CN115105868A - Organic silicon defoaming agent and preparation method thereof - Google Patents
Organic silicon defoaming agent 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 organic silicon defoaming agent, which comprises the following raw materials: the water-based paint comprises hydroxyl-containing polysiloxane, a network structural agent, a condensation catalyst, organic silicon resin, inorganic particles, a basic catalyst, water and an organic solvent. Also provides a preparation method of the organic silicon defoaming agent: adding water, an organic solvent, a network-structured agent and a condensation catalyst into a reactor, stirring, raising the temperature for reaction so as to enable the network-structured agent to generate hydrolysis and condensation reactions to obtain condensation oligosiloxane; adding hydroxyl-containing polysiloxane for reaction, and distilling out volatile component to obtain viscous oily matter component XI; adding an organic solvent, inorganic particles and organic silicon resin into the other reactor, stirring, heating and preserving heat until the solid is dissolved to obtain a component XII; and finally, mixing the component XI and XII in a reactor, adding a basic catalyst, stirring, heating for reaction, and distilling out the solvent to obtain the organic silicon defoaming agent, wherein the defoaming agent has good hydrophilicity and defoaming durability.
Description
Technical Field
The invention relates to the field of fine chemical engineering, and particularly relates to an organic silicon defoaming agent and a preparation method thereof.
Background
The defoaming agent is one of essential fine chemical assistants in industrial production process, is mainly used for eliminating harmful foams in the industrial production process, and can be divided into organic silicon, polyether, mineral oil, fatty alcohol and the like according to different components of the defoaming agent. The products have the advantages that the organic silicon defoaming agent is suitable for the fields of sewage treatment, oil exploitation, textile printing and dyeing, pulping and papermaking and the like, has higher defoaming speed and longer foam inhibition function, but in coating, printing ink, metal working fluid and simple organic silicon defoaming agent, the problem of compatibility exists, the organic silicon defoaming agent is easy to separate out of a system and influences the surface performance, such as shrinkage cavity, fish eye, floating, net blocking and the like, and at the moment, the organic silicon is required to be modified, and the modified groups comprise polyether, olefin, alkyne and the like. The defoaming agent of polyether and fatty alcohol is generally used for defoaming and degassing white water of papermaking wet end paper, and the defoaming agent of mineral oil is generally used in coating, printing ink and adhesive, although the defoaming speed is not high, the defoaming agent generally does not influence the coating, and belongs to the favour of medium and low grade coating printing ink.
Silicone antifoams are, in general, a major concern of numerous antifoam manufacturers and research institutions. 202011350420.4 discloses a silicone defoamer for landfill leachate, which comprises polyether modified polydimethylsiloxane, nano fumed silica, modified silicone oil, polyoxyethylene fatty acid ester, emulsifier, thickener and biological inhibitor; US5271868A describes that a defoaming agent for high-temperature dyeing is prepared by two polyether modified silicone oils plus silicon paste, low-viscosity hydroxyl silicone oil and white carbon black; CN103814072A introduces methyl silicone oil, hydroxyl silicone oil, amino silicone oil and white carbon black to prepare defoaming agent emulsion; US2014316015A1 introduces the preparation of defoaming agent silicon paste, polysiloxane, hydrophilic white carbon black, hydrophobic white carbon black and silicone resin are treated at 50-250 ℃ to enable the viscosity of the obtained silicone grease to be half of the original viscosity, and the introduction shows that the defoaming performance is greatly improved; US2009234029a1 describes the preparation of silicone greases by treating a mixture of silicone oil, white carbon black, a small amount of a treating agent, water or ammonia water in a kneader; EP0516109A1 describes the effect of silicones using strong shear and strong alkaline conditions, which silicones are prepared with methyl silicone oil, hydrogen-containing silicone oil, vinyl silicone oil, catalyst.
The information described in these patents falls into two categories, one is the preparation of silicon pastes and the other is the preparation of compositions such as silicon pastes, modified polysiloxanes and the like. The silicon paste is the core of the organic silicon defoamer, the viscosity of the silicon paste prepared by the prior patent technology is unstable in the disposal period, and the defoaming performance needs to be further improved.
The organic silicon defoaming agent 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 gradually become large particles, thereby losing the defoaming function. Therefore, in order for the silicon paste to function sufficiently in the foaming medium, it is necessary to keep the defoaming particulate unit in a fine form without aggregating particles for a long time.
At present, the organic silicon defoaming agent is prepared by compounding polydimethylsiloxane, polyether modified polysiloxane or olefin modified polysiloxane with hydroxyl-containing polysiloxane and hydrophobic particles, and the organic silicon active substances can stably exist in a polyether system for a long time through the synergistic winding and wrapping effects of the polyether modified polysiloxane and linear polyether modified polysiloxane with spatial structures. The defoaming effect is improved by crosslinking and compounding technologies, but the polyether system of the silicon paste contains fewer hydrophilic groups and has the problem of poor hydrophilicity; and the embedding of hydrophobic particles in the system is not stable enough, so that the defoaming durability is not enough. Some of the emulsion is added with a surfactant to increase hydrophilicity and prepared into a defoaming agent emulsion, and the emulsion has large occupied volume and short effective period in the storage process, and is easy to aggregate and separate out precipitated particles, so that the performance is unstable; however, the organic defoaming agent silicon paste has the advantages of small storage volume, good stability and good safety, can prepare defoaming agent emulsion with various contents and purposes according to needs, and has higher practical value than the emulsion.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a silicone defoaming agent, in particular to use a net-shaped structural agent, wherein the net-shaped structural agent with a silane structure is subjected to hydrolysis and condensation reaction to obtain a cage-shaped structural object, and then is combined with hydroxyl-containing polysiloxane to obtain a unique structural object with a similar structure to an octopus structure, and the defoaming agent with the structural object has the advantages of good hydrophilicity and good defoaming durability.
The second purpose of the invention is to provide a preparation method of the organic silicon defoaming agent, namely, water, organic solvent, net-shaped structural agent and condensation catalyst are added into a reactor, and the mixture is stirred and heated to react so that the net-shaped structural agent undergoes hydrolysis and condensation reaction to obtain semi-condensed oligosiloxane; adding hydroxyl-containing polysiloxane for reaction, and distilling out volatile component to obtain viscous oily matter component XI; adding an organic solvent, inorganic particles and organic silicon resin into the other reactor, stirring, heating and preserving heat until the solid is dissolved to obtain a component XII; and finally, mixing the components XI and XII in a reactor, adding a basic catalyst, stirring, heating for reaction, and distilling out the solvent to obtain the organic silicon defoaming agent, wherein the organic silicon defoaming agent has good hydrophilicity and defoaming durability.
One of the purposes of the invention is realized by adopting the following technical scheme:
the organic silicon defoaming agent comprises the following raw materials in parts by weight:
the net-shaped structural agent is silane which can react with the hydroxyl-containing polysiloxane to form a net-shaped structure after hydrolysis and condensation reaction.
(1) Hydroxyl group-containing polysiloxane:
the molecular formula of the hydroxyl-containing polysiloxane is shown as the 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 formula I
Wherein, subscript x ═ 2 or 3, y ═ 0 or 1, and x + y ═ 3; subscripts a, b, c, d, e are the minimum of the number of four segments with at least one hydroxyl group on the side chain;
in formula I, the substituent R 1 The carbon atoms are hydrocarbyl groups which are free of functional groups or hydrocarbyl groups which contain functional group substituents, and the substituents R1 can be the same or different.
The hydroxyl-containing polysiloxane is a composition of one or more than two of compounds with a structure shown in a formula I.
Further, the viscosity of the hydroxyl-containing polysiloxane is 5-100000 mPa & s;
further, said R 1 The hydrocarbyl without functional groups 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 is chloromethyl;
further, the cyano-substituted hydrocarbon group is one of 3,3, 3-trifluoropropyl and 2-cyanoethyl.
Preferably, R is 1 Methyl, vinyl and phenyl.
(2) A network-structuring agent:
the reticular structure agent is silane which can react with the hydroxyl-containing polysiloxane to form a reticular structure after hydrolysis and condensation reaction, and the molecular formula of the silane is shown as a formula II:
(R 2 ) f —Si—(OR 3 ) g formula II
Wherein R is 2 Is one of alkyl with 1-18 carbon atoms and alkyl substituted by hydrophilic groups; the hydrocarbyl is alkyl, alkenyl, alkynyl or arylAnd an alkylaryl group or an arylalkyl group.
Further, said R 2 The hydrophilic group in (2) is one or more of a hydroxyl group, an amino group, an oxacyclo group, a nitrogen heterocyclic group, a nitrogen oxygen heterocyclic group and an amido group.
Wherein R is 3 Is a hydrocarbon group having 1 to 10 carbon atoms; the alkyl is straight chain alkyl or branched chain alkyl.
Wherein, subscript f takes the values of 0, 1, 2 and 3; g takes values of 1, 2, 3 and 4, and f + g is 4.
The reticular structure agent is one or a composition of more than two of silanes shown in a formula II, and at least comprises one silane with a trialkoxy structure.
Further, the network-structure agent is trimethyl methoxy silane, triethyl methoxy silane, tripropyl methoxy silane, tributyl methoxy silane, trihexyl methoxy silane, trioctyl methoxy silane, trimethylethoxy silane, triethylethoxy silane, tributylethoxy silane, trihexyl ethoxy silane, trioctyl ethoxy silane, trimethylbutoxy silane, triethylbutoxy silane, tripropyl butoxy silane, tributyl butoxy silane, trihexyl butoxy silane, trioctyl butoxy silane, trivinyl methoxy silane, trivinyl ethoxy silane, trivinyl butoxy silane, triphenylmethoxy silane, triphenylethoxy silane, triphenylbutoxy silane, dimethyldimethoxy silane, diethyldimethoxy silane, dipropyldimethoxy silane, dibutyldimethoxy silane, di-n-butyldimethoxy silane, tri-n-butylmethoxy silane, tri-n-butylethoxy silane, tri-n-butylbutoxy silane, triethylbutoxy silane, triphenylmethoxy silane, triphenyldimethoxy silane, di-n-t-butoxy silane, di-methoxy-silane, di-n-t-butyl-ethoxy silane, Dihexyldimethoxysilane, dioctyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dibutyldiethoxysilane, dihexyldiethoxysilane, dioctyldiethoxysilane, dimethyldibutoxysilane, diethyldibutoxysilane, dipropyldibutoxysilane, dibutyldibutoxysilane, dihexyldibutoxysilane, dioctyldibutoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldibutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, diethyltriethoxysilane, diethyldibutoxysilane, dibutyldimethoxysilane, dihexyldibutoxysilane, dibutyldimethoxysilane, di-octyltrimethoxysilane, di-ethyltrimethoxysilane, di-ethyltriethoxysilane, di-ethyltrimethoxysilane, di-n-vinyldiethoxysilane, di-n-butoxysilane, di-ethoxysilane, di-ethyltrimethoxysilane, di-n-vinyldi-ethoxysilane, di-ethyltriethoxysilane, di-butyltrimethoxysilane, di-ethyltriethoxysilane, di-n-butyltrimethoxysilane, di-vinyldi-butyltrimethoxysilane, dimethyltriethoxysilane, dimethyldiethoxysilane, dimethyltrimethoxysilane, dimethyldiethoxysilane, dimethyltrimethoxysilane, dimethyltriethoxysilane, dimethyldiethoxysilane, dimethyltriethoxysilane, dimethyltrimethoxysilane, dimethyldiethoxysilane, dimethyltrimethoxysilane, dimethyltriethoxysilane, dimethyldiethoxysilane, dimethyltrimethoxysilane, dimethyldiethoxysilane, dimethyltrimethoxysilane, and a, Butyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, methyltributoxysilane, ethyltributoxysilane, propyltributoxysilane, butyltributoxysilane, hexyltributoxysilane, octyltributoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, tetraethoxysilane, hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, trimethylaminomethoxysilane, dibutylaminomethyltributoxysilane, cyclohexylaminomethyltrimethoxysilane, cyclohexylaminomethyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, 3-dimethylaminopropylaminomethyltrimethoxysilane, one or more of morpholinyl methyl trialkoxy silane, dibutyl aminomethyl triethoxy silane, morpholinyl methyl triisopropoxy silane and morpholinyl methyl triethoxy silane, and at least one silane with trialkoxy structure.
The reticular structure agent is not only in a plane reticular shape, but also in a three-dimensional reticular structure, due to the chemical bond between alkoxy in silane and silicon atoms, the silane is easy to hydrolyze in water to form silanol hydroxyl, the hydroxyl is subjected to dehydration condensation between intermolecular silanol hydroxyl under the conditions of acid, alkali and heating to form a silicon ether bond, a huge three-dimensional structure of a space network is formed through condensation of intermolecular hydroxyl, and part of silanol hydroxyl does not participate in the reaction due to the stereochemical factors, so that the silanol hydroxyl keeps good hydrophilic performance. Unreacted silanol hydroxyl is reacted with the hydroxyl-containing polysiloxane, and the obtained compound has more hydroxyl with good hydrophilicity, so that the hydrophilicity 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 a composition of more than two of hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, cesium hydroxide, dibutyltin dilaurate, stannous octoate, diethylhydroxylamine, triethyl phosphate, cyclohexanone oxime and potassium acetate which can act together.
(4) Silicone resin:
the organic silicon resin is nonlinear siloxane resin, namely MQ silicon resin, and consists of an organic silicon compound containing monofunctional siloxane chain links (M groups) and an organic silicon compound containing tetrafunctional siloxane chain links (Q groups), wherein the value range of the molar ratio of the M groups to the Q groups is selected to be 0.4: 1-2.5: 1.
Preferably, the molar ratio of the M groups to the Q groups in the silicone resin ranges from 0.4: 1-1.1: 1.
The MQ silicon resin has high thermal stability and chemical stability, low surface tension and strong foam breaking capability. The MQ silicon resin is composed of M units and Q units, wherein M groups are most of trimethylchlorosilane, hexamethyldisiloxane and trimethylmethoxysilane, and Q groups are most of water glass and tetraethoxysilane. The smaller the M/Q ratio is, the larger the molecular weight of the silicone resin is, and the final product is powdery; the larger the M/Q ratio, the smaller the molecular weight of the silicone resin, and not even the resin-like structure in the end, 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 composition of more than two of silicon dioxide, aluminum oxide, zinc oxide and magnesium oxide. The specific surface area of these materials is 50m by BET method 2 More than g.
Further, the preferred inorganic particles are silica, which can be classified into fumed silica and precipitated silica according to their standard manufacturing techniques.
The surface of the inorganic particles may be hydrophilic or hydrophobic in order to render the foam control composition sufficiently effective in aqueous systems. The hydrophobic silica has an average particle size in the range of 0.1 to 20 μm. The silicon dioxide has an important function of adsorption in the defoaming agent, and because the silicon dioxide has small particle size, large specific surface area, high surface energy and a three-dimensional network structure, the silicon dioxide can form a huge acting force for adsorbing bubbles and attack the bubbles together with the polysiloxane, namely the silicon dioxide adsorbs and impacts the weak points of the bubbles to break the bubbles under the action of low surface tension of the polysiloxane. Thus, silica acts as a "needle point" in defoamers, using a small amount but with a great effect. The composite defoaming agent and polysiloxane are used as active ingredients of the high-efficiency defoaming agent together, and have a composite high-efficiency and synergistic defoaming effect. Meanwhile, due to the existence of the silica particles, the polysiloxane can be rapidly dispersed in the foaming liquid, the dispersion efficiency of the polysiloxane is improved, and the defoaming effect is provided.
Preferably, the silicon dioxide particles are one or a combination of more than two of hydrophilic silicon dioxide 383DS, hydrophilic silicon dioxide HL200, hydrophobic silicon dioxide H2000, hydrophobic silicon dioxide R974, hydrophobic silicon dioxide R972 and hydrophobic silicon dioxide D10.
If the inorganic particles are desired to be hydrophobic, this can be accomplished by treating the hydrophilic inorganic particles with a treating agent comprising a fatty acid, a reactive silane or a siloxane-based compound, such as stearic acid, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, hydroxy-and methyl-terminated polydimethylsiloxanes, and siloxane resins, among others.
(6) Basic catalyst:
the alkaline catalyst is one or a composition of more than two of sodium hydroxide, potassium hydroxide, cesium hydroxide, tetramethyl ammonium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate.
(7) Water (W)
The water is deionized water.
(8) Organic solvent
The organic solvent is one or a composition of more than two of toluene, xylene and trimethylbenzene.
In order to achieve the second purpose, the invention provides the following technical scheme:
the preparation method of the organic silicon defoaming agent comprises the following steps:
s1, adding water, an organic solvent, a net-shaped structural agent and a condensation catalyst in a formula ratio into a reactor, stirring, raising the temperature and carrying out heat preservation reaction to enable the net-shaped structural agent to be hydrolyzed and subjected to intermolecular condensation to form a condensation oligomeric siloxane core cage-type structure;
s2, adding hydroxyl-containing polysiloxane with the formula amount into the step S1, carrying out condensation reaction to form an octopus structure, and distilling out volatile components to obtain a viscous oily substance, namely the component XI;
s3, adding the organic solvent, the inorganic particles and the organic silicon resin in the formula ratio into the other reactor, stirring, heating and keeping the temperature until the solid is dissolved to obtain a solution, namely a component XII;
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 basic catalyst in a formula amount, stirring, raising the temperature, keeping the temperature for reaction, and distilling off the solvent to obtain the organic silicon defoaming agent.
In the reaction step of the preparation method:
further, in the step S1, adding water, an organic solvent, a network structure agent and a condensation catalyst in a formula amount into a reactor, stirring, raising the temperature within the range of 40-100 ℃, and keeping the temperature for reaction for 0.5-3 hours;
further, in the step S2, 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 evaporation temperature for evaporating the volatile components is 40-150 ℃, and the vacuum degree is 0-minus 0.1 MPa;
further, in the step S3, adding the organic solvent, the inorganic particles and the organic silicon resin in the formula amount into another reactor, stirring, heating and keeping the temperature at 60-130 ℃ for 10-60 min;
further, in the step S4, adding a formula amount of an alkaline catalyst, stirring, raising the temperature to react at 50-200 ℃ for 3-8 h, and then evaporating the solvent to obtain the organic silicon defoaming agent.
Further, in the step S4, the temperature at which the solvent is distilled off is 40 to 150 ℃ and the degree of vacuum is 0 to-0.1 MPa.
The organic silicon defoaming agent obtained by the invention can be used for preparing an internal defoaming agent and is used in systems such as metal working fluid, laundry detergent, printing ink and the like.
The organic silicon defoaming agent has the beneficial effects that:
(1) the organosilicon defoamer is prepared by hydrolyzing siloxy into silanol hydroxyl in water by a network structurant at least containing silane with a trialkoxy structure, and condensing the silanol hydroxyl under the action of a condensation catalyst; in particular, trialkoxysilanes have three silanol hydroxyl structures after hydrolysis, the hydroxyl groups are unstable, intermolecular silanol hydroxyl groups are subjected to dehydration condensation under the action of a condensation catalyst and heating, and a 'cage' structure with an intricate three-dimensional net-shaped spatial structure can be formed, and the silanol hydroxyl groups which are not subjected to dehydration condensation exist in the polymers due to the spatial effect and have better hydrophilicity. Then the polymer with the cage structure is condensed with silanol hydroxyl on hydroxyl-containing polysiloxane, and the cage structure and the hydroxyl-containing polysiloxane are connected together to form a structure similar to an octopus with a larger space structure; the hydrophilic silanol groups are staggered with each other, so that the hydrophilicity of a polysiloxane structure formed by hydroxyl-containing polysiloxane is enhanced due to the existence of a plurality of hydrophilic silanol hydroxyl groups in the molecule, and the defoaming performance is improved.
(2) In the network structure agent of the invention, the hydrocarbyl substituent has hydrophilic groups, such as hydroxyl, amino, oxacyclyl, nitrogen heterocyclic group and amido, which can also contribute to increasing the hydrophilicity of the polysiloxane structure and the defoaming performance.
(3) The inorganic particles, particularly the silicon dioxide, have an important function in the defoaming agent, namely the adsorption function, and because the particles are small in size, large in specific surface area, high in surface energy and three-dimensional in network structure, the silicon dioxide can form a huge bubble adsorption force and attack bubbles together with the polysiloxane, namely the silicon dioxide adsorbs and impacts the weak points of the bubbles to break the bubbles under the action of low surface tension of the polysiloxane. Thus, silica acts as a "needle point" in defoamers, using a small amount but with a great effect. The composite defoaming agent and polysiloxane are used as active ingredients of the high-efficiency defoaming agent together, and have a composite high-efficiency and synergistic defoaming effect. Meanwhile, due to the existence of the silica particles, the polysiloxane can be rapidly dispersed in the foaming liquid, the dispersion efficiency of the polysiloxane is improved, and the defoaming effect is provided.
(4) The organic silicon defoaming agent disclosed 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. Organic silicon resin and inorganic particles are heated and dissolved in toluene, solid particles are fully dissolved, so that the inorganic particles can be well embedded into the organic silicon resin, the inorganic particles can be well dispersed and uniformly mixed, and the defoaming effect of the organic silicon resin and the inorganic particles is fully increased.
(5) In order to better utilize the defoaming performance of inorganic particles, the organic silicon defoaming agent disclosed by the invention combines an octopus-like structure with good hydrophilicity and organic silicon resin in which the inorganic particles are dissolved, and the inorganic particle particles with defoaming effect are firmly embedded into the octopus-like structure, so that the inorganic particles are not easy to agglomerate and have good stability in the storage and use processes.
(6) The silicone defoaming agent obtained by the method for preparing the silicone defoaming agent has the advantages of good hydrophilicity, difficult aggregation and agglomeration when being sheared, and maintained durability of defoaming function because inorganic particles are difficult to precipitate.
The invention researches and designs the structure of carrier polysiloxane, inorganic particles are embedded in the carrier polysiloxane through the cage structure of the polysiloxane, different cage structures are connected through the polysiloxane, and the polysiloxane composition similar to an octopus structure is formed.
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 symbols 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 a dynamic viscosity at 25 ℃ of 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 a dynamic viscosity at 25 ℃ of 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 ]a dynamic viscosity at 25 ℃ of 65,800 mPas;
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 ]a dynamic viscosity at 25 ℃ of 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 and a dynamic viscosity at 25 ℃ of 15 mPas.
Example 1:
adding 5 parts of water, 50 parts of toluene, 12 parts of butyltriethoxysilane and 0.2 part of condensation catalyst potassium hydroxide into a reaction flask, stirring, raising the temperature to 40 ℃, and keeping the temperature for 3 hours to enable the butyltriethoxysilane to undergo hydrolysis and intermolecular condensation reactions to form a condensation oligomeric siloxane core cage-type 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 to form a structure with a core similar to that of octopus, and volatile components are evaporated to obtain a viscous oily component XI;
adding toluene, 5 parts of hydrophilic silica 383DS and 10 parts of methyl MQ silicon resin (the molar ratio of M to Q is 0.66:1) into another reaction bottle, heating to 100 ℃, and stirring until the solid is dissolved to obtain a component XII;
adding the component XI and the component XII into a flask, starting stirring, adding 0.5 part of basic catalyst cesium hydroxide, reacting at 55 ℃ for 7.5 hours, and evaporating the solvent under reduced pressure to obtain the organic silicon defoamer CP 1.
Example 2:
adding 10 parts of water, 50 parts of dimethylbenzene, 10 parts of trimethylethoxysilane, 15 parts of dibutylaminomethyltributoxysilane and 2 parts of cyclohexanone oxime serving as a condensation catalyst into a reaction bottle, stirring, raising the temperature to 75 ℃, and keeping the temperature for 2 hours to enable the dimethyldiethoxysilane and the dibutylaminomethyltributoxysilane to undergo hydrolysis and intermolecular condensation reactions to form a condensation oligomeric siloxane core cage-type structure.
Then adding 48.5 parts of hydroxyl-containing polysiloxane A-2 into the structure, further carrying out condensation reaction for 2h to form a core octopus structure, and finally evaporating volatile components to obtain a transparent viscous liquid component XI;
adding 60 parts of dimethylbenzene, 10 parts of hydrophilic silicon dioxide HL200 and 4 parts of methyl MQ silicon resin (the molar ratio of M to Q is 0.45:1) into another reaction bottle, heating to 125 ℃, and stirring until the solid is dissolved to obtain a component XII;
adding the component XI and the component XII into a flask, starting stirring, adding 1 part of alkaline catalyst potassium hydroxide, reacting at 135 ℃ for 5 hours, and evaporating the solvent under reduced pressure to obtain the organic silicon defoamer CP 2.
Example 3:
adding 10 parts of water, 50 parts of xylene, 10 parts of phenyltrimethoxysilane, 5 parts of dimethyldimethoxysilane, 35 parts of aminoethylaminopropyltrimethoxysilane and 0.5 part of condensation catalyst stannous octoate into a reaction bottle, stirring, raising the temperature to 95 ℃, and keeping the temperature for 0.5h to ensure that the phenyltrimethoxysilane, the dimethyldimethoxysilane and the aminoethylaminopropyltrimethoxysilane undergo hydrolysis and intermolecular condensation reactions to form a condensation oligomeric siloxane core cage structure.
Then, adding 21 parts of hydroxyl-containing polysiloxane A-3 into the structure, further carrying out condensation reaction for 4.5h to form a core octopus structure, and finally evaporating volatile components to obtain a transparent viscous liquid component XI;
adding benzene, 10 parts of hydrophobic silicon dioxide H2000 and 8 parts of methyl MQ silicon resin (the molar ratio of M to Q is 0.8:1) into another reaction bottle, heating to 65 ℃, and stirring until the solid is dissolved to obtain a component XII;
adding the component XI and the component XII into a flask, starting stirring, adding 2 parts of basic catalyst sodium bicarbonate, reacting at 195 ℃ for 3 hours, and evaporating the solvent under reduced pressure to obtain the organosilicon defoamer CP 3.
Example 4:
adding 0.5 part of water, 80 parts of toluene, 10 parts of methyltrimethoxysilane, 15 parts of tetraethoxysilane and 1 part of condensation catalyst tetramethylammonium hydroxide into a reaction flask, stirring, raising the temperature to 65 ℃, and keeping the temperature for 1.5 hours to ensure that the methyltrimethoxysilane and the tetraethoxysilane are subjected to hydrolysis and intermolecular condensation reaction to form a condensation oligomeric siloxane 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 to form a core octopus structure, and finally volatile is evaporated to obtain a transparent viscous liquid component XI;
adding 60 parts of toluene, 3 parts of hydrophobic silicon dioxide R974 and 0.5 part of methyl MQ silicon resin (molar ratio of M: Q is 1.1:1) into another reaction bottle, heating to 85 ℃, and stirring until the solid is dissolved to obtain a component XII;
adding the component XI and the component XII into a flask, starting stirring, adding 0.02 part of basic catalyst cesium hydroxide, reacting at 135 ℃ for 4.5 hours, and evaporating the solvent under reduced pressure to obtain the organic silicon defoamer CP 4.
Example 5:
adding 5 parts of water, 100 parts of toluene, 3 parts of trivinylbutoxysilane, 10 parts of phenyltrimethoxysilane and 1 part of condensation catalyst tetramethylammonium hydroxide into a reaction bottle, stirring, raising the temperature to 80 ℃, and keeping the temperature for 3 hours to enable the trivinylbutoxysilane and the phenyltrimethoxysilane to perform hydrolysis and intermolecular condensation reactions to form a condensation oligomeric siloxane 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, further carrying out condensation reaction for 4 hours to form a core octopus structure, and finally evaporating volatile components to obtain a transparent viscous liquid component XI;
adding 60 parts of xylene, 5 parts of hydrophobic silicon dioxide R972 and 5 parts of methyl MQ silicon resin (molar ratio of M to Q is 0.75:1) into another reaction bottle, heating to 120 ℃, and stirring until the solid is dissolved to obtain a component XII;
adding the component XI and the component XII into a flask, starting stirring, adding 1 part of basic catalyst cesium hydroxide, reacting at 155 ℃ for 3 hours, and evaporating the solvent under reduced pressure to obtain the organosilicon defoamer CP 5.
Example 6:
adding 2 parts of water, 75 parts of toluene, 7 parts of methyltriethoxysilane, 10 parts of phenyltrimethoxysilane and 1 part of triethyl phosphate serving as a condensation catalyst into a reaction flask, stirring, raising the temperature to 90 ℃, and keeping the temperature for 3 hours to enable the methyltriethoxysilane and the phenyltrimethoxysilane to perform hydrolysis and intermolecular condensation reactions 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 2.5h to form a core octopus structure, and finally evaporating volatile components to obtain a transparent viscous liquid component XI;
adding 30 parts of xylene, 4 parts of hydrophobic silica D10 and 4 parts of methyl MQ silicon resin (molar ratio of M: Q is 0.65:1) into another reaction bottle, heating to 100 ℃, and stirring until the solid is dissolved to obtain a component XII;
adding the component XI and the component XII into a flask, starting stirring, adding 2 parts of basic catalyst sodium carbonate, reacting at 65 ℃ for 7 hours, and evaporating the solvent under reduced pressure to obtain the organic silicon defoamer CP 6.
Example 7:
adding 2 parts of water, 75 parts of toluene, 17 parts of hydroxymethyl triethoxysilane and 1 part of condensation catalyst triethyl phosphate into a reaction flask, stirring, raising the temperature to 90 ℃, and keeping the temperature for 2.5 hours to enable the hydroxymethyl triethoxysilane to undergo hydrolysis and intermolecular condensation reactions to form a condensation oligosiloxane core cage structure.
Then, adding 50 parts of hydroxyl-containing polysiloxane A-4 into the structure, further carrying out condensation reaction for 2h to form a core octopus structure, and finally evaporating volatile components to obtain a transparent viscous liquid component XI;
adding 30 parts of xylene, 4 parts of hydrophobic silica D10 and 5 parts of methyl MQ silicon resin (molar ratio of M: Q is 0.65:1) into another reaction bottle, heating to 95 ℃, and stirring until the solid is dissolved to obtain a component XII;
adding the component XI and the component XII into a flask, starting stirring, adding 0.3 part of basic catalyst sodium hydroxide, reacting at 50 ℃ for 6 hours, and evaporating the solvent under reduced pressure to obtain the organic silicon defoamer CP 7.
Example 8:
adding 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 into a reaction flask, stirring, raising the temperature to 90 ℃, and keeping the temperature for 3 hours, so that the hydroxymethyl triethoxysilane and the phenyl trimethoxysilane are subjected to hydrolysis and intermolecular condensation reactions 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 2.5h to form a core octopus structure, and finally evaporating volatile components to obtain a transparent viscous liquid component XI;
adding 30 parts of xylene, 4 parts of hydrophobic silica D10 and 4 parts of methyl MQ silicon resin (molar ratio of M: Q is 0.65:1) into another reaction bottle, heating to 100 ℃, and stirring until the solid is dissolved to obtain a component XII;
adding the component XI and the component XII into a flask, starting stirring, adding 2 parts of basic catalyst sodium carbonate, reacting at 65 ℃ for 7 hours, and evaporating the solvent under reduced pressure to obtain the organic silicon defoamer CP 8.
Example 9:
adding 2 parts of water, 75 parts of toluene, 22 parts of morpholinyl methyl triisopropoxysilane and 1 part of triethyl phosphate serving as a condensation catalyst into a reaction bottle, stirring, raising the temperature to 90 ℃, and preserving the temperature for 3 hours to ensure that the morpholinyl methyl triisopropoxysilane is subjected to hydrolysis and intermolecular condensation reaction to form a condensation oligomeric siloxane core cage 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 2.5h to form a core octopus structure, and finally evaporating volatile components to obtain a transparent viscous liquid component XI;
adding 30 parts of xylene, 3 parts of hydrophilic silicon dioxide HL200 and 4 parts of methyl MQ silicon resin (the molar ratio of M to Q is 0.65:1) into another reaction bottle, heating to 100 ℃, and stirring until the solid is dissolved to obtain a component XII;
adding the component XI and the component XII into a flask, starting stirring, adding 2 parts of basic catalyst sodium carbonate, reacting at 65 ℃ for 7 hours, and evaporating the solvent under reduced pressure to obtain the organic silicon defoamer CP 9.
Comparative example 1:
adding 5 parts of water, 75 parts of toluene, 5 parts of butyl triethoxysilane and 1 part of triethyl phosphate as a condensation catalyst into a reaction flask, stirring, raising the temperature to 90 ℃, and keeping the temperature for 3 hours to enable the butyl triethoxysilane to undergo hydrolysis and intermolecular condensation reactions 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 2.5h to form a core octopus structure, and finally evaporating volatile components to obtain a transparent viscous liquid component XI;
adding 30 parts of xylene, 8 parts of hydrophobic silica D10 and 9 parts of methyl MQ silicon resin (molar ratio of M to Q is 0.65:1) into another reaction bottle, heating to 100 ℃, and stirring until the solid is dissolved to obtain a component XII;
adding the component XI and the component XII into a flask, starting stirring, adding 2 parts of basic catalyst sodium carbonate, reacting at 65 ℃ for 7 hours, and evaporating the solvent under reduced pressure to obtain the organic silicon defoamer CP 6-1.
Comparative example 2:
adding 10 parts of water, 75 parts of toluene and 1 part of triethyl phosphate serving as a condensation catalyst into a reaction bottle, stirring, raising the temperature to 90 ℃, preserving the temperature and reacting 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 components to obtain a transparent viscous liquid component XI;
adding 30 parts of xylene, 8 parts of hydrophobic silica D10 and 9 parts of methyl MQ silicon resin (molar ratio of M to Q is 0.65:1) into another reaction bottle, heating to 100 ℃, and stirring until the solid is dissolved to obtain a component XII;
adding the component XI and the component XII into a flask, starting stirring, adding 2 parts of basic catalyst sodium carbonate, reacting at 65 ℃ for 7 hours, and evaporating the solvent under reduced pressure to obtain the organic silicon defoamer CP 6-2.
Comparative example 3:
adding 5 parts of water, 75 parts of toluene, 30 parts of methyltriethoxysilane, 30 parts of phenyltrimethoxysilane and 1 part of triethyl phosphate serving as a condensation catalyst into a reaction flask, stirring, raising the temperature to 90 ℃, and keeping the temperature for 3 hours to enable the methyltriethoxysilane and the phenyltrimethoxysilane to perform hydrolysis and intermolecular condensation reactions 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 2.5h to form a core octopus structure, and finally evaporating volatile components to obtain a transparent viscous liquid component XI;
adding 30 parts of xylene, 8 parts of hydrophobic silica D10 and 9 parts of methyl MQ silicon resin (molar ratio of M to Q is 0.65:1) into another reaction bottle, heating to 100 ℃, and stirring until the solid is dissolved to obtain a component XII;
adding the component XI and the component XII into a flask, starting stirring, adding 2 parts of basic catalyst sodium carbonate, reacting at 65 ℃ for 7 hours, and evaporating the solvent under reduced pressure to obtain the organic silicon defoamer CP 6-3.
Comparative example 4:
adding 5 parts of water, 75 parts of toluene, 15 parts of tributyl ethoxy silane, 15 parts of dimethyl dibutoxy silane, 15 parts of tetraethoxy silane and 1 part of triethyl phosphate serving as a condensation catalyst into a reaction bottle, stirring, raising the temperature to 90 ℃, and keeping the temperature for 3 hours to enable the tributyl ethoxy silane, the dimethyl dibutoxy silane and the tetraethoxy silane to perform hydrolysis and intermolecular condensation reaction to obtain the 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 distilling out volatile components to obtain a transparent viscous liquid component XI;
adding 30 parts of xylene, 8 parts of hydrophobic silica D10 and 9 parts of methyl MQ silicon resin (molar ratio of M to Q is 0.65:1) into another reaction bottle, heating to 100 ℃, and stirring until the solid is dissolved to obtain a component XII;
adding the component XI and the component XII into a flask, starting stirring, adding 2 parts of basic catalyst sodium carbonate, reacting at 65 ℃ for 7 hours, and evaporating the solvent under reduced pressure to obtain the organic silicon defoamer CP 6-4.
Comparative example 5:
adding 5 parts of water, 75 parts of toluene, 7 parts of methyltriethoxysilane, 10 parts of phenyltrimethoxysilane and 1 part of triethyl phosphate serving as a condensation catalyst into a reaction flask, stirring, raising the temperature to 90 ℃, and keeping the temperature for 3 hours to ensure that the methyltriethoxysilane undergoes hydrolysis and intermolecular condensation reaction to form a condensed 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 condensing for 2.5h to form a core octopus structure, and finally distilling out volatile components to obtain a transparent viscous liquid component XI;
adding 30 parts of xylene and 9 parts of methyl MQ silicon resin (the molar ratio of M to Q is 0.65:1) directly into the component XI in the reaction bottle in the last step, stirring, and heating to 100 ℃ to dissolve the solid; obtaining a component XII;
stirring the component XII, adding 2 parts of alkaline catalyst sodium carbonate, reacting at 65 ℃ for 7 hours, and evaporating under reduced pressure to remove the solvent to obtain the organic silicon defoamer CP 6-5.
Comparative example 6:
adding 5 parts of water, 75 parts of toluene, 7 parts of methyltriethoxysilane, 10 parts of phenyltrimethoxysilane and 1 part of triethyl phosphate serving as a condensation catalyst into a reaction flask, stirring, raising the temperature to 90 ℃, and keeping the temperature for 3 hours to ensure that the methyltriethoxysilane undergoes hydrolysis and intermolecular condensation reaction to form a condensed 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 condensing for 2.5h to form a core octopus structure, and finally evaporating volatile components to obtain a transparent viscous liquid component XI;
adding 30 parts of dimethylbenzene and 8 parts of hydrophobic silica D10 into the component XI in the reaction bottle in the last step, stirring, and heating to 100 ℃ to dissolve the solid; obtaining a component XII;
adding 2 parts of alkaline catalyst sodium carbonate into the component XII in the previous step, starting stirring, reacting at 65 ℃ for 7 hours, and then evaporating under reduced pressure to remove the solvent to obtain the organic silicon defoamer CP 6-6.
Comparative example 7:
silicone defoamer CP6-7 was prepared according to example 1 of patent US 4639489.
Comparative example 8:
a silicone defoamer CP6-8 was prepared according to example 1 of patent WO2018024859A 1.
Performance testing and comparative experiments of the antifoam agent
In order to verify the excellent performance of the silicone defoamer of the present invention, the silicone defoamers of the above examples and comparative examples were prepared as emulsions by the following method:
30 parts of silicone defoaming agents (comparative examples CP 1-CP 9, examples CP 6-1-8), 10 parts of span 60 and 10 parts of tween prepared in the examples or the comparative examples were added to a vessel, stirred at 500rpm for 20min, then 60 parts of water was slowly added and ground into an emulsion of a target particle size by a colloid mill, and finally an alkali-swellable thickener was added to adjust the viscosity, to obtain silicone defoaming agent emulsions ECP (1-9) and ECP6- (1-8), respectively.
Performance test experiment one:
the resulting emulsions ECP 1-ECP 9 and ECP 6-1-8 were each tested according to the following method:
2 wt% sodium dodecylbenzenesulfonate +2 wt% sodium dodecylbenzenesulfonateNP10+96 wt% water as test medium, tested by the shake flask method. At room temperature, 50ml of the test medium was added to the flask, 30. mu.L of the antifoam emulsion was added, shaking vertically 50 times, and the time for the foam to reach the surface was recorded. The shorter the time, the higher the defoaming speed. And the precipitation in the shake flask after shaking was recorded and indicated by "+", the more "+" indicates less precipitation. The test results are shown in table 1:
TABLE 1 comparative experiment result of defoaming and foam inhibiting performance and stability of emulsion
| Sample name | Defoaming time/s | Precipitation behavior in Shake flasks 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 two:
2 wt% of silicone defoamer emulsion ECP 1-ECP 9 and ECP 6-1-8 are added into the fully synthetic cutting fluid, then the fully synthetic cutting fluid is put into an oven at 50 ℃ for aging for 4 weeks, and the precipitation and floating conditions in the fully synthetic cutting fluid are observed, and the results are shown in Table 2:
TABLE 2 compatibility comparison of emulsions with fully synthetic cutting fluids
| Sample name | Appearance of cutting fluid | Surface precipitation of cutting fluid |
| ECP1 | Is transparent | A little white oil point |
| ECP2 | Is transparent | A little white oil point |
| ECP3 | Is transparent | A little white oil point |
| ECP4 | Semi-transparent | A little white oil point |
| ECP5 | Is transparent | Little white oil point |
| ECP6 | Is transparent | A little white oil point |
| ECP7 | Is transparent | A little white oil point |
| ECP8 | Is transparent | A little white oil point |
| ECP9 | Is transparent | Little white oil point |
| ECP6-1 | Semi-transparent | White floating object |
| ECP6-2 | Semi-transparent | White floating object |
| ECP6-3 | Is transparent | White floating object |
| ECP6-4 | Semi-transparent | White floating object |
| ECP6-5 | Semi-transparent | White floating object |
| ECP6-6 | Turbidity | A little white oil point |
| ECP6-7 | Turbidity | White floating object |
| ECP6-8 | Turbidity | White floating object |
Analysis and discussion of test experiment results:
as can be seen from the test data results in table 1, the defoaming performance of the silicone defoaming agent prepared by the methods in examples 1 to 6 has a better effect, and when the network-structure agent contains hydrophilic groups, that is, the silicone defoaming agent prepared by the methods in examples 7 to 9 contains a certain amount of hydrophilic groups, the hydrophilicity and the hydrophobicity of the defoaming agent are balanced, that is, the defoaming agent has a better defoaming performance and excellent compatibility. In conclusion, the organosilicon defoaming agent prepared by the method has good defoaming performance and stability, on one hand, the hydrophilicity of a cage structure caused by a net-shaped structural agent is present, and after the organosilicon defoaming agent is condensed with polysiloxane containing hydroxyl, the comprehensive performance of a polymer is more remarkable, so that the stability of the polymer is improved, and the defoaming performance is improved; in addition, the foam breaking capability of the organic silicon resin and the firmly embedded foam pricking effect of the inorganic particles enable the hydrophilicity of the whole system to be better and the defoaming performance to be more durable.
In contrast, the defoaming speed of the obtained silicone defoamer decreased significantly after the network-forming agent was reduced or removed in comparative examples 1 and 2; in comparative example 3, the amount of the network-shaped structuring agent is too much, the hydrophilicity is particularly good, but inorganic particles are easy to separate out and aggregate, and the defoaming performance is influenced; the reticular structure agent in the comparative example 4 does not contain silane with trialkoxy structure, so that the defoaming performance is poor, and the important function of the reticular structure agent in the defoaming agent is fully illustrated; the defoaming agent prepared by the method without adding inorganic particles in comparative example 5 is also much inferior in performance; however, in comparative example 6 in which no silicone resin was added, the embedding effect of the inorganic particles in the polysiloxane composition was insufficient, resulting in a significant deterioration in defoaming performance; the performance of the silicone defoaming agent prepared by the conventional methods in comparative examples 7 and 8 is obviously insufficient.
In summary, it can be shown that the polysiloxane structural composition containing a similar "octopus" structure designed by this patent has good hydrophilicity, good stability per se, and good stability of the whole system, so that defoaming is more durable, and especially, defoaming performance is improved.
From the compatibility experiment results of the defoaming agent emulsion and the fully-synthetic cutting fluid in the table 2, the emulsions of the silicone defoaming agents ECP 1-ECP 9 prepared by the method of the present invention all show excellent compatibility, which is mainly attributed to the fact that the silicone composition with the structure of octopus is prepared by a series of reactions through the network-shaped structuring agent, and the silicone defoaming agent containing the structure has good hydrophilicity.
In comparative examples, no good performance was obtained without the use of a network-forming agent or with little or no silane structure containing a trialkoxy structure in comparative examples 1, 2 and 4; in comparative example 3, too much network structure agent resulted in easy precipitation of inorganic particles, which affected the performance deterioration; comparative examples 5 and 6 also show that the organic silicon resin and the inorganic particles have better assistance effect to the special structure of the octopus structure to a certain extent; compared with the effects of the defoaming agents of comparative examples 7 and 8, the silicone defoaming agent of the method of the invention has obvious improvement effect.
Claims (10)
1. The organic silicon defoaming agent is characterized by comprising the following raw materials in parts by weight:
the net-shaped structural agent is silane which can react with the hydroxyl-containing polysiloxane to form a net-shaped structure after hydrolysis and condensation reaction.
2. The silicone defoamer of claim 1, wherein the hydroxyl-containing polysiloxane has the formula of 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 formula I
Wherein, subscript x ═ 2 or 3, y ═ 0 or 1, and x + y ═ 3; subscripts a, b, c, d, e are the minimum of the number of four segments with at least one hydroxyl group on the side chain;
in formula I, the substituent R 1 Is a C1-12 hydrocarbon group without functional group or a hydrocarbon group with functional group substituent, and the substituent R 1 May be the same or different;
the hydroxyl-containing polysiloxane is a composition of one or more than two of compounds with a structure shown in a formula I.
3. The silicone defoamer according to claim 2, wherein the hydroxyl-containing polysiloxane has a viscosity of 5 to 100000 mPa-s; the R is 1 The hydrocarbyl 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.
4. The silicone defoamer according to claim 3,
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 hydrocarbyl is one of 3,3, 3-trifluoropropyl and 2-cyanoethyl.
5. The silicone defoamer of claim 1, wherein said network structurant has the formula shown in formula ii:
(R 2 ) f —Si—(OR 3 ) g formula II
Wherein R is 2 Is one of alkyl with 1-18 carbon atoms and alkyl containing hydrophilic groups;
wherein R is 3 Is a hydrocarbon group having 1 to 10 carbon atoms;
wherein, subscript f takes values of 0, 1, 2, and 3; g takes the values of 1, 2, 3 and 4, and f + g is 4;
the reticular structure agent is one or a composition of more than two of silanes shown in a formula II, and at least comprises one silane with a trialkoxy structure.
6. The silicone defoamer of claim 5, wherein said network structurant is selected from the group consisting of trimethylmethoxysilane, triethylmethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, trihexylmethoxysilane, trioctylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, tributylethoxysilane, trihexethoxysilane, trioctylethoxysilane, trimethylbutoxysilane, triethylbutoxysilane, tripropylbutoxysilane, tributylbutoxysilane, trihexyloxysilane, trioctybutoxysilane, trivinylmethoxysilane, trivinylethoxysilane, trivinylbutoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylbutoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, tri-vinylethoxysilane, tri-vinylbutoxysilane, tri-vinyldimethoxysilane, tri-vinylethoxysilane, tri-vinyldimethoxysilane, and tri-vinyldimethoxysilane, Dipropyldimethoxysilane, dibutyldimethoxysilane, dihexyldimethoxysilane, dioctyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dibutyldiethoxysilane, dihexyldiethoxysilane, dioctyldiethoxysilane, dimethyldibutoxysilane, diethyldibutoxysilane, dipropyldibutoxysilane, dibutyldibutoxysilane, dihexyldibutoxysilane, dioctyldibutoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldibutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, methyltributoxysilane, ethyltributoxysilane, propyltributoxysilane, butyltributoxysilane, hexyltributoxysilane, octyltributoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, tetraethoxysilane, hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, trimethylaminomethoxysilane, dibutylaminomethyltributoxysilane, cyclohexylaminomethyltrimethoxysilane, aminoaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, butyltriethoxysilane, butyltributoxysilane, vinyltributoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aminotriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aminotriethoxysilane, and the like-N-triethoxysilane, and the like-N-triethoxysilane, and the like, 3-dimethyl aminopropyl amino methyl trimethoxy silane, morpholinyl methyl trialkoxy silane, dibutyl amino methyl triethoxy silane, morpholinyl methyl triisopropoxy silane and morpholinyl methyl triethoxy silane, and at least contains one trialkoxy silane.
7. The silicone defoamer of claim 1, wherein the condensation catalyst is one or a combination of two or more of hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, cesium hydroxide, dibutyltin dilaurate, stannous octoate, diethylhydroxylamine, triethyl phosphate, cyclohexanone oxime, and potassium acetate;
the organic silicon resin is nonlinear siloxane resin, namely MQ silicon resin, and consists of an organic silicon compound containing a monofunctional siloxane chain link M group and an organic silicon compound containing a tetrafunctional siloxane chain link Q group, wherein the molar ratio value range of the M group to the Q group is 0.4: 1-2.5: 1;
the inorganic particles are one or a composition of more than two of silicon dioxide, aluminum oxide, zinc oxide and magnesium oxide;
the alkaline catalyst is one or a composition 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 a composition of more than two of toluene, xylene and trimethylbenzene.
8. A method for preparing the silicone defoaming agent according to any one of claims 1 to 7, characterized by comprising the steps of:
s1, adding water, an organic solvent, a net-shaped structural agent and a condensation catalyst in a formula ratio into a reactor, stirring, raising the temperature and carrying out heat preservation reaction to enable the net-shaped structural agent to be hydrolyzed and subjected to intermolecular condensation to form a condensation oligomeric siloxane core cage-type structure;
s2, adding hydroxyl-containing polysiloxane with the formula amount into the step S1, carrying out condensation reaction to form an octopus structure, and distilling out volatile components to obtain a viscous oily substance, namely the component XI;
s3, adding the organic solvent, the inorganic particles and the organic silicon resin in the formula ratio into the other reactor, stirring, heating and keeping the temperature until the solid is dissolved to obtain a solution, namely a component XII;
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, keeping the temperature for reaction, and distilling off the solvent to obtain the organic silicon defoamer.
9. The method for preparing a silicone defoaming agent according to claim 8,
in the step S1, adding water, an organic solvent, a net-shaped structural agent and a condensation catalyst in a formula amount into a reactor, stirring, raising the temperature within the range of 40-100 ℃, and keeping the temperature for reaction for 0.5-3 hours;
in the step S2, adding hydroxyl-containing polysiloxane with a formula amount, and carrying out condensation reaction for 2-5 h;
in the step S3, adding the organic solvent, the inorganic particles and the organic silicon resin in the formula ratio into the other reactor, stirring, heating and keeping the temperature at 60-130 ℃ for 10-60 min;
in the step S4, adding a formula amount of alkaline catalyst, stirring, raising the temperature to react at 50-200 ℃ for 3-8 h, and evaporating the solvent to obtain the organic silicon defoamer.
10. The method according to claim 8, wherein in step S2, the temperature for evaporating volatile components is 40 to 150 ℃, and the vacuum degree is 0 to-0.1 MPa; in the step S4, the evaporating temperature of the evaporated solvent is 40 to 150 ℃, and the vacuum degree is 0 to-0.1 MPa.
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