CN113512196A - Alcohol solution of alkyl silanol and preparation method - Google Patents
Alcohol solution of alkyl silanol and preparation method Download PDFInfo
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- CN113512196A CN113512196A CN202110814981.3A CN202110814981A CN113512196A CN 113512196 A CN113512196 A CN 113512196A CN 202110814981 A CN202110814981 A CN 202110814981A CN 113512196 A CN113512196 A CN 113512196A
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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Abstract
The application discloses an alcoholic solution of alkyl silanol and a preparation method thereof, wherein the alcoholic solution comprises the following components: the catalyst comprises hydrocarbyl alkoxy silane, water, a mixed catalyst and a neutralizing agent, wherein the molar ratio of the hydrocarbyl alkoxy silane to the water is 1: 1-1: 6, the mass ratio of the mixed catalyst to the total mass of the hydrocarbyl alkoxy silane and the water is 1: 100-10: 100, and the mass ratio of the neutralizing agent to the total mass of the hydrocarbyl alkoxy silane and the water is 0: 100-10: 100. The preparation method is characterized in that the alcoholic solution of the alkyl silanol is prepared by acidic hydrolysis of alkyl alkoxy silane. The alcoholic solution of the hydrocarbyl silanol not only can provide active monomers required by synthesizing various organic silicon polymers and active intermediates required by synthesizing various silicon-containing compounds, but also can be directly used as or mixed with other coupling agents to be used as interface modifiers such as inorganic solid particle oleophylic modifiers, inorganic solid surface waterproof treatment agents, concrete anti-permeability anticorrosion impregnants and the like, and has wide application fields and good application prospects.
Description
Technical Field
The application belongs to the technical field of organic silicon materials, and particularly relates to an alcoholic solution of alkyl silanol and a preparation method thereof.
Background
The hydrocarbyl silanol is an important active monomer for synthesizing various organic silicon polymers, is an important active intermediate for synthesizing various silicon-containing compounds, can also be used as an active component of an interface modifier such as an inorganic solid particle oleophylic modifier, an inorganic solid surface waterproof agent, a concrete anti-permeability anticorrosion impregnant and the like, and is widely applied in the technical field of organic silicon materials.
The hydrocarbyl silanol is mainly obtained by hydrolyzing a corresponding hydrocarbyl alkoxy silane, and the commonly used catalyst in the hydrolysis process is small molecular acid such as sulfuric acid, hydrochloric acid, nitric acid, formic acid and acetic acid or small molecular alkali such as sodium hydroxide, potassium hydroxide, ammonia and tetramethylammonium hydroxide, and the catalyst has strong acidity or alkalinity, has certain corrosivity to equipment, is not beneficial to the stability of the hydrocarbyl silanol and the subsequent application of the hydrocarbyl silanol, needs to be neutralized and removed, and can cause the waste and pollution of raw materials; in addition, most of the hydrocarbyl hydrocarbyloxysilane is not soluble in water, and the common catalyst is relatively more soluble in water and insoluble in hydrocarbyl hydrocarbyloxysilane, so that hydrolysis reaction only occurs on a water-hydrocarbyl hydrocarbyloxysilane interface, the reaction is very slow without other additives, in order to promote mutual solubility and accelerate reaction of the raw materials, a large amount of small molecular alcohol is usually required to be added as a solvent, and a distillation step is additionally added after the reaction is finished to remove the alcohol, so that energy waste is caused, and environmental pollution and potential safety hazards can be caused. Therefore, there is a need to improve catalyst components, optimize hydrolysis process, and develop an alcoholic solution of hydrocarbyl silanol and a preparation method thereof.
Disclosure of Invention
In view of the above disadvantages, the present application provides an alcoholic solution of a hydrocarbyl silanol and a method for preparing the same.
In order to solve the technical problem, the application is realized by the following technical scheme:
in one aspect, the present application provides an alcoholic solution of a hydrocarbyl silanol, comprising: the catalyst comprises hydrocarbyl alkoxy silane, water, a mixed catalyst and a neutralizing agent, wherein the molar ratio of the hydrocarbyl alkoxy silane to the water is 1: 1-1: 6, the mass ratio of the mixed catalyst to the total mass of the hydrocarbyl alkoxy silane and the water is 1: 100-10: 100, and the mass ratio of the neutralizing agent to the total mass of the hydrocarbyl alkoxy silane and the water is 0: 100-10: 100.
Preferably, the alcohol solution of the above-mentioned hydrocarbyl silanol, wherein the composition and the mass ratio of the mixed catalyst are as follows:
acid titanate coupling agent: 100, respectively;
medium or high carbon alcohol: 0 to 150 parts by weight;
nonionic surfactant: 0 to 150 parts by weight;
quaternary ammonium salt type cationic surfactant or betaine type amphoteric surfactant: 0 to 300 parts by weight;
and/or the neutralizing agent is an anionic surfactant or small-molecule organic amine.
Preferably, the alcoholic solution of the hydrocarbyl silanol, wherein the hydrocarbyl alkoxy silane has a structural formula: r1 mSi(OR2)4-mOr (R)2O)3Si(CH2)xSn(CH2)ySi(OR2)3Wherein R is1Represents a C1-18 alkyl group, a C0-18 alkyl group substituted by a hetero atom-containing functional group which is stable in a weakly acidic alcohol-water system and has neutral to weakly acidic pH, and R2Represents C1-3 alkyl, and polyoxyethylene group or polyoxypropylene group with 2-3 polymerization degree and terminated by C1-3 alkoxy, wherein m is more than or equal to 0 and less than or equal to 3, n is more than or equal to 0 and less than or equal to 6, x is more than or equal to 1 and less than or equal to 18, and y is more than or equal to 1 and less than or equal to 18;
further, the heteroatom-containing functional group which can be stable in a weakly acidic alcohol-water system and has neutral to weakly acidic basicity includes: a combination of one or more of an acyl group or acyloxy group having 1 to 18 carbon atoms, a halogenated hydrocarbon group or pseudohalogenated hydrocarbon group having 1 to 18 carbon atoms, an hydrocarbyloxy group or hydrocarbylthio group having 1 to 18 carbon atoms, a hydrocarbon group having 0 to 18 carbon atoms substituted by a neutral quaternary ammonium salt or quaternary phosphonium salt group, a hydrocarbon group or hydrocarbyloxy group having 2 to 18 carbon atoms or acyloxy group substituted by an epoxy group or hydroxyl group, a polyoxyethylene group or polyoxypropylene group having a molecular weight of less than 8000, and a linear or branched polysiloxane group having a ratio of carbon to silicon atoms of less than 18:1 and a molecular weight of less than 8000;
still further, the hydrocarbyloxysilane includes: tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, chloromethyltrimethoxysilane, (dichloromethyl) trimethoxysilane, (trifluoromethyl) trimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, ethylmethyldimethoxysilane, cyanoethylmethyldimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, cyclopentyltrimethoxysilane, mercaptopropyltrimethoxysilane, acetoxypropyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane, 2- (3, 4-epoxycyclohexylethyl triethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltris (methoxyethoxy) silane, methyltrimethoxysilane, and a mixture of the like, Butyl triethoxysilane, octyl triethoxysilane, decyl triethoxysilane, dodecyl trimethoxysilane, octadecyl trimethoxysilane, tridecafluorooctyl trimethoxysilane, dimethyldodecyl [3- (triethoxysilyl) propyl ] ammonium chloride, dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, ethylenebis (trimethoxysilane), bis- [3- (trimethoxysilyl) propyl ] disulfide, or bis- [3- (triethoxysilyl) propyl ] tetrasulfide.
Preferably, the acidic titanate coupling agent is a pyrophosphoric acid type monoalkoxy titanate coupling agent, a pyrophosphoric acid type chelating titanate coupling agent, a phosphoric acid coordination titanate coupling agent or a phosphate titanate composite coupling agent, and the structural formula of the acidic titanate coupling agent is (R) respectively2O)Ti[OP(O)(OH)OP(O)(OR1)2]3、[(CH2O)2Ti][OP(O)(OH)OP(O)(OR1)2]2、[(R2O)4Ti][HOP(O)(OR1)2]2And (R)2O)Ti[OP(O)(OR1)2]3·m(R1O)nP(O)(OH)3-nWherein R is1Represents a C1-18 alkyl group, a C0-18 alkyl group substituted by a hetero atom-containing functional group which is stable in a weakly acidic alcohol-water system and has neutral to weakly acidic pH, and R2Represents an alkyl group having 1 to 3 carbon atoms, a polyoxyethylene group or a polyoxypropylene group having a degree of polymerization of 2 to 3 and terminated with an alkoxy group having 1 to 3 carbon atoms, wherein m is 1 or more and n is 1 or more and 2 or less;
further, the acidic titanate coupling agent comprises: isopropyl tri (dioctyloxypyrophosphato acyloxy) titanate, bis (dioctyloxypyrophosphato) ethylene titanate, tetraisopropyl di (dioctylphosphato) titanate, 2-di (allyloxymethyl) -1-butoxytri (dioctyloxypyrophosphato) titanate, titanate coupling agent TC-27, and the like.
Preferably, the alcohol solution of the above-mentioned hydrocarbon-based silanol is an alcohol solution of a medium or high carbon alcohol, wherein the medium or high carbon alcohol is a hydrocarbon having 4 to 18 carbon atoms substituted with a hydroxyl group, a hydrocarbon having 0 to 18 carbon atoms substituted with at least 1 hydroxyl group, which is stable in a weakly acidic alcohol-water system and has a neutral to weakly acidic basicity, and a β -dicarbonyl compound having 3 to 18 carbon atoms, which is stable in the presence of the enol-type tautomeric solid;
further, the medium or high carbon alcohol includes: n-butanol, t-butanol, cyclohexanol, n-octanol, isooctanol, lauryl alcohol, palmityl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isomeric tridecyl alcohol, guerbet alcohol, ethylene glycol, pinacol, glycerol, trimethylolpropane, diethylene glycol, dipropylene glycol, glucose, xylitol, mannitol, erythritol, inositol, butyl lactate, tributyl citrate, diisostearyl malate, methyl 12-hydroxystearate, methyl ricinoleate, glycerol distearate, glycerol dioleate, ethylene glycol monoisostearate, pentaerythritol tristearate, castor oil, ethylene glycol mono-t-butyl ether, 2-perfluorooctyl ethanol, nonylphenol, octyl salicylate, abietyl alcohol, 4-enol, hydroxyethylethylene bis-stearamide, acetylacetone, trifluoroacetylacetone, 1, 3-cyclopentanedione, pentaerythritol, ethylene glycol mono-t-butyl ether, 2-perfluorooctyl alcohol, nonylphenol, octyl salicylate, abietyl alcohol, 4-enol, hydroxyethylethylene bis-stearamide, acetylacetone, trifluoroacetylacetone, 1, 3-cyclopentanedione, hexadecanol, octadecanol, isomeric decanol, octadecanol, isomeric tridecanol, diisostearyl alcohol, and mixtures thereof, Diethyl malonate or isopropylidene malonate, etc. in any proportion.
Preferably, the non-ionic surfactant is a surfactant which is formed by connecting hydrophilic groups such as ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, inositol, monosaccharide, glycoside, methyl sulfoxide and the like, condensation polymers or phosphate esters thereof as hydrophilic terminals, hydrocarbon groups with 1-18 carbon atoms, hydrocarbon groups with 0-18 carbon atoms substituted by heteroatom-containing functional groups which can be stable in a weak acid alcohol-water system and have neutral to weak acidity in acid-base property as hydrophobic terminals, and groups such as single bonds, ester bonds, carbonyl groups, amide bonds, ether bonds, sulfoxide groups, sulfone groups and the like between the hydrophilic terminals and the hydrophobic terminals;
further, the nonionic surfactant includes: ethylene glycol monolaurate, propylene glycol monostearate, glycerol monostearate, pentaerythritol monoisostearate, dipentaerythritol distearate, dipropylene glycol monooleate, hexaglycerol pentaoleate, fatty alcohol polyoxyethylene ether, hydrogenated castor oil polyoxyethylene ether, fatty acid polyoxyethylene ester, alkylphenol polyoxyethylene ether, polyoxyethylene ether phosphate triester, one or more of fatty aldehyde glycerol acetal, alkylamide polyoxyethylene ether, alkyl glycoside, block polyoxyethylene-polyoxypropylene ether, polysiloxane-polyether block copolymer, span, tween, methyl glucoside stearate, sapindus saponin, quillaja saponin, laurocapram, octyl methyl sulfoxide or 4-octyloxy-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-1-oxide in any proportion.
Preferably, the quaternary ammonium salt cationic surfactant is a surfactant which is formed by taking a quaternary ammonium salt group as a hydrophilic end, taking a hydrocarbon group with 1-18 carbon atoms and a heteroatom functional group-substituted hydrocarbon group with neutral to weakly acidic acidity, which can be stable in a weakly acidic alcohol-water system, as a hydrophobic end, and linking the hydrophilic end and the hydrophobic end by a single bond, an ester bond, a carbonyl group, an amide bond, an ether bond, a sulfoxide group, a sulfone group and other groups;
further, the quaternary ammonium salt type cationic surfactant includes: benzyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, bromo cetyl pyridine, octadecyl trihydroxyethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, docosyl amide dimethyl hydroxypropyl ammonium chloride, didodecyl dimethyl ammonium chloride, N-dodecyl isoquinoline bromide, guar gum hydroxypropyl trimethyl ammonium chloride, cetyl amide propyl trimethyl ammonium chloride or distearyl hydroxyethyl methyl ammonium methyl sulfate.
Preferably, the betaine amphoteric active agent is a surfactant which is formed by linking an inner salt group consisting of an acidic anion group such as a carboxylic acid group, a sulfuric acid group, a sulfenic acid group, a sulfonic acid group, a phosphoric acid group or a phosphorous acid group and a basic cation group such as a quaternary ammonium group or a quaternary phosphonium group as a hydrophilic end, a hydrocarbon group having 1 to 18 carbon atoms, a hydrocarbon group having 0 to 18 carbon atoms and substituted by a heteroatom-containing functional group which is stable in a weakly acidic alcohol-water system and has neutral to weakly acidic acidity as a hydrophobic end, and a single bond, an ester bond, a carbonyl group, an amide bond, an ether bond, a sulfoxide group, a sulfone group and the like between the hydrophilic end and the hydrophobic end;
further, the betaine-type amphoteric active agent includes: octadecyl dihydroxyethyl betaine, dodecyl dimethyl betaine, cocamidopropyl betaine, lauramidopropyl hydroxysultaine, hexadecyl dimethyl hydroxypropyl sultaine, caprylamidopropyl betaine, erucamidopropyl betaine, oleamidophosphate betaine, dodecyl phosphate betaine, polysiloxane phosphate betaine, or dodecyl dimethyl (2-sulfurous acid) ethyl ammonium.
Preferably, the above alcoholic solution of a hydrocarbyl silanol is an anionic surfactant, wherein the anionic surfactant is an anionic surfactant which is formed by using an alkali metal salt, an alkaline earth metal salt, ammonium salt or quaternary ammonium salt of a sulfonic acid group, a sulfuric acid group, a carboxylic acid group, a boric acid group or a phosphoric acid group as a hydrophilic end, using a hydrocarbyl group with 1-18 carbon atoms, and a heteroatom-containing functional group which is stable in a weakly acidic alcohol-water system and has neutral to weakly acidic acidity as a hydrophobic end, and using groups such as a single bond, an ester bond, a carbonyl group, an amide bond, an ether bond, a sulfoxide group and a sulfone group for connection between the hydrophilic end and the hydrophobic end;
further, the anionic surfactant includes: sodium lauryl sulfate, sodium dodecylbenzene sulfonate, magnesium lauryl sulfate, sodium laureth sulfate, sodium stearate, sodium oleate, sodium fatty alcohol isethionate, sodium lauroyl glutamate, magnesium amidopolyoxyethylene ether sulfate, sodium laureth carboxylate, potassium lauryl phosphate, disodium laureth sulfosuccinate, fatty acid methyl ester sulfonate, fatty acid methyl ester ethoxylate sulfonate, potassium fatty alcohol polyoxyethylene ether phosphate, sodium methylene dinaphthalene sulfonate, sodium dodecylbenzoate, sodium dodecylsalicylate, sodium perfluorooctanoate, perfluorooctane, sodium sulfonate, sodium butylnaphthalene sulfonate, sodium cellulose sulfate, or the like.
Preferably, the alcoholic solution of the above-mentioned hydrocarbyl silanol, wherein the small molecule organic amine is a primary amine, a secondary amine or a tertiary amine having not more than 18 carbon atoms and not more than 6 nitrogen atoms.
Further, the small molecule organic amine comprises: ethylamine, dodecylamine, octadecylamine, diethylamine, triethylamine, tri-N-butylamine, ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, trimethylolmethylamine, aniline, p-phenylenediamine, 1,3, 5-triaminobenzene, ethylenediamine, tetramethylethylenediamine, diethylenetriamine, dipropylenetriamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenetetramine, propylenediamine, N- (2-aminopropyl) propane-1, 2-diamine, laurylamine dipropylenediamine, triethylenediamine, hydroxyethylethylenediamine, 1,4, 7-triazacyclononane, 1,4,7, 10-tetraazacyclododecane, 1, 8-diazacyclo [5,4,0] undecene, urea, biuret, tetramethylurea, hydroxyethylurea, guanidine, tetramethylguanidine, biguanide, dimethylbiguanide, and mixtures thereof, One or more of hexabasic bicyclic guanidine, melamine or 1-azabicyclo [2.2.2] octane and the like in any proportion.
The application also provides a preparation method of the alcoholic solution of the hydrocarbyl silanol, wherein the alcoholic solution of the hydrocarbyl silanol is prepared by acidic hydrolysis of hydrocarbyl alkoxy silane.
Preferably, the preparation method comprises the following steps:
weighing 1 molar part of hydrocarbyl alkoxy silane, and weighing alkoxy (OR) connected with silicon atom in hydrocarbyl alkoxy silane2) Water with equal mole number, the hydrocarbyl alkoxy silane and the water are respectively divided into 1 to 6 parts, and each part of the hydrocarbyl alkoxy silane and each part of the water are used as a group of materials1-6 groups of materials;
when preparing the mixed catalyst, respectively weighing 100 parts by mass of an acidic titanate coupling agent, 0-150 parts by mass of medium-carbon alcohol or high-carbon alcohol, 0-150 parts by mass of a nonionic surfactant and 0-300 parts by mass of a quaternary ammonium salt type cationic surfactant or a betaine type amphoteric surfactant;
when the neutralizer is prepared, a certain amount of anionic surfactant or micromolecular organic amine is weighed;
taking a first group of hydrocarbyl alkoxy silane, adding a mixed catalyst into the first group of hydrocarbyl alkoxy silane, wherein the mass ratio of the mixed catalyst to the total mass of the hydrocarbyl alkoxy silane and water is 1: 100-10: 100, stirring and emulsifying the mixture until the mixed catalyst is dissolved in the hydrocarbyl alkoxy silane, if the selected mixed catalyst cannot be completely dissolved, stirring the mixture until the mixed catalyst forms uniform emulsion or suspension in the hydrocarbyl alkoxy silane, then adding the first group of water into the system, and continuing stirring until the system becomes a clear and transparent solution; specifically, a high-speed shearing emulsifying machine is used for stirring and emulsifying, and the rotating speed is 2000 r/min-10000 r/min;
then stirring is continued, and the rest groups of hydrocarbyl alkoxy silane and water are added in turn, wherein when each group of materials is added, the hydrocarbyl alkoxy silane is added firstly, then the water is added, and after each group of materials is added, the next group of materials can be added continuously after the system becomes a clear and transparent solution;
after all the alkyl alkoxy silane and the water are added and the system becomes a clear and transparent solution, continuously stirring, and simultaneously adding a neutralizing agent, wherein the mass ratio of the neutralizing agent to the total mass of the alkyl alkoxy silane and the water is 0: 100-10: 100;
stirring was continued until the system became a homogeneous liquid, and then stirring was stopped and cooled to room temperature. Wherein, if the system is not transparent, the method indicates that insoluble inorganic salt or organic salt precipitates are generated in the system by adding the neutralizing agent, the system is stood for 0-4 h and then the precipitates are filtered to obtain clear and transparent solution, and if the system is transparent, the system does not need to be stood and filtered.
Optionally, in the preparation method, according to the application requirement of the alcoholic solution of the hydrocarbyl silanol, partial alcohol can be removed by reduced pressure distillation, wherein the temperature of the system is raised to 70 ℃ or lower, the distillation is performed under the condition that the vacuum degree is less than or equal to 0.005MPa, the distilled alcohol is collected to determine the residual alcohol content in the system, the distillation is stopped after the residual alcohol content meets the application requirement of the alcoholic solution of the hydrocarbyl silanol, the heating and the vacuum pumping are stopped, and the alcoholic solution of the hydrocarbyl silanol can be obtained after the system is cooled to room temperature.
It should also be noted that the hydrolysis of the hydrocarbyloxysilane to hydrocarbylsilanol is completed before the neutralizing agent is added, and the neutralizing agent is selected based on the application requirements of the alcoholic hydrocarbyl silanol solution, such as: if the final pH of the alcoholic solution of the hydrocarbyl silanol is required to be neutral, the neutralizing agent may be selected from small molecule monoamines, such as triethylamine, to neutralize the acidity of the acidic titanate coupling agent; if the final alcoholic solution of the hydrocarbyl silanol is required to contain no acidic titanate coupling agent, the neutralizing agent can be small molecular polyamine such as diethylenetriamine, and salt generated by the reaction of the polyamine and the acidic titanate coupling agent is precipitated as precipitate due to larger volume of anions and cations, higher electricity price and low solubility, and can be removed in the subsequent filtration step; if the final alcoholic solution of the hydrocarbyl silanol does not contain the quaternary ammonium salt cationic surfactant, the neutralizing agent can be selected from anionic surfactants, such as sodium stearate, and the anionic surfactants and the quaternary ammonium salt cationic surfactants react to generate inorganic salts and organic salts consisting of large-volume anions and cations, and the inorganic salts and the organic salts are both insoluble in a reaction system, so that the precipitates are separated out as precipitates and can be removed in a subsequent filtration step; if the pH value of the final alcoholic solution of the hydrocarbyl silanol and the residue of the auxiliary agent are not required, the neutralizing agent may not be added, and the filtration may not be performed. Likewise, the step of removing part of the alcohol by distillation is optional, and whether distillation is needed is reasonably selected mainly according to the concentration requirement of the alcohol solution of the alkyl silanol, and if the concentration of the final alcohol solution of the alkyl silanol is not required, the distillation can be omitted. In addition, the high temperature during distillation is not good for the stability of the hydrocarbyl silanol and may promote the polycondensation of the hydrocarbyl silanol, so the distillation temperature should not exceed 70 ℃ and should be as low as possible, and the vacuum degree of distillation should not exceed 0.005MPa and should be as low as possible in order to allow the distillation to be performed at as low a temperature as possible.
Compared with the prior art, the method has the following technical effects:
(1) the alcoholic solution of the hydrocarbyl silanol not only can provide active monomers required by synthesizing various organic silicon polymers and active intermediates required by synthesizing various silicon-containing compounds, but also can be directly used as or mixed with other coupling agents to be used as interface modifiers such as inorganic solid particle oleophylic modifiers, inorganic solid surface waterproof treatment agents, concrete anti-permeability anticorrosion impregnants and the like, and has wide application fields and good application prospects;
(2) compared with the micromolecular acid or alkali catalyst used in the prior art, the mixed catalyst prepared and used in the application has higher efficiency, less dosage and faster reaction, and the main principle is that the acid titanate coupling agent molecule has acid pyrophosphate and titanate group, the former provides stronger acidity to catalyze the hydrolysis of hydrocarbyl alkoxy silane, the latter and activated hydrocarbyl alkoxy silane, has obvious catalytic action on hydrolysis reaction, in addition, the acid titanate coupling agent, medium-carbon alcohol or high-carbon alcohol and the coordination compound of the acid titanate coupling agent, the nonionic surfactant, the quaternary ammonium salt type cationic surfactant and the betaine type amphoteric surfactant jointly form a phase transfer catalytic system, promotes the fusion or mutual diffusion of water and hydrocarbyl alkoxy silane by various chemical actions such as coordination, hydrogen bond and the like, and has catalytic action on hydrolysis reaction. The components with different functions cooperate to form a high-efficiency mixed catalyst, so that the using amount of the catalyst can be effectively reduced, the reaction speed can be improved, the preparation time can be shortened, and the high-efficiency mixed catalyst has good economy;
(3) the preparation process does not need to add any solvent, the components are emulsified by the surfactant at the initial stage of the reaction, the reaction area is increased, the reaction is promoted, and the alcohol generated by the hydrolysis of the alkyl alkoxy silane is used as the solvent at the middle stage and the later stage of the reaction to further promote the reaction, so that the solvent does not need to be additionally added, and the preparation method has good economy, safety and environmental protection.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The starting materials used in the following examples are commercial industrial-grade chemical raw materials unless otherwise specified.
Example 1
The alcoholic solution of the hydrocarbyl silanol of this example was prepared as follows:
220.381g (1.0mol) of butyltriethoxysilane, 54.045g (3.0mol) of water and 27.443g of isopropyl tris (dioctyloxypyrophosphato-yloxy) titanate are respectively weighed, namely only an acidic titanate coupling agent is used as a catalyst, and the mass ratio of the acidic titanate coupling agent to the total mass of the hydrocarbyl hydrocarbyloxysilane and water is 10: 100;
adding isopropyl tri (dioctyloxy pyrophosphato acyloxy) titanate into butyl triethoxysilane, starting a high-speed shearing emulsifying machine, stirring at the rotating speed of 2000r/min, adding water when the isopropyl tri (dioctyloxy pyrophosphato acyloxy) titanate is completely dissolved and the system becomes transparent, and continuously stirring until the system is transparent again to obtain an alcoholic solution of the hydrocarbyl silanol, namely an alcoholic solution of the butyl silanol.
Stirring is started until the total time of the prepared butyl silanol ethanol solution is 20min, and the prepared butyl silanol ethanol solution is sealed and stored in a dark environment at the temperature of 20 ℃ and can be kept clear and transparent for 72h without deterioration.
Example 2
The alcoholic solution of the hydrocarbyl silanol of this example was prepared as follows:
178.301g (1.0mol) of isobutyl trimethoxy silane and 54.045g (3.0mol) of water are weighed respectively;
respectively weighing 10.628g of isopropyl tri (dioctyloxy pyrophosphato acyloxy) titanate and 12.607g of benzyl trimethyl ammonium chloride, and uniformly mixing to obtain a mixed catalyst, wherein the mass ratio of the acidic titanate coupling agent to the quaternary ammonium cationic surfactant in the mixed catalyst is 100: 118.631; the ratio of the mass of the mixed catalyst to the total mass of the hydrocarbyloxysilane and water is 10: 100;
respectively weighing 2.428g of laurylamine dipropylene diamine and 20.807g of sodium stearate, and uniformly mixing the materials to obtain a neutralizing agent, wherein the mass ratio of the neutralizing agent to the total mass of the alkyl alkoxy silane and the water is 10: 100;
adding the mixed catalyst into isobutyltrimethoxysilane, starting a high-speed shearing emulsifying machine, stirring at the rotating speed of 4000r/min, adding water when the mixed catalyst forms uniform turbid liquid in the isobutyltrimethoxysilane, stirring until the system is transparent again, adding a neutralizing agent, continuously stirring until the system becomes uniform turbid liquid, stopping stirring, cooling to room temperature, standing the system for 0-4 h, and performing suction filtration to remove precipitates to obtain an alcoholic solution of the alkyl silanol, namely a methanol solution of the isobutylsilanol.
The cooling and standing time is not counted, the stirring is started until the total time of the methanol solution of the isobutyl silanol is 35min, and the prepared methanol solution of the isobutyl silanol is sealed and stored in a light-proof environment at the temperature of 20 ℃, and can be kept clear and transparent for 120h without deterioration.
Example 3
The alcoholic solution of the hydrocarbyl silanol of this example was prepared as follows:
368.269g (1.0mol) of nonafluorohexyltrimethoxysilane and 54.045g (3.0mol) of water are weighed respectively;
respectively weighing 6.000g of isopropyl tri (dioctyloxy pyrophosphato acyloxy) titanate, 9.000g of cetyl alcohol, 9.000g of diglycerol dioleate and 18.000g of bromohexadecyl pyridine, and uniformly mixing to obtain a mixed catalyst, wherein the mass ratio of an acidic titanate coupling agent, higher alcohol, a nonionic surfactant and a quaternary ammonium cationic surfactant in the mixed catalyst is 100:150:150: 300; the ratio of the mass of the mixed catalyst to the total mass of the hydrocarbyloxysilane and water is 9.945: 100;
adding the mixed catalyst into nonafluorohexyltrimethoxysilane, starting a high-speed shearing emulsifying machine, stirring at the rotating speed of 6000r/min, adding water when the mixed catalyst forms a uniform suspension in the nonafluorohexyltrimethoxysilane, and continuously stirring until the system is transparent again to obtain an alcoholic solution of the hydrocarbyl silanol, namely a methanol solution of the nonafluorohexylsilanol.
Stirring is started until the total time of the methanol solution of the nonafluorohexylsilanol is 30min, and the prepared methanol solution of the nonafluorohexylsilanol is sealed and stored in a dark environment at the temperature of 20 ℃ and can be kept clear and transparent for 24h without deterioration.
Example 4
The alcoholic solution of the hydrocarbyl silanol of this example was prepared as follows:
290.514g (1.0mol) of dodecyl trimethoxy silane and 54.045g (3.0mol) of water are respectively weighed, and the dodecyl trimethoxy silane and the water are respectively and equally divided into 6 parts;
respectively weighing 1.500g of isopropyl tri (dioctyloxy pyrophosphato acyloxy) titanate, 0.400g of octadecanol, 0.600g of span 85 and 0.946g of bromohexadecyl pyridine, and uniformly mixing to obtain a mixed catalyst, wherein the mass ratio of an acidic titanate coupling agent, medium-carbon alcohol or high-carbon alcohol, a nonionic surfactant and a quaternary ammonium cationic surfactant in the mixed catalyst is 100:26.67:40: 63.04; the ratio of the mass of the mixed catalyst to the total mass of the hydrocarbyl alkoxy silane and the water is 1: 100;
adding a mixed catalyst into dodecyl trimethoxy silane, starting a high-speed shearing emulsifying machine, stirring at the rotating speed of 4000r/min, adding water when the mixed catalyst forms a uniform suspension in the dodecyl trimethoxy silane, and continuously stirring until the system becomes a clear and transparent solution;
then adding the dodecyl trimethoxy silane and the water in turn, wherein after each part of water is added, the next part of dodecyl trimethoxy silane is continuously added until the system becomes a clear and transparent solution, after all the dodecyl trimethoxy silane and the water are added, the system is continuously stirred until the system is transparent again, the temperature of the system is raised to 70 ℃, and 70.000g of methanol is distilled and removed under the vacuum degree of 0.005MPa to obtain an alcoholic solution of the alkyl silanol, namely a methanol solution of the dodecyl silanol;
the distillation time is not counted, the stirring is started until the total time of preparing the methanol solution of the dodecyl silanol is 160min, and the prepared methanol solution of the dodecyl silanol is sealed and stored in a dark environment at the temperature of 20 ℃ and can be kept clear and transparent for 5h without deterioration.
Example 5
The alcoholic solution of the hydrocarbyl silanol of this example was prepared as follows:
116.234g (1.0mol) of dimethylvinylethoxysilane, 18.015g (1.0mol) of water and 6.712g of isopropyl tris (dioctyloxy pyrophosphato-yloxy) titanate are respectively weighed, namely only an acidic titanate coupling agent is used as a catalyst, and the mass ratio of the acidic titanate coupling agent to the total mass of hydrocarbyl alkoxy silane and water is 5: 100;
adding isopropyl tri (dioctyloxy pyrophosphato acyloxy) titanate into dimethyl vinyl ethoxysilane, starting a high-speed shearing emulsifying machine, stirring at the rotating speed of 4000r/min, adding water when the isopropyl tri (dioctyloxy pyrophosphato acyloxy) titanate is completely dissolved and the system becomes transparent, and continuously stirring until the system is transparent again to obtain an alcoholic solution of the hydrocarbyl silanol, namely an alcoholic solution of the dimethyl vinyl silanol.
Stirring is started until the total time of the ethanol solution of the dimethyl vinyl silanol is 45min, and the prepared ethanol solution of the dimethyl vinyl silanol is sealed and stored in a dark environment at the temperature of 20 ℃ and can be kept clear and transparent for 72h without deterioration.
Example 6
The alcoholic solution of the hydrocarbyl silanol of this example was prepared as follows:
538.953g (1.0mol) of bis- [3- (triethoxysilyl) propyl ] tetrasulfide and 108.090g (6.0mol) of water are respectively weighed and are respectively divided into 3 parts;
respectively weighing 19.411g of isopropyl tri (dioctyloxy pyrophosphato acyloxy) titanate and 19.411g of dodecyl bromide, and uniformly mixing to obtain a mixed catalyst, wherein the mass ratio of the acidic titanate coupling agent to the quaternary ammonium cationic surfactant in the mixed catalyst is 100: 100; the ratio of the mass of the mixed catalyst to the total mass of the hydrocarbyloxysilane and water is 6: 100;
adding a mixed catalyst into bis- [3- (triethoxysilyl) propyl ] tetrasulfide, starting a high-speed shearing emulsifying machine, stirring at the rotating speed of 10000r/min, adding water in portions when the mixed catalyst forms uniform suspension in the bis- [3- (triethoxysilyl) propyl ] tetrasulfide, wherein after each portion of water is added, continuing to add the next portion of water until the system becomes a clear and transparent solution, and after all the water is added, continuing to stir until the system becomes a clear and transparent solution to obtain an alcoholic solution of the alkyl silanol, namely a methanol solution of the bis- [3- (trihydroxy silicon) propyl ] tetrasulfide.
Stirring is started until the total time of preparing the methanol solution of the bis- [3- (trihydroxy silicon) propyl ] tetrasulfide is 30min, and the prepared methanol solution of the bis- [3- (trihydroxy silicon) propyl ] tetrasulfide is sealed and stored in a dark environment at the temperature of 20 ℃ and can be kept clear and transparent for 24h without deterioration.
The alcoholic solution of the hydroxyl silanol prepared by the method is an intermediate, is mainly used for synthesizing other organic silicon materials or is mixed with other coupling agents for use, and the property of the alcoholic solution of the hydroxyl silanol is mainly determined by the chemical property of the hydroxyl silanol; the preparation of the alcoholic solution of the hydroxyl silanol prepared by the method has short time and higher production efficiency; the alcohol solution of the hydroxyl silanol prepared by the method also has certain stability, namely the alcohol solution of the hydroxyl silanol can be stored in a sealed and light-proof environment at 20 ℃ for a period of time of being clear, transparent and unchangeable, and the property is mainly determined by the chemical properties (acid-base property, chemical steric hindrance and the like) of the hydroxyl silanol, but is also influenced by the catalyst dosage in the preparation process, whether the alcohol solution is heated and other factors. It should also be noted, however, that the alcoholic solution of the hydroxysilanol is an intermediate and is generally ready for use, i.e. immediately after the alcoholic solution of the hydroxysilanol has been removed for further processing or use.
In conclusion, in the application, the mixed catalyst is used, and the synergistic effect of the components of the mixed catalyst is utilized to play a more efficient catalytic performance, so that the problems of material and energy waste, equipment corrosion, environmental pollution, potential safety hazards and the like caused by the use of small molecular acid or alkali catalysts and alcohol solvents in the prior art are solved, the catalyst dosage can be effectively reduced, the reaction speed is increased, the preparation time is shortened, no solvent is required, and the economic performance is good; the alcoholic solution of the hydrocarbyl silanol can provide active monomers required by synthesizing various organic silicon polymers and active intermediates required by synthesizing various silicon-containing compounds, can be directly used as or mixed with other coupling agents to be used as interface modifiers such as inorganic solid particle oleophylic modifiers, inorganic solid surface waterproof agents, concrete anti-permeability anticorrosion impregnants and the like, and has wide application fields and good application prospects.
The above embodiments are merely to illustrate the technical solutions of the present application and are not limitative, and the present application is described in detail with reference to preferred embodiments. It will be understood by those skilled in the art that various modifications and equivalent arrangements may be made in the present invention without departing from the spirit and scope of the present invention and shall be covered by the appended claims.
Claims (22)
1. An alcoholic solution of a hydrocarbyl silanol, comprising: the catalyst comprises hydrocarbyl alkoxy silane, water, a mixed catalyst and a neutralizing agent, wherein the molar ratio of the hydrocarbyl alkoxy silane to the water is 1: 1-1: 6, the mass ratio of the mixed catalyst to the total mass of the hydrocarbyl alkoxy silane and the water is 1: 100-10: 100, and the mass ratio of the neutralizing agent to the total mass of the hydrocarbyl alkoxy silane and the water is 0: 100-10: 100.
2. Alcoholic solution of hydroxysilanol according to claim 1, wherein the mixed catalyst has the following composition and mass ratio:
acid titanate coupling agent: 100, respectively;
medium or high carbon alcohol: 0 to 150 parts by weight;
nonionic surfactant: 0 to 150 parts by weight;
quaternary ammonium salt type cationic surfactant or betaine type amphoteric surfactant: 0 to 300 parts by weight;
and/or the neutralizing agent is an anionic surfactant or small-molecule organic amine.
3. Root of herbaceous plantAn alcoholic solution of a hydrocarbyloxysilane of claim 1, wherein the hydrocarbyloxysilane has the formula: r1 mSi(OR2)4-mOr (R)2O)3Si(CH2)xSn(CH2)ySi(OR2)3Wherein R is1Represents a C1-18 alkyl group, a C0-18 alkyl group substituted by a hetero atom-containing functional group which is stable in a weakly acidic alcohol-water system and has neutral to weakly acidic pH, and R2Represents C1-3 alkyl, and polyoxyethylene group or polyoxypropylene group with 2-3 polymerization degree, which is terminated by C1-3 alkoxy, wherein m is more than or equal to 0 and less than or equal to 3, n is more than or equal to 0 and less than or equal to 6, x is more than or equal to 1 and less than or equal to 18, and y is more than or equal to 1 and less than or equal to 18.
4. The alcoholic solution of hydrocarbyl silanol of claim 3, wherein the heteroatom-containing functional group that is stable in a weakly acidic alcohol-water system and neutral to weakly acidic in acidity and basicity comprises: a C1-18 acyl or acyloxy group, a C1-18 halogenated or pseudohalogenated alkyl group, a C1-18 hydrocarbyloxy or hydrocarbylthio group, a C0-18 alkyl group substituted by a neutral quaternary ammonium salt or quaternary phosphonium salt group, a C2-18 alkyl or hydrocarbyloxy group substituted by an epoxy group or hydroxyl group, an acyloxy group, a polyoxyethylene group or polyoxypropylene group having a molecular weight of less than 8000, or a linear or branched polysiloxane group having a C/Si ratio of less than 18:1 and a molecular weight of less than 8000.
5. The alcoholic solution of hydrocarbyloxysilane of claim 1,3 or 4, wherein the hydrocarbyloxysilane comprises: tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, chloromethyltrimethoxysilane, (dichloromethyl) trimethoxysilane, (trifluoromethyl) trimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, ethylmethyldimethoxysilane, cyanoethylmethyldimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, cyclopentyltrimethoxysilane, mercaptopropyltrimethoxysilane, acetoxypropyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane, 2- (3, 4-epoxycyclohexylethyl triethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltris (methoxyethoxy) silane, methyltrimethoxysilane, and a mixture of the like, Butyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, dimethyldodecyl [3- (triethoxysilyl) propyl ] ammonium chloride, dimethyloctadecyl [3- (trimethoxysilyl) propyl ] ammonium chloride, ethylenebis (trimethoxysilane), bis- [3- (trimethoxysilane) propyl ] disulfide or bis- [3- (triethoxysilyl) propyl ] tetrasulfide.
6. The alcoholic solution of a hydrocarbyl silanol of claim 2, wherein the acidic titanate coupling agent is a pyrophosphoric acid type monoalkoxy titanate coupling agent, a pyrophosphoric acid type chelating titanate coupling agent, a phosphoric acid coordination titanate coupling agent, or a phosphoric acid ester titanate composite coupling agent, each of which has the structural formula (R)2O)Ti[OP(O)(OH)OP(O)(OR1)2]3、[(CH2O)2Ti][OP(O)(OH)OP(O)(OR1)2]2、[(R2O)4Ti][HOP(O)(OR1)2]2And (R)2O)Ti[OP(O)(OR1)2]3·m(R1O)nP(O)(OH)3-nWherein R is1Represents a C1-18 alkyl group, a C0-18 alkyl group substituted by a hetero atom-containing functional group which is stable in a weakly acidic alcohol-water system and has neutral to weakly acidic pH, and R2Represents an alkyl group having 1 to 3 carbon atoms, a polyoxyethylene group or a polyoxypropylene group having a degree of polymerization of 2 to 3 and terminated with an alkoxy group having 1 to 3 carbon atoms, wherein m is 1 or more and n is 1 or more and 2 or less.
7. Alcoholic solution of a hydrocarbyl silanol according to claim 2 or 6, characterized in that the acidic titanate coupling agent comprises: one or more of isopropyl tri (dioctyloxypyrophosphato acyloxy) titanate, bis (dioctyloxypyrophosphato) ethylene titanate, tetraisopropyl di (dioctylphosphato) titanate, 2-di (allyloxymethyl) -1-butoxytri (dioctyloxypyrophosphato) titanate and titanate coupling agent TC-27.
8. The alcoholic solution of a hydrocarbyl silanol as claimed in claim 2, wherein the medium-or high-carbon alcohol is a hydrocarbon having 4 to 18 carbon atoms substituted with a hydroxyl group, a hydrocarbon having 0 to 18 carbon atoms substituted with at least 1 hydroxyl group which is substituted with a hetero atom-containing functional group which is stable in a weakly acidic alcohol-water system and neutral to weakly acidic in acid-base property, and a β -dicarbonyl compound having 3 to 18 carbon atoms which stabilizes the enol-type tautomeric solid.
9. Alcohol solution of a hydrocarbon-based silanol according to claim 2 or 8, wherein said medium or higher alcohol comprises: n-butanol, t-butanol, cyclohexanol, n-octanol, isooctanol, lauryl alcohol, palmityl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isomeric tridecyl alcohol, guerbet alcohol, ethylene glycol, pinacol, glycerol, trimethylolpropane, diethylene glycol, dipropylene glycol, glucose, xylitol, mannitol, erythritol, inositol, butyl lactate, tributyl citrate, diisostearyl malate, methyl 12-hydroxystearate, methyl ricinoleate, glycerol distearate, glycerol dioleate, ethylene glycol monoisostearate, pentaerythritol tristearate, castor oil, ethylene glycol mono-t-butyl ether, 2-perfluorooctyl ethanol, nonylphenol, octyl salicylate, abietyl alcohol, 4-enol, hydroxyethylethylene bis-stearamide, acetylacetone, trifluoroacetylacetone, 1, 3-cyclopentanedione, pentaerythritol, ethylene glycol mono-t-butyl ether, 2-perfluorooctyl alcohol, nonylphenol, octyl salicylate, abietyl alcohol, 4-enol, hydroxyethylethylene bis-stearamide, acetylacetone, trifluoroacetylacetone, 1, 3-cyclopentanedione, hexadecanol, octadecanol, isomeric decanol, octadecanol, isomeric tridecanol, diisostearyl alcohol, and mixtures thereof, Diethyl malonate or isopropylidene malonate.
10. The alcoholic solution of a hydrocarbon-based silanol as claimed in claim 2, wherein the nonionic surfactant is a surfactant having a hydrophilic group such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, inositol, monosaccharide, glycoside, methyl sulfoxide, a polycondensate thereof, or a phosphate ester thereof as a hydrophilic end, a hydrocarbon group having 1 to 18 carbon atoms, a hydrocarbon group having 0 to 18 carbon atoms and being substituted with a hetero atom-containing functional group which is stable in a weakly acidic alcohol-water system and has neutral to weakly acidic basicity as a hydrophobic end, and a single bond, an ester bond, a carbonyl group, an amide bond, an ether bond, a sulfoxide group, a sulfone group, or the like between the hydrophilic end and the hydrophobic end.
11. Alcoholic solution of a hydrocarbyl silanol according to claim 2 or 10, characterized in that the non-ionic surfactant comprises: ethylene glycol monolaurate, propylene glycol monostearate, glycerol monostearate, pentaerythritol monoisostearate, dipentaerythritol distearate, dipropylene glycol monooleate, hexaglycerol pentaoleate, fatty alcohol polyoxyethylene ether, hydrogenated castor oil polyoxyethylene ether, fatty acid polyoxyethylene ester, alkylphenol polyoxyethylene ether, polyoxyethylene ether phosphate triester, one or more of fatty aldehyde glycerol acetal, alkylamide polyoxyethylene ether, alkyl glycoside, block polyoxyethylene-polyoxypropylene ether, polysiloxane-polyether block copolymer, span, tween, methyl glucoside stearate, sapindus saponin, quillaja saponin, laurocapram, octyl methyl sulfoxide or 4-octyloxy-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-1-oxide.
12. The alcoholic solution of a alkylsilicanol as claimed in claim 2, wherein said quaternary ammonium salt cationic surfactant is a surfactant comprising a quaternary ammonium salt group as a hydrophilic end, a hydrocarbon group having 1 to 18 carbon atoms, a hydrocarbon group having 0 to 18 carbon atoms which is substituted with a hetero atom-containing functional group which is stable in a weakly acidic alcohol-water system and has neutral to weakly acidic acidity, as a hydrophobic end, and a single bond, an ester bond, a carbonyl group, an amide bond, an ether bond, a sulfoxide group, a sulfone group and the like between the hydrophilic end and the hydrophobic end.
13. Alcoholic solution of a hydrocarbyl silanol according to claim 2 or 12, characterized in that the quaternary cationic surfactant comprises: benzyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, bromo cetyl pyridine, octadecyl trihydroxyethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, docosyl amide dimethyl hydroxypropyl ammonium chloride, didodecyl dimethyl ammonium chloride, N-dodecyl isoquinoline bromide, guar gum hydroxypropyl trimethyl ammonium chloride, cetyl amide propyl trimethyl ammonium chloride or distearyl hydroxyethyl methyl ammonium methyl sulfate.
14. The alcoholic solution of a hydrocarbon-based silanol as claimed in claim 2, wherein the betaine-type amphoteric active agent is a surfactant comprising an inner salt group comprising an acidic anionic group such as a carboxylic acid group, a sulfuric acid group, a sulfonic acid group, a phosphoric acid group or a phosphorous acid group and a basic cationic group such as a quaternary ammonium group or a quaternary phosphonium group as a hydrophilic terminal, a hydrocarbon group having 1 to 18 carbon atoms, a hydrocarbon group having 0 to 18 carbon atoms which is substituted with a hetero atom-containing functional group which is stable in a weakly acidic alcohol-water system and has neutral to weakly acidic acidity as a hydrophobic terminal, and a single bond, an ester bond, a carbonyl group, an amide bond, an ether bond, a sulfoxide group or a sulfone group between the hydrophilic terminal and the hydrophobic terminal.
15. Alcoholic solution of a hydrocarbyl silanol according to claim 2 or 14, characterized in that the betaine-type amphoteric active agent comprises: octadecyl dihydroxyethyl betaine, dodecyl dimethyl betaine, cocamidopropyl betaine, lauramidopropyl hydroxysultaine, hexadecyl dimethyl hydroxypropyl sultaine, caprylamidopropyl betaine, erucamidopropyl betaine, oleamidophosphate betaine, dodecyl phosphate betaine, polysiloxane phosphate betaine or dodecyl dimethyl (2-sulfurous acid) ethyl ammonium.
16. The alcoholic solution of a hydrocarbon-based silanol as claimed in claim 2, wherein the anionic surfactant is an anionic surfactant comprising a hydrophilic end comprising an alkali metal salt, an alkaline earth metal salt, an ammonium salt or a quaternary ammonium salt of a sulfonic acid group, a sulfuric acid group, a carboxylic acid group, a boric acid group or a phosphoric acid group, a hydrophobic end comprising a hydrocarbon group having 1 to 18 carbon atoms, a hetero atom-containing functional group which is stable in a weakly acidic alcohol-water system and has neutral to weakly acidic acid and a hetero atom-containing functional group which is substituted with the hydrocarbon group having 0 to 18 carbon atoms, and a single bond, an ester bond, a carbonyl group, an amide bond, an ether bond, a sulfoxide group, a sulfone group or the like bonded between the hydrophilic end and the hydrophobic end.
17. Alcoholic solution of a hydrocarbyl silanol according to claim 2 or 16, characterized in that the anionic surfactant comprises: sodium lauryl sulfate, sodium dodecylbenzene sulfonate, magnesium lauryl sulfate, sodium laureth sulfate, sodium stearate, sodium oleate, sodium fatty alcohol isethionate, sodium lauroyl glutamate, magnesium amidopolyoxyethylene ether sulfate, sodium laureth carboxylate, potassium lauryl phosphate, disodium laureth sulfosuccinate, fatty acid methyl ester sulfonate, fatty acid methyl ester ethoxylate sulfonate, potassium fatty alcohol polyoxyethylene ether phosphate, sodium methylene dinaphthalene sulfonate, sodium dodecylbenzoate, sodium dodecylsalicylate, sodium perfluorooctanoate, perfluorooctane, sodium sulfonate, sodium butylnaphthalene sulfonate or sodium cellulose sulfate, in any proportion.
18. The alcoholic solution of a hydrocarbylsilanol according to claim 2, wherein the small organic amine is a primary, secondary or tertiary amine having not more than 18 carbon atoms and not more than 6 nitrogen atoms.
19. Alcoholic solution of a hydrocarbon-based silanol according to claim 2 or 18, wherein said small molecule organic amine comprises: ethylamine, dodecylamine, octadecylamine, diethylamine, triethylamine, tri-N-butylamine, ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, trimethylolmethylamine, aniline, p-phenylenediamine, 1,3, 5-triaminobenzene, ethylenediamine, tetramethylethylenediamine, diethylenetriamine, dipropylenetriamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenetetramine, propylenediamine, N- (2-aminopropyl) propane-1, 2-diamine, laurylamine dipropylenediamine, triethylenediamine, hydroxyethylethylenediamine, 1,4, 7-triazacyclononane, 1,4,7, 10-tetraazacyclododecane, 1, 8-diazacyclo [5,4,0] undecene, urea, biuret, tetramethylurea, hydroxyethylurea, guanidine, tetramethylguanidine, biguanide, dimethylbiguanide, and mixtures thereof, One or more of hexabasic bicyclic guanidine, melamine or 1-azabicyclo [2.2.2] octane in any proportion.
20. The method for preparing an alcoholic solution of an alkylsilicol as claimed in any one of claims 1 to 19, wherein the alcoholic solution of an alkylsilicol is prepared by acidic hydrolysis of an alkyl hydrocarbyloxysilane.
21. The method of claim 20, comprising the steps of:
weighing 1 molar part of hydrocarbyl alkoxy silane, and weighing alkoxy (OR) connected with silicon atom in hydrocarbyl alkoxy silane2) Water with equal mole number, wherein the hydrocarbyl alkoxy silane and the water are respectively divided into 1-6 parts, and each part of the hydrocarbyl alkoxy silane and each part of the water are used as a group of materials, so that 1-6 groups of materials are formed;
when preparing the mixed catalyst, respectively weighing 100 parts by mass of an acidic titanate coupling agent, 0-150 parts by mass of medium-carbon alcohol or high-carbon alcohol, 0-150 parts by mass of a nonionic surfactant and 0-300 parts by mass of a quaternary ammonium salt type cationic surfactant or a betaine type amphoteric surfactant;
when the neutralizer is prepared, a certain amount of anionic surfactant or micromolecular organic amine is weighed;
taking a first group of hydrocarbyl alkoxy silane, adding a mixed catalyst into the first group of hydrocarbyl alkoxy silane, wherein the mass ratio of the mixed catalyst to the total mass of the hydrocarbyl alkoxy silane and water is 1: 100-10: 100, stirring and emulsifying the mixture until the mixed catalyst is dissolved in the hydrocarbyl alkoxy silane, if the selected mixed catalyst cannot be completely dissolved, stirring the mixture until the mixed catalyst forms uniform emulsion or suspension in the hydrocarbyl alkoxy silane, then adding the first group of water into the system, and continuing stirring until the system becomes a clear and transparent solution;
then stirring is continued, and the rest groups of hydrocarbyl alkoxy silane and water are added in turn, wherein when each group of materials is added, the hydrocarbyl alkoxy silane is added firstly, then the water is added, and after each group of materials is added, the next group of materials can be added continuously after the system becomes a clear and transparent solution;
after all the alkyl alkoxy silane and the water are added and the system becomes a clear and transparent solution, continuously stirring, and simultaneously adding a neutralizing agent, wherein the mass ratio of the neutralizing agent to the total mass of the alkyl alkoxy silane and the water is 0: 100-10: 100;
stirring was continued until the system became a homogeneous liquid, and then stirring was stopped and cooled to room temperature.
22. The preparation method of claim 21, wherein a portion of the alcohol is removed by distillation under reduced pressure, wherein the system is heated to 70 ℃ or less, the distillation is performed under a vacuum degree of 0.005MPa or less, the distilled alcohol is collected to determine the residual alcohol content in the system, the distillation is stopped after the residual alcohol content meets the application requirement of the alcoholic solution of the hydrocarbyl silanol, the heating and the vacuum pumping are stopped, and the alcoholic solution of the hydrocarbyl silanol is obtained after the system is cooled to room temperature.
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| CN116804153A (en) * | 2023-08-24 | 2023-09-26 | 上海柯珑清洁技术有限公司 | Acrylamide surfactant composition and preparation method thereof |
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