CN100372764C - Nano organic solvent silicasol and preparation method thereof - Google Patents
Nano organic solvent silicasol and preparation method thereof Download PDFInfo
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- CN100372764C CN100372764C CNB2005100209272A CN200510020927A CN100372764C CN 100372764 C CN100372764 C CN 100372764C CN B2005100209272 A CNB2005100209272 A CN B2005100209272A CN 200510020927 A CN200510020927 A CN 200510020927A CN 100372764 C CN100372764 C CN 100372764C
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Abstract
The present invention discloses an organic solvent of silica sol which is mainly composed of the components of the following proportion: 5 to 15% of silica particle, 94.5 to 83.5% of organic solvent and 0.5 to 1.5% of blocking agent. The silica sol is colorless, clear and transparent; the particle diameter of silica is between 10 and 100 nanometers; the pH value of the sol system is between 6 and 9. The present invention also discloses an economical, convenient, practical and general method for preparing the organic solvent of silica sol whose boiling point is higher than that of water by taking sodium silicate as a raw material. In the method, sodium silicate is taken as a raw material; the method comprises: firstly, an ion-exchange method is adopted; secondly, a stabilizing agent playing a role of a blocking agent and preventing gelatification is added during the polymerization process of H4SiO4 so as to obtain stable silica hydrosol; thirdly, the silica hydrosol after being prepared is mixed with an organic solvent with a certain volume and a high boiling point; finally, a solvent displacement method is adopted to displace water in the mixture by making use of the difference of the boiling points of water and the added solvent so as to prepare the organic solvent of silica sol with a high boiling point.
Description
Technical field
The invention belongs to technical field of nano material, particularly relate to the preparation method of organic solvent silicasol.
Background technology
SiO
2Colloidal sol (also claiming silicon sol) is polymer amorphous Si O
2The colloidal solution of microparticulate in solvent.After nineteen forty-one American Bird invention utilized ion exchange method to produce silicon sol, silicon sol was used widely in manufacturing fields such as fiber, fabric, papermaking, coating, caking agent, paint, pottery, medicine, food, precision casting and electronic industries gradually.Now, in semi-conductor industry, silicon sol is used to silicon chip is carried out precise polished again, and application prospect is very wide.
Silicon sol can be divided into water solvent silicon sol or organic solvent silicasol according to the difference of solvent property.Water solvent silicon sol SiO
2Concentration be generally 10-40%, its size is 5-100nm, specific surface area is 50-400m
2/ g, outward appearance is creamy white translucent, and is most at PH〉stable under 9 the alkaline condition, adopt Na
2O, NH
3Deng as stablizer, minority is stable under the acidic conditions of PH＜4, adopts Al
2O
3, NH
4 +, Cl
-Deng as stablizer.Water-sol silicon sol is used widely in manufacturing fields such as fiber, fabric, papermaking, coating, caking agent, paint, pottery, medicine, food, precision casting and electronic industries.
Since the nineties in 20th century, the research of organic solvent silicon dioxide gel (abbreviating organic solvent silicasol as) and application have also obtained developing rapidly.The SiO of the low boiling point organic solvent silicon sol that has made
2Concentration be generally 10-40%, its size is 5-100nm, specific surface area is 200-500m
2/ g, water content＜7.5, outward appearance is creamy white translucent, and stable under acidic conditions, stablizer commonly used has Al
2O
3, HCl, HNO
3, H
2SO
4And H
2C
2O
4Deng, with the water dilution low boiling point organic solvent silicon sol of equal volume, its pH＜4.Organic solvent silicasol can be applicable to non-aqueous system, as all needing organic solvent silicasol at manufacturing magnetic colloid and fields such as recording medium, high-performance ceramics compound, support of the catalyst, heavy body colloid storage battery and working electrolyte for aluminium electrolytic capacitor.
SiO commonly used at present
2The preparation method of colloidal sol has following several: 1. tetraethoxy (TEOS) hydrolysis method; 2. ion exchange method; 3. electrolytic electro-dialysis method; 4. microemulsion method etc.Tang Yongliang is at " Zhejiang chemical industry ", and 2003,23 (5): 4-6: people such as Wang Zixin are at " chemical propellant and macromolecular material ", and 2003,1 (5): 34-39; Wan Qijin etc. are at " Hubei Normal University's journal (natural science edition) ", and 1994,14 (3): in above three pieces of articles of 86-92, the preparation method and the application of having summarized silicon sol, and main silicon sol manufacturer's silicon sol product situation both at home and abroad.That the most patents quoted in three pieces of survey articles and bibliographical information all is SiO in the above
2The preparation method of the water-sol.The product of silicon sol also all is SiO both at home and abroad
2The water-sol.And its SiO
2The PH stable range of the water-sol is acid PH＜4 and alkaline PH〉9.Though domestic and international product SiO
2Water-sol concentration can reach 10-40%, but that the outward appearance of product is creamy white is translucent.SiO
2Though the water-sol is used widely in manufacturing fields such as fiber, fabric, papermaking, coating, caking agent, paint, pottery, medicine, food, precision casting and electronic industries, because SiO
2The colloidal sol of the water-sol is water, can not be applied to those and refuse aqueous systems; In addition, existing stable SiO
2The water-sol is present under acidity (PH＜4) or alkalescence (PH〉9) condition, is not suitable for using under the neutral system environment.Organic solvent silicasol can be applicable to non-aqueous system, as making magnetic colloid and fields such as recording medium, high-performance ceramics compound, support of the catalyst, heavy body colloid storage battery and working electrolyte for aluminium electrolytic capacitor.
So development can be applicable to the focus that the organic solvent silicasol of anhydrous water-based system has become scientific worker's research.
The preparation method of existing organic solvent silicasol is to be raw material with water glass, adopts ion exchange method to make SiO
2The water-sol, or directly adopt common silicon sol, adopt the solvent azeotrope distillation technique of " solvent azeotropic " method then, dehydration obtains organic solvent silicasol.Such as, the United States Patent (USP) 5902226 on May 11st, 1999 has been reported the method for preparing propyl alcohol and Virahol silicon sol.But the boiling point of the organic solvent propyl alcohol of the organic solvent silicasol that this method obtains is 97.2 ℃, the boiling point of Virahol is 82.4 ℃, all be lower than 100 ℃ of the boiling points of water, so this method is only applicable to prepare the low-boiling organic solvent silicasol of the boiling point of organic solvent than water.And adopt " solvent azeotropic " can't obtain water-free organic solvent silicasol.And for example United States Patent (USP) 5885485 in 1999 has been reported the method for preparing the organic solvent silicasol of lower boiling pure and mild ketone with similar approach.Above two patents all can't obtain water-free substantially organic solvent silicasol, though the concentration of resulting silicon sol can arrive 10-40%, outward appearance still is an oyster white, does not obtain appearance colorless, clarification, transparent organic solvent silicasol.
Existing organic silicon sol preparation method only is applicable to the lower boiling organic silicon sol of preparation, and as ethanol, propyl alcohol and Virahol silicon sol, its boiling point of solvent for use is all below 100 ℃.And the organic silicon sol outward appearance for preparing is creamy white translucently, and water content＜7.5 could be stablized under acidic conditions.Such organic silicon sol can't be used for those and definitely refuse water, and the energy withstand temp is feared the field of acid and alkali corrosion greater than 100 ℃.As the used organic silicon sol of sheet type aluminum electrolytic capacitor, just requiring its pH value is 6-8, and the organic silicon sol water white transparency is definitely refused water, also must bear the temperature of 250 ℃ reflow welding.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of economy, easy and practical high boiling point waterless nano organic solvent silicasol, prepared colloidal sol appearance colorless, clarification, transparent, particle diameter is between 10nm-100nm, and system pH is 6-9.
The present invention is raw material with the water glass, adopts ion exchange method to generate orthosilicic acid (H earlier
4SiO
4); Then at H
4SiO
4Polymerization process in add the stablizer that a kind of effect that can play end-capping reagent stops gelation to take place, obtain stable SiO
2The water-sol; After water-sol preparation is finished, with the water-sol with distill after the high boiling organic solvent of certain volume mixes, because the boiling point of water is 100 ℃, boiling point than organic solvent is low, use " solvent exchange method ", utilize both boiling-point differences the water in the mixture all can be cemented out, thereby make waterless nano organic solvent SiO
2Colloidal sol.
Preparing SiO with ion exchange method
2In the process of the water-sol, work as Na
2SiO
3When the aqueous solution passed through hydrogen type cation exchange resin, the sodium ion in the solution was by the H in the ion exchange resin
+Displacement generates orthosilicic acid (H
4SiO
4), H
4SiO
4The intermolecular polymerization of dewatering forms SiO
2Particle, these SiO
2Particle is dispersed in and has just formed SiO in the water
2The water-sol.
The orthosilicic acid structural formula is:
Because H
4SiO
4Molecule has four activity hydroxies, so each molecule can intermolecular polyreaction take place with molecule on every side and slough a water molecules.So just cause the polymerization between the molecule, formed SiO gradually
2Particle.But if this polymerization process does not add control, polyreaction constantly goes on, and will form a huge tridimensional network, SiO
2Colloidal sol will gelation, and whole system becomes the frozen glue shape, can't utilize again.Therefore, adopt suitable means that polyreaction is stopped when proceeding to certain phase, and be that SiO is stablized in preparation no longer again
2The key of colloidal sol.The present invention passes through at H
4SiO
4Polymerization process in add the effect that a kind of material plays end-capping reagent, can stop the generation of gelation.For example, adopt in system, to add organo-silicon coupling agent (for example: the hydroxy silicon oil of various models, alkoxyl group silicone oil, organoalkoxysilane etc.) etc., just can in process of the test, play the effect that stops gelation preferably.
With certain organoalkoxysilane RSi (OR)
3Be example, its end-capping reagent stops the action principle of gelation as follows: at H
4SiO
4Polymerization process in add a kind of organo-silicon coupling agent RSi (OR) that can play the end-capping reagent effect
3, RSi (OR)
33 alkoxyl groups and polymerization process in be exposed to 3 activity hydroxies reactions of outside, make H
4SiO
4The R reaction of polyreaction in activity hydroxy and OR generate corresponding alkanol after, active end is closed, and makes H
4SiO
4Polyreaction end, effectively stoped SiO
2The continuing to grow up of colloidal particle and the gel phenomenon that occurs.
Detailed technology scheme according to the preparation method of a kind of nano organic solvent silicasol that basic thought proposed of above-mentioned preparation method is as follows:
A kind of preparation method of nano organic solvent silicasol may further comprise the steps:
(1), preparation Na
2SiO
3The aqueous solution.With analytically pure water glass reagent (Na
2SiO
39H
2O) be mixed with the Na of 10-35% with high purity deionized water
2SiO
3The aqueous solution.
(2), ion-exchange.With Na
2SiO
3The aqueous solution imports the exchange column that hydrogen type cation exchange resin is housed from the exchange column inlet, opens cationic exchange column outlet piston, collects exchange liquid, and detects the pH value in exit at any time.When the pH value of exchange liquid becomes 4～5, change collector, collect exchange liquid as the silicon sol sample.Can find that in this process along with the generation of exchange column intermediate ion exchange, the color of exchange column intermediate ion exchange resin shoals from top to bottom gradually, is become light yellow by dark-brown.As whole Na
2SiO
3After the solution adding finishes, continue in exchange column, to inject high purity deionized water,, collect whole products so that displace the silicon sol that keeps in the exchange column.When the pH value of exchange liquid returns to 6～7, stop to collect.Detect the Na in the silicon sol collect with uranyl acetate zinc test solution
+, detect less than Na
+It is qualified to be.
(3), underpressure distillation.Method with underpressure distillation boils off excessive water, and obtaining concentration is 5-15%SiO
2The water-sol.Exchange resin can be regenerated after losing efficacy, and reused.Need the thing of explanation, this step is not indispensable step, and its effect just boils off excessive water, if the resulting SiO of step (2)
2Water-sol concentration between 5-15%, can omit by this step.
(4), place ageing.With the H that obtains
4SiO
4Solution is placed ageing 1-24 hour under 60-80 ℃ of temperature.The homothermic purpose is to make polymerization carry out for some time, thereby makes SiO
2Particle is grown up to requiring size, finds by the pH value of continuous test system during this period, and the pH value of system can constantly raise, and this is because H
4SiO
4Polymerization generates SiO
2The cause of particle.
(5), end-blocking.The end-capping reagent that adds 0.5-1.5% (mass percent).Room temperature ageing 24 hours again after mixing.The purpose that adds end-capping reagent is in order to prevent the gelation of colloidal sol.
(6), solvent exchange.SiO with the concentration known of top step preparation
2Colloidal sol mixes with a certain amount of high boiling organic solvent.The ratio of the water-sol and high boiling organic solvent is calculated by the concentration of the high boiling organic solvent colloidal sol of required preparation and to be fed intake.Mixture packed into distill in the water distilling apparatus, answer organic solvent boiling point, system pH that the temperature of the hierarchy of control is lower than adding during distillation between 6-9, and stir with magnetic stirring apparatus.Methods such as employing oil bath are hierarchy of control temperature accurately, different controlled temperature, heating medium kind difference (as using boiling range at the whiteruss more than 230 ℃).Water is easier to distill from mixture in order to make, and can adopt the method for underpressure distillation.Regulate the pH value and adopt the method that adds ammoniacal liquor or higher fatty acid.After water in the system reduced to a certain degree, the viscosity of system had certain increase, and temperature can sharply raise.Draw small amount of liquid from system this moment, uses anhydrous CuSO
4Detect and whether contain water.If anhydrous CuSO
4Constant indigo plant, not moisture in the explanation system, solvent exchange just can stop.
Supplementary notes: foreign ion such as the Cl of purified colloidal sol in detecting colloidal sol
-, SO4
2-, Na
+The time, should: use AgNO
3Solution detects Cl
-Not having precipitation produces; Use BaCl
2Solution detects SO
4 2-Not having precipitation produces; Detect Na with the uranyl acetate zincon
+, do not detect.With SiO in the Sears alkali determination of adsorption method colloidal sol
2The specific surface area of particle is tried to achieve SiO according to specific surface area
2Particle diameter.With measuring pH value with the water dilution back of organic solvent silicasol equal volume.Record the viscosity of organic solvent silicasol with rotational viscosimeter.
The adoptable end-capping reagent of step (4) can be hydroxy silicon oil, alkoxyl group silicone oil, organoalkoxysilane, metatitanic acid coupling agent of various models etc., is polydimethylsiloxane, 209-hydroxy silicon oil, methyl phenyl silicone oil, monomethyl triethoxyl silane, monomethyl Trimethoxy silane, dimethyldiethoxysilane, dimethyldimethoxysil,ne of dimethyl-silicon hydroxyl etc. as low viscosity, low-molecular-weight end group.
The employed high boiling solvent of step (5) can be butanols, isopropylcarbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, glycerine, methylformamide, dimethyl formamide, diethylformamide, methyl-sulphoxide, glycerine, methyl 2-furoate, γ-Wu Neizhi, γ-Ding Suan lactone, tetramethylene sulfone and methyl-2-pyrrolidone etc.
The prepared nano organic solvent silicasol according to the present invention is mainly by SiO
2Particulate, organic solvent and end-capping reagent are formed.This organic solvent silicasol contains the SiO of 5-15% mass percent
2Particulate; The organic solvent that contains the 94.5%-83.5% mass percent; The end-capping reagent that contains the 0.5-1.5% mass percent.Its appearance colorless, clarification, transparent, SiO
2Particle diameter is between 10-100nm, and the sol system pH value is between the 6-9.
In the above-mentioned organic solvent silicasol, organic solvent adopts boiling point to be higher than 100 ℃ type, can be butanols, isopropylcarbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, glycerine, methylformamide, dimethyl formamide, diethylformamide, methyl-sulphoxide, glycerine, methyl 2-furoate, γ-Wu Neizhi, γ-Ding Suan lactone, tetramethylene sulfone and methyl-2-pyrrolidone etc.
In the above-mentioned anhydrous organic solvent silicon sol, end-capping reagent is a kind of organo-silicon coupling agent, can be hydroxy silicon oil, alkoxyl group silicone oil, organoalkoxysilane of various models etc.As low viscosity, low-molecular-weight end group polydimethylsiloxane, 209-hydroxy silicon oil, methyl phenyl silicone oil, monomethyl triethoxyl silane, monomethyl Trimethoxy silane, dimethyldiethoxysilane, dimethyldimethoxysil,ne of dimethyl-silicon hydroxyl etc.
Beneficial effect of the present invention:
The present invention can prepare the boiling point anhydrous organic solvent silicon sol higher than the boiling point of water, comprises ethylene glycol silicon sol, glycerine silicon sol, dimethyl formamide silicon sol and γ-butyrolactone silicon sol etc.
The anhydrous organic silicon sol outward appearance of the high boiling point clear that the present invention is prepared has good stability, and places after 1 year, and any variation does not take place its outward appearance.If do not require appearance colorless, the clarification, transparent of high boiling point anhydrous organic solvent silicon sol, can make concentration according to the method described above is the high boiling organic solvent silicon sol of 15-40%.
Use " solvent exchange method " has been proposed from SiO
2The water-sol prepares the universal method of high boiling organic solvent silicon sol---and the boiling point that utilizes organic solvent all cements out the water in the mixture by distillation than high boths' of water boiling-point difference, thereby makes high boiling anhydrous organic solvent silicon sol.This method economy, easy, practical is easy to apply.
By adding end-capping reagent, can effectively prevent SiO as stablizer
2The gelation of the water-sol, obtaining PH is the stable SiO of 6-9
2The water-sol.Simultaneously, preparing with the solvent exchange method in the high boiling organic solvent silicasol process, also can well prevent the gelation of silicon sol.Product use with the dilution of the water of organic solvent silicasol equal volume after, its PH remains between the 6-9.
Can prepare the organic solvent silicasol that concentration is 5-15%, contain end-capping reagent 0.5-1.5%, contain organic solvent 94.5%-83.5%, its appearance colorless, clarification, transparent, gH is 6-9, SiO
2Particle diameter at 10nm-100nm, specific surface area is 100-450m
2/ g.Organic solvent silicasol stability with the present invention's preparation is good, can display more than 1 year.
Description of drawings
Fig. 1: end-capping reagent stops the action principle figure of gelation
Fig. 2: organic silicon sol preparation process schema
Embodiment
Embodiment one
(1). take by weighing analytically pure water glass reagent (Na
2SiO
39H
2O) 116.25 grams are dissolved in 383.75 milliliters of high purity deionized water the aqueous solution that preparation obtains 10% water glass.
(2). with Na
2SiO
3The aqueous solution is opened the ion-exchange column outlet piston that hydrogen type cation exchange resin is housed from ion-exchange importing suitable for reading, collects exchange liquid.And constantly detect mouthful pH value of place's exchange liquid, in time replenish Na simultaneously
2SiO
3Solution.When the pH value of exchange liquid becomes 4～5, collect and flow out exchange liquid as the silicon sol sample.As whole Na
2SiO
3After the solution adding finishes, continue in pipe, to inject high purity deionized water,, collect whole products so that displace the silicon sol that keeps in the exchange column.When the pH value of exchange liquid returns to 6～7, stop to collect.With deionized water exchange column is rinsed well, removed remaining silicic acid in order to using next time.If Zeo-karb lost efficacy, after then needing to regenerate, re-use.Detect the Na in the silicon sol collect with uranyl acetate zinc test solution
+, as detecting less than Na
+Be qualified product.
(3). excessive water is removed in the method distillation with underpressure distillation, and obtaining mass percent concentration is 5%SiO
2The water-sol.
(4). with the H that obtains
4SiO
4Solution is placed ageing 2 hours under 70 ℃ of temperature.
(5). add a certain amount of end-capping reagent by the silicic acid quality in the solution, as: triethoxy-silicane [CH
3Si (OC
2H
5)
3] etc., making its mass percent concentration in solution is 0.5%, room temperature ageing 24 hours again after mixing.
(6). mix SiO by 10: 9 volume ratios
2The water-sol and high boiling point ethylene glycol solvent are packed mixture into and are carried out underpressure distillation in the water distilling apparatus.The PH of control mixing solutions is 7, regulates the pH value and adopts the method that adds ammoniacal liquor or higher fatty acid.In still-process, constantly stir with magnetic stirring apparatus.After water in the system reduced to a certain degree, the viscosity of system had certain increase, and temperature can sharply raise.Draw small amount of liquid from system this moment, uses anhydrous CuSO
4Detect and whether contain water.If anhydrous CuSO
4Constant indigo plant, content not moisture or water is few in the explanation system, stops the distillation of solvent exchange.Foreign ion such as Cl in the product reply colloidal sol
-, SO
4 2-, Na
+Detect, if: AgNO used
3Aqueous assay Cl
-Do not have precipitation and produce, use BaCl
2Aqueous assay SO
4 2-Not having precipitation produces, detects Na with the uranyl acetate zincon
+Not detecting, then is qualified product.High boiling point ethylene glycol silicon sol appearance colorless, the clarification, transparent of preparing.The organic silicon sol that makes contains SiO
2Micelle concentration 5%, end-capping reagent CH
3Si (OC
2H
5)
30.5%, ethylene glycol 94.5%.With SiO in the alkali determination of adsorption method colloidal sol of Sears
2The specific surface area of particle is 390m
2/ g, median size is 22 nanometers.With measuring pH value with the water dilution back of organic solvent silicasol equal volume is 7.The viscosity that records organic solvent silicasol with rotational viscosimeter is 19.4 centipoises.
Embodiment two
Press the step of embodiment 1, take by weighing analytically pure water glass reagent (Na
2SiO
39H
2O) 232.5 grams are dissolved in 267.5 milliliters of high purity deionized water, and preparation obtains the aqueous solution of 20% water glass.After ion-exchange, remove excessive water with the method distillation of underpressure distillation, obtaining concentration is 10%SiO
2The water-sol.With the H that obtains
4SiO
4Solution was placed ageing after 2 hours under 70 ℃ of temperature, add a certain amount of end-capping reagent by the quality of solution mesosilicic acid, as triethoxy-silicane [CH
3Si (OC
2H
5)
3], making its mass percent concentration in solution is 1.0%.Room temperature ageing 24 hours again after mixing.Mix SiO by 10: 9 volume ratios
2The water-sol and high boiling point ethylene glycol solvent are packed mixture into and are carried out underpressure distillation in the water distilling apparatus, and the pH of control mixing solutions is 9, removes all water, prepares the ethylene glycol silicon sol.Its appearance colorless, clarification, transparent.In the silicon sol, contain SiO
2Micelle concentration is 10%, end-capping reagent CH
3Si (OC
2H
5)
31.0%, ethylene glycol 89%.With SiO in the alkali determination of adsorption method colloidal sol of Sears
2The specific surface area of particle is 258m
2/ g, median size is 30nm, and using and measuring the pH value with the water dilution back of organic solvent silicasol equal volume is 9, and viscosity is 22.6 centipoises.
Embodiment three
Press the step of embodiment 1, take by weighing analytically pure water glass reagent (Na
2SiO
39H
2O) 384.8 grams are dissolved in 151.2 milliliters and go in high-purity ionized water, and preparation obtains the aqueous solution of 30% water glass.After ion-exchange, remove excessive water with the method distillation of underpressure distillation, obtaining concentration is 15%SiO
2The water-sol.With the H that obtains
4SiO
4Solution was placed ageing after 2 hours under 70 ℃ of temperature, add a certain amount of end-capping reagent by the quality of the silicic acid of solution, as monomethyl triethoxyl silane [CH
3Si (OC
2H
5)
3], making its percentage concentration in solution is 1.5%.Room temperature ageing 24 hours again after mixing.Mix SiO by 10: 9 volume ratios
2The water-sol and high boiling point ethylene glycol solvent are packed mixture into and are carried out underpressure distillation in the water distilling apparatus, and the pH of control mixing solutions is 9, prepares the ethylene glycol silicon sol.Its appearance colorless, clarification, transparent.Contain SiO in the silicon sol
2Micelle concentration is 15%, end-capping reagent CH
3Si (OC
2H
5)
31.5%, ethylene glycol 83.5%.With SiO in the alkali determination of adsorption method colloidal sol of Sears
2The specific surface area of particle is 190m
2/ g, median size is 38nm, and using and measuring the pH value with the water dilution back of organic silicon sol equal volume is 9, and viscosity is 25.7 centipoises.
Embodiment four
Press the step of embodiment 1, only ethylene glycol is changed into the γ-Ding Suan lactone, prepare γ-Ding Suan lactone silicon sol.Its appearance colorless, clarification, transparent.Contain SiO in the silicon sol
2Micelle concentration is 5%, end-capping reagent CH
3Si (OC
2H
5)
30.5%, ethylene glycol 94.5%.With SiO in the alkali determination of adsorption method colloidal sol of Sears
2The specific surface area of particle is 395m
2/ g, median size is 25nm, and the pH value is 7, and viscosity is 18.2 centipoises.
Embodiment five
Press the same steps as of embodiment 2, only ethylene glycol is changed into the γ-Ding Suan lactone, prepare γ-Ding Suan lactone silicon sol.Its appearance colorless, clarification, transparent.Contain SiO in the silicon sol
2Micelle concentration is 10%, end-capping reagent CH
3Si (OC
2H
5)
31.0%, ethylene glycol 89%.With SiO in the alkali determination of adsorption method colloidal sol of Sears
2The specific surface area of particle is 330m
2/ g, median size is 37nm, and the pH value is 8, and viscosity is 20.5 centipoises.
Embodiment six
Press the same steps as of embodiment 3, only ethylene glycol is changed into the γ-Ding Suan lactone, prepare γ-Ding Suan lactone silicon sol.Its appearance colorless, clarification, transparent.Contain SiO in the silicon sol
2Micelle concentration is 15%, end-capping reagent CH
3Si (OC
2H
5)
31.5%, ethylene glycol 83.5%.With SiO in the alkali determination of adsorption method colloidal sol of Sears
2The specific surface area of particle is 220m
2/ g, median size is 45 nanometers, and pH value is 8, and viscosity is 24.2 centipoises.
Embodiment seven
Press the step of embodiment 1, only change ethylene glycol into dimethyl formamide, prepare the dimethyl formamide silicon sol.Its appearance colorless, clarification, transparent.Contain SiO in the silicon sol
2Micelle concentration is 5%, end-capping reagent CH
3Si (OC
2H
5)
30.5%, ethylene glycol 94.5%.With SiO in the alkali determination of adsorption method colloidal sol of Sears
2The specific surface area of particle is 470m
2/ g, median size is 30nm, and the pH value is 7, and viscosity is 10.8 centipoises.
Embodiment eight
Press the step of embodiment 3, only change ethylene glycol into tetramethylene sulfone, prepare the tetramethylene sulfone silicon sol.Its appearance colorless, clarification, transparent.Containing SiO2 micelle concentration in the silicon sol is 15%, end-capping reagent CH
3Si (OC
2H
5)
31.5%, ethylene glycol 83.5%.With SiO in the alkali determination of adsorption method colloidal sol of Sears
2The specific surface area of particle is 228m
2/ g, median size is 40nm, and the pH value is 9, and viscosity is 14.5 centipoises.
Embodiment nine
Press the step of embodiment 3, only change ethylene glycol into glycerine, prepare the glycerine silicon sol.Its appearance colorless, clarification, transparent.Contain SiO in the silicon sol
2Micelle concentration is 15%, end-capping reagent CH
3Si (OC
2H
5)
31.5%, ethylene glycol 83.5%.With SiO in the alkali determination of adsorption method colloidal sol of Sears
2The specific surface area of particle is 112m
2/ g, median size is 40 nanometers, and the pH value is 9, and viscosity is 935.1 centipoises.
Claims (4)
1. the preparation method of an organic solvent silicasol is characterized in that, it may further comprise the steps:
(1), preparation Na
2SiO
3The aqueous solution is with analytically pure Na
2SiO
39H
2O is mixed with the Na of 10-35% with high purity deionized water
2SiO
3The aqueous solution;
(2), ion-exchange, with Na
2SiO
3The aqueous solution imports the exchange column that hydrogen type cation exchange resin is housed from the exchange column inlet, opens cationic exchange column outlet piston, collects exchange liquid, and detects the pH value in exit at any time; When the pH value of exchange liquid becomes 4～5, change collector, collect exchange liquid as the silicon sol sample; As whole Na
2SiO
3After the solution adding finishes, continue in exchange column, to inject high purity deionized water,, collect whole products so that displace the silicon sol that keeps in the exchange column; When the pH value of exchange liquid returns to 6～7, stop to collect;
(3), place ageing, with the H that obtains
4SiO
4Solution is placed ageing 1-24 hour under 60-80 ℃ of temperature;
(4), end-blocking, the hydroxy silicon oil, alkoxyl group silicone oil or the organoalkoxysilane that add mass percent and be the various models of 0.5-1.5% be as end-capping reagent, room temperature ageing 24 hours again after mixing;
(5), solvent exchange, with the SiO of the concentration known of top step preparation
2Colloidal sol and a certain amount of boiling point are higher than 100 ℃ butanols, isopropylcarbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, glycerine, methylformamide, dimethyl formamide, diethylformamide, methyl-sulphoxide, methyl 2-furoate, γ-Wu Neizhi, γ-Ding Suan lactone, tetramethylene sulfone or methyl-2-pyrrolidone organic solvent mix; Mixture packed into distill in the water distilling apparatus, answer the temperature of the hierarchy of control to be lower than the organic solvent boiling point of adding during distillation, and hierarchy of control pH value is between 6-9, and stir with magnetic stirring apparatus; When not moisture, promptly check constant indigo plant with anhydrous cupric sulfate in the system, solvent exchange just can stop.
2. the preparation method of organic solvent silicasol according to claim 1 is characterized in that, adds the step of underpressure distillation between described step (2) and the step (3), with the method for underpressure distillation rare silicon water-sol is concentrated, and obtaining concentration is 5-15%SiO
2The water-sol.
3. the preparation method of organic solvent silicasol according to claim 1 is characterized in that, adopts accurately hierarchy of control temperature of bath oiling in described step (5) operating process.
4. the preparation method of organic solvent silicasol according to claim 1 is characterized in that, adopts the method for underpressure distillation in described step (5) operating process, distills from mixture so that water is easier; Regulating the pH value adopts the method that adds ammoniacal liquor or higher fatty acid to regulate.
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| CN103626192B (en) * | 2013-12-13 | 2015-08-19 | 中国乐凯集团有限公司 | A kind of preparation method of organic solvent type silica sol |
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| CN110304635A (en) * | 2019-06-13 | 2019-10-08 | 南通大学 | The method that non-protonic solvent extraction prepares silica polyhedron organosol |
| CN111289493B (en) * | 2020-03-27 | 2021-08-06 | 电子科技大学 | Surface-enhanced Raman substrate and preparation method thereof |
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