silicon dioxide, aluminum oxide, zinc oxide and magnesium oxide; the alkaline catalyst is one or a combination of more than two of sodium hydroxide, potassium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate;
the organic solvent is one or more of toluene, xylene and trimethylbenzene.
6. The method for preparing the organic silicon defoamer according to claim 1, wherein in the step S1, the formula amount of water, the organic solvent, the network structure agent and the condensation catalyst are added into a reactor, the stirring and the temperature raising range is 40-100 ℃, and the heat preservation reaction time is 0.5-3 hours;
In the step S2, hydroxyl-containing polysiloxane with the formula amount is added, and the condensation reaction is carried out for 2-5 hours;
in the step S3, adding organic solvent, inorganic particles and organic silicon resin with the formula amount into another reactor, stirring, heating and preserving heat for 10-60 min at the temperature of 60-130 ℃;
in the step S4, after adding the basic catalyst with the formula amount, stirring and raising the temperature for reaction to 50-200 ℃,
the reaction time is 3-8 h, and then the solvent is distilled off, thus obtaining the organosilicon defoamer.
7. The method for producing an organosilicon defoamer according to claim 1, wherein in the step S2, the evaporating temperature of the evaporating volatile matters is 40 to 150 ℃ and the vacuum degree is 0 to-0.1 MPa; in the step S4, the evaporating temperature of the evaporating solvent is 40-150 ℃ and the vacuum degree is 0-0.1 MPa.
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| US3666681A (en) * | 1970-03-16 | 1972-05-30 | Dow Corning | Antifoam preparation for aqueous systems |
| DE19936289A1 (en) * | 1999-08-02 | 2001-02-15 | Wacker Chemie Gmbh | Defoamer formulation |
| DE10255649A1 (en) * | 2002-11-28 | 2004-06-17 | Wacker-Chemie Gmbh | defoamer |
| CN100408138C (en) * | 2006-07-28 | 2008-08-06 | 南京四新科技应用研究所有限公司 | Prepn process of active defoaming agent composition |
| CN101632908B (en) * | 2009-08-19 | 2011-07-20 | 南京四新科技应用研究所有限公司 | Method for preparing defoaming agent composition |
| CN102337031B (en) * | 2011-06-29 | 2013-02-13 | 南京四新科技应用研究所有限公司 | Organosilicon composition with low viscosity and preparation method thereof |
| CN105498304B (en) * | 2015-12-15 | 2017-10-03 | 江苏四新科技应用研究所股份有限公司 | A kind of defoaming composition and preparation method thereof |
| CN113577835B (en) * | 2020-04-30 | 2024-03-29 | 江苏四新科技应用研究所股份有限公司 | Organic silicon composition |
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