CN102719129B - Preparation method of silica aerogel aqueous heat-insulating coating - Google Patents
Preparation method of silica aerogel aqueous heat-insulating coating Download PDFInfo
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- CN102719129B CN102719129B CN 201210230531 CN201210230531A CN102719129B CN 102719129 B CN102719129 B CN 102719129B CN 201210230531 CN201210230531 CN 201210230531 CN 201210230531 A CN201210230531 A CN 201210230531A CN 102719129 B CN102719129 B CN 102719129B
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Abstract
The invention discloses a preparation method of a silica aerogel aqueous heat-insulating coating, and is characterized in that: prepared SiO2 microspheres are hydrophobic inside and hydrophilic outside; and the aerogel microspheres can be added into an aqueous coating carrier to prepare a good heat-insulating material. The main preparation method comprises the following steps of: before drying the prepared wet gel microspheres, performing surface modification by using an organic silane or an organic chlorosilane, so that the prepared wet gel microspheres are hydrophobic by grafting a large number of alkoxy groups or alkyl groups on the surfaces thereof, or directly preparing the hydrophobic wet gel microspheres; performing surface modification on the microspheres by using a hydrophilic silane coupling agent, and drying to obtain the SiO2 microspheres which are hydrophobic inside and hydrophilic outside; and adding the prepared microspheres into an aqueous coating for preparing the aqueous heat-insulating coating.
Description
Technical field
The present invention relates to a kind of outside hydrophilic SiO of inner hydrophobic that adopts
2Aerogel microball is as insulating unit, and use coating prepares a kind of water-borne heat-insulating coating as carrier.Be a kind of composite environmental-friendly coating that is widely used in heat insulation field.
Background technology
SiO
2Aerogel (silica aerogel) is a kind of novel nano porous material of controllable structure, and its porosity is up to 80%-99%, and specific surface area is up to 800-1000m
2G
-1, typical bore hole size is 1-50nm, solid-state network structure elements is of a size of 1～20nm, the low 0.01Wm that reaches of the total heat conductance under its normal temperature and pressure
-1K
-1, be the minimum a kind of material of thermal conductivity in the present solid material.SiO
2Aerogel is as a kind of thermal insulation material of efficient and light weight (the Schmidt M that is with a wide range of applications in fields such as aerospace, chemical industry, metallurgy and energy saving buildings, Schwertfeger F. Applications for silica aerogel products, J. Non-Cryst.Solids, 1998, (225): 364-368).
SiO
2The application of aerogel block body material has certain limitation, the SiO very big as preparation
2Aerogel block body material is difficult on technology.In addition, preparation special shape block materials and block size control also is not easy.So, prepare SiO often earlier
2Aerogel microball (aerogel beads) (Duan Li Qu, Hai Ching Lee, George L. Gould, Methods for manufacture of aerogels, US patent, 2006/0084707 A1), be applied SiO in some special fields
2Aerogel microball in aerospace as application (the Fesmire J.E. aspect the insulating back-up materials such as liquid hydrogen storing box of airship, Aerogel insulation systems for space launch applications, Cryogenics, 2006,46(2-3), 111-117).But, SiO
2Inconvenience when aerogel directly is to use with the maximum problem of powder form application needs the outer container that install powder additional.Particularly use in erose occasion, the thermofin occupation space is big, if having living space when limiting, is difficult to use.
With SiO
2When aerogel microball and polymer coating are mixed with compound heat-insulation coating, can not be subjected to the restriction of space, area and heat insulation object shapes, only need this thermal insulating coating is coated on the heat insulation object.The convenience of coating application and the characteristics of two aspects of aerogel heat-proof excellent property have been taken full advantage of.But, can be divided into two kinds of oil paint and water-borne coatingss for present coating, because water-borne coatings in use, does not have the release of volatile organic matter, be considered to feature of environmental protection coating, so water-borne coatings has the very big market requirement.Present prepared SiO
2Aerogel microball also has only two kinds, and a kind of is wetting ability SiO
2Aerogel microball, the prepared SiO of general method
2Aerogel microball all is hydrophilic.Another kind is hydrophobicity SiO
2Aerogel microball, be that the wetting ability aerogel is become the hydrophobicity aerogel by finishing, used method is the modifier with trimethylchlorosilane and so on, the hydroxyl of its hole surface is become alkyl or alkoxyl group, as document (Ming long Liu, De an Yang, Yuan fang Qu, Preparation of super hydrophobic silica aerogel and study on its fractal structure, Journal of Non-Crystalline Solids, 2008,354, given method 4927-4931), because it is prepared aerogel microball is hydrophobic fully, inconsistent fully with water.Oxyalkyl or the alkyl of main grafting in the time of in joining water-borne coatings, can not form uniform composite coating in the hydrophobicity aerogel pores, demixing phenomenon appears, after the coating drying, inhomogeneous, obscission can appear in coating, influences the work-ing life of effect of heat insulation and thermal insulating coating.When the hydrophobicity microballoon joins in the oil paint, because microballoon outside mainly is oxyalkyl or alkyl, be inertia group, can not with oil paint in polymkeric substance crosslinked action is arranged, in conjunction with insecure.In addition, some solvents of oiliness system may enter into aerogel microball inside, influence whole composite coating heat-proof quality, and the structure of aerogel microball is also had certain influence.The not enough environmental protection of oiliness system coating also is the reason of present common concern aqueous coating system.If the wetting ability aerogel microball is joined in the aqueous coating system, the structure of aerogel microball can be subsided, and the composite coating of preparation does not have effect of heat insulation.If the wetting ability aerogel microball is joined in the oil paint system, can not form even liquid-phase system, demixing phenomenon appears.
The hydrophilic aerogel microball in outside is used for water-borne coatings so prepare a kind of inner hydrophobic, and preparation compound heat-insulation coating is a kind of idea very ingenious.
Summary of the invention
Purpose of the present invention is just in order to provide a kind of preparation method of aerosil water-borne heat-insulating coating.Method of the present invention is by preparing the outside hydrophilic SiO of a kind of inner hydrophobic
2Aerogel microball joins in the water-borne coatings, prepares the heat insulation composite coating of high-performance water-based environmental protection.When adopting water-borne coatings of the present invention as the thermal insulating coating carrier, outside hydrophilic radical and the water-borne coatings of aerogel microball have good consistency, and only there is the outside of microballoon in water-borne coatings, can not enter into the inside of microballoon.
Purpose of the present invention can realize by following technical measures:
Method of the present invention is to adopt the SiO of atomising method or the preparation of other method
2The wet gel microballoon, it is hydrophobically modified that it is carried out internal surface of hole, then it handled with hydroaropic substance, makes the external portion of microballoon hydrophobic, after the drying the inner hydrophilic SiO in thin outside
2Aerogel microball joins and prepares SiO in the water-borne coatings
2Aerogel compound heat-insulation coating.But method of the present invention does not limit the method that adopts atomizing, the SiO of other method preparation
2The aerogel microball method also is fine, and the microballoon of atomising method preparation is best, sphere diameter size 1-1000 micron.Also can be that block materials is broken into certain particle size size SiO
2Aerogel, size range generally are the 1-1000 microns.
When microsphere surface was modified, the volume ratio of trimethylchlorosilane and ethanol was 1:0.1-10, and used coating materials is not only trimethylchlorosilane, can also be other organosilane, and its form is as (R
1R
2R
3Si)
2O, R
1R
2R
3It is respectively the group that is on the different positions, chain length is generally 1-5 carbon atom, it can be identical or different group, as alkyl, fluoroalkyl, aryl radical, aromatic hydrocarbons alkyl etc., representational modifier is that hexamethyldisiloxane (hexamethyldisilonane), hexamethyldisilazane (hexamethyldisilazane) etc. can be used as coating materials.
Of the present inventionly also can directly prepare hydrophobicity SiO
2The wet gel microballoon, so, do not need to carry out the surface hydrophobicity sex modification.
In addition, when carrying out the processing of hydrophobicity wet gel microballoon wetting ability, used coupling agent is not only 3-aminopropyl ortho-siliformic acid, in addition, some reagent that also have other, as: γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan, γ-(2,3-epoxy, third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan etc.As long as the coupling agent and the SiO that add
2The a spot of hydroxyl of wet gel hydrophobicity microsphere surface reacts, and it is just passable to increase its surperficial hydrophilicity.The volume ratio of coupling agent consumption and wet gel microballoon is 1:(0.1-20), different coupling agents, the amount of adding also is different.
The method of drying of the present invention is not limited only to supercritical CO
2, the method for Supercritical Ethanol, methyl alcohol, Virahol or constant pressure and dry can be as the method for drying.
The SiO that the present invention is prepared
2Aerogel microball must be inner hydrophobic and outside hydrophilic, the place is with in the water-based system, the structure of microballoon can not be subsided, and when making aqueous composite paint, can play heat insulation effect.
When preparation water-borne heat-insulating coating, SiO
2The volume ratio of aerogel microball and coating has relation with the character of water-borne coatings, and microsphere volume is generally and accounts for whole dope layer volume 10%-95%.Used coating vehicles is water-based system, as acrylic acid or the like or acrylic acid copolymer class, and interpolymer latex of polystyrene and acrylic ester, organic silicon-acrylate copolymer emulsion and polyurethane-acrylate copolymer emulsion etc.
The material that also can add some anti-infrared radiation in described this thermal insulating coating increases effect of heat insulation, as: TiO
2, powder such as carbon black, Z 250.
More specifically: preparation method of the present invention adopts following step to realize:
A, SiO
2Colloidal sol preparation: with SiO
2Silicon source, Union carbide A-162, dehydrated alcohol and deionized water evenly mix, and add nitric acid again and form silicon sol, and its mol ratio is: SiO
2Silicon source: Union carbide A-162: dehydrated alcohol: deionized water: nitric acid=1:0-10:1-30:1-10:0.0005-0.08; The silicon sol of preparation is sent in the water-bath water-bath 0-30 hour under temperature 20-70 ℃ condition, and set aside for use at room temperature; Described SiO
2Any one in tetraethoxy TEOS, methyl silicate TMOS, the acidic silicasol taken from the silicon source; The mass percent concentration of described nitric acid is 63%;
B, SiO
2The preparation of wet gel microballoon: step a gained sol solutions is passed through atomisation unit, be under the condition of 5-30Mpa at atomizing pressure, colloidal sol is evenly sprayed in the oil phase that is positioned in the whipping appts that rotating speed is 400-3000r/min, spraying in per 10 seconds 1 time, spray 3-100 time altogether, after the end to be atomized, continue stir about 1-60min, begin to drip concentration and be 2% ammoniacal liquor, drip quantity by silicon sol: the ammoniacal liquor mole ratio is 1:10
-6-10
-2Ratio adds; Stirring velocity is adjusted in dropping ammonia about 400-3000 r/m, proceeds stir about 1-60 minute; The microballoon that the obtains mixing solutions with oil is sealed with preservative film, aging 1-5 days, filter out oil after, obtain SiO
2Wet gel microballoon, the size of resultant microballoon are 1 micron-1000 microns; Described oil phase is taken from peanut oil, tori seed oil, and silicone oil or other oil phase can form in the water-in-oil system any one with silicon sol, and the consumption of described oil phase is 82 ~ 87% of sol solutions weight;
C, exchange of solvent: after the generation gel leaves standstill 10-72 hour, after treating that gel micro-ball is sunken to container bottom, absorption floats on the mixing solutions of gel surface, when drawing, note to make gel micro-ball to be exposed in the air, must guarantee that existing liquid level is higher than gel micro-ball in the container, get 120 milliliters of microspheres prepared, then with the water in the normal hexane exchange gel, clean 3～7 times each 6～72 hours timed intervals according to above method; In order to carrying out SiO
2The surface modified use of collosol and gel;
D, SiO
2Wet gel microballoon hydrophobicity is handled: the volume ratio by trimethylchlorosilane and ethanol is 1:5 preparation mixing solutions, and mixing solutions accounts for SiO
2Wet gel microsphere volume 20% adds above-mentioned cleaned SiO with this solution
2In the wet gel microballoon, carry out surface modification with the above-mentioned decorating liquid for preparing, modification 2～5 days; Use the mixing solutions of dehydrated alcohol: water=5:1 to clean then, the impurity element in exchange gel 3-10 time is till the impurity element exchange finishes; Adopt silver nitrate solution to detect in the gelating soln whether also contain the existence of Cl-, if the solution that cleans out is through AgNO
3White precipitate appears in detection, then also needs further to clean; Owing to be to carry out finishing with organosilane or organochlorosilane, the SiO that obtains
2The grafting of wet gel microballoon hole surface has a large amount of alkyl or alkoxyl group and is hydrophobic, removes SiO
2Behind the wet gel microballoon intermediate ion, use SiO
2Wet gel microballoon and ethanol volume ratio are 1:1 exchange 3-6 time, each 1-5 days at interval, remove the water in the system;
E, be that 1:1-10 mixes as the silicon source with the mol ratio of Union carbide A-162 MTES:TEOS, prepare SiO by atomizing or other method
2Wet gel hydrophobicity microballoon;
F, SiO
2The outside wetting ability of wet gel microballoon is handled: come microsphere surface is carried out the wetting ability processing with silane coupling agent 3-aminopropyl ortho-siliformic acid, wherein 3 milliliters of 3-aminopropyl ortho-siliformic acids with join 100 milliliters of SiO after 17 milliliters of ethanol mix
2The wet gel microballoon, modification 1-5 days;
G, SiO
2The drying of wet gel microballoon: with resulting SiO
2Wet gel microballoon supercritical CO
2Drying obtains SiO
2Aerogel microball;
H, with SiO
2Aerogel microball joins in the water-borne coatings, preparation compound heat-insulation coating, and the ratio of 5%:95% is with SiO by volume
2Aerogel microball joins in the pure acrylic emulsion, obtains composite coating; In order to improve the ability of thermal radiation resistant, add the TiO of 0-10% volume
2As opalizer.
SiO among the present invention
2The colloidal sol preparation can be adopted some document institute reported method, also can be with raw material (the silicon source of as document adopting: Pradip B. S. of water glass as the preparation microballoon, Jong-Kil K., Askwar H., Hee T.K., Production of low-density sodium silicate-based hydrophobic silica aerogel beads by a novel fast gelation process and ambient pressure drying process, Solid State Sciences, May 2010,5,911-918).
SiO among the present invention
2The preparation method of wet gel microballoon can be with churned mechanically method (M. Alnaief, S. Antonyuk, C.M. Hentzschel, C.S. Leopold, S. Heinrich, I. Smirnova, A Novel Process for Coating of silica aerogel Microspheres for Controlled Drug Release Applications, Microporous and Mesoporous Materials, doi:10.1016/j.micromeso.2012.02.009) or the atomizing method (Duan Li Qu, Hai Ching Lee, George L.Gould, Moethods for manufacture of aerogels, US patent, 2006/0084707 A1), after also the block aerogel of preparation can being smashed, screening obtains the irregular particle of certain particle size distribution shape.
Atomizing among the present invention prepares SiO
2The method that the wet gel microballoon adds base gel is to be different from document (Duan Li Qu, Hai Ching Lee, George L.Gould, Moethods for manufacture of aerogels, US patent, 2006/0084707 A1) method is directly to add in oil phase, rather than when atomizing or before the atomizing, add, such benefit is to be not easy to make atomizer nozzle to stop up.
Exchange of solvent among the present invention is in order to remove the water in the wet gel microballoon, to be conducive to next step hydrophobicity processing.Exchange of solvent number of times and pitch time can adjust, with except to anhydrate be standard.
SiO
2When wet gel microballoon hydrophobicity is handled, the reagent of used hydrophobic treatment is not limited only to trimethylchlorosilane, the ratio of itself and ethanol is not limited only to 1:5, can in very large range be adjusted into 1:(0.1-100), the solution that mixes with modifier also is not limited to ethanol, can be that other does not react with it, and the reagent of fine intermiscibility is arranged, as methyl alcohol, acetone etc.
SiO
2When wet gel microballoon hydrophobicity was handled, the mixing solutions of hydrophobic treatment accounts for the volume ratio of wet gel microballoon can 5-200%.
SiO
2When wet gel microballoon hydrophobicity was handled, this step of removing effects of ion can cut.Directly prepare SiO
2During the hydrophobic microballoon of wet gel, used reagent is not limited only to Union carbide A-162, also can use trimethylethoxysilane (TMES), and its ratio may take place to have any different with used reagent.
SiO
2When the outside wetting ability of wet gel microballoon was handled, the reagent that used wetting ability is modified was not limited to the agent of silane idol, also can be the reagent of other more hydrophilic radicals of generation that can react with the hydroxyl of microsphere surface.The key issue in this step is, because SiO
2After wet gel microballoon hydrophobicity is handled, its surface almost is alkoxyl group or alkyl, still there is a spot of hydroxyl to exist, but its performance is hydrophobicity, be not all to be alkoxyl group or alkyl in its hole, so, when wetting ability is handled, during with the wetting ability modifier can with a spot of hydroxyl reaction wherein, generate more hydrophilic radical, as 3-aminopropyl ortho-siliformic acid, when a hydroxyl of one of them hydroxyl and hydrophobicity microsphere surface reacts, slough a water, form silica silicon key, simultaneously, in the grafting of hydrophobicity microsphere surface two hydroxyls and an aminopropyl, these three groups all are hydrophilic.So, to SiO
2When the wet gel microballoon is made hydrophilic treatment, be quite crucial to used hydrophilic agent amount and the control of modification time.Different wetting ability modifiers, its consumption has difference.The volume ratio of 3-aminopropyl ortho-siliformic acid and ethanol is at 1:(4-100), its mixing solutions and SiO
2The volume ratio of wet gel microballoon is at 1:(0.01-10), modification 1-5 days.
SiO
2The dry used method of wet gel microballoon can be not limited only to supercritical CO with the method for drying
2, the method for Supercritical Ethanol, methyl alcohol, Virahol or constant pressure and dry can be as the method for drying.
During the preparation composite coating, it is benzene emulsion or pure acrylic emulsion that aqueous coating system is not limited to, and other water-based system can coating vehicles.
During the preparation composite coating, SiO
2Aerogel microball accounts for that volume ratio is 5%-95% in the coating.
During the preparation composite coating, opalizer can add powder such as TiO2, carbon black, Z 250, and it accounts for whole composite coating volume ratio is 0.1%-5%.
Beneficial effect of the present invention is as follows:
When adopting water-borne coatings of the present invention as the thermal insulating coating carrier, outside hydrophilic radical and the water-borne coatings of aerogel microball have good consistency, and only there is the outside of microballoon in water-borne coatings, can not enter into the inside of microballoon.
Embodiment
Embodiment 1
(1) SiO
2Colloidal sol preparation: positive silicon ethyl ester (TEOS), dehydrated alcohol, distilled water are calculated with the mole proportioning of 1:5:4, then the quality of TEOS, dehydrated alcohol, distilled water is respectively 208.33g, 230.35g, 72.04g, 4 milliliters in nitric acid (mass percent concentration is 63%), water-bath is 2 hours under 40 ℃ of conditions;
(2) SiO
2The preparation of wet gel microballoon: connect atomisation unit, adopt the atomizer of 0.2mm, atomizing pressure is 20Mpa, so that sol solutions is sprayed in institute is tiny, intensive, even; Colloidal sol is evenly sprayed in 500 milliliters the peanut oil that is positioned in the whipping appts that rotating speed is 900r/min, and spraying in per 10 seconds 1 time is sprayed 3-100 time altogether, after the end to be atomized, continues stir about 10min, beginning 2 milliliters of dropping ammonia (concentration is 2%); Stirring velocity is adjusted in dropping ammonia about 500 r/m, proceeds stir about 5 minutes; The microballoon that the obtains mixing solutions with oil is sealed with preservative film, aging 3 days, filter out oil after, obtain SiO
2The wet gel microballoon;
(3) exchange of solvent: after the gel of generation leaves standstill 10 hours, gel micro-ball will be sunken to beaker bottom, this moment, available rubber suction bulb was drawn the mixing solutions that floats on gel surface, when drawing, note to make gel micro-ball to be exposed in the air, must guarantee that existing liquid level exceeds gel micro-ball in the beaker, get 120 milliliters of microspheres prepared, then with the water in the normal hexane exchange gel, clean 3 times each 6 hours at interval according to above method; Resultant SiO
2The wet gel microballoon is in order to carrying out surface modified use;
(4) SiO
2Wet gel microballoon hydrophobicity is handled: the volume ratio by trimethylchlorosilane and ethanol is 24 milliliters of 1:5 preparation mixing solutionss, and mixing solutions accounts for SiO
2Wet gel microsphere volume 20% adds above-mentioned cleaned SiO with this solution
2In the wet gel microballoon, carry out surface modification with the above-mentioned decorating liquid for preparing, modification 3 days, use dehydrated alcohol then: water=20 milliliter: 4 milliliters mixing solutions cleans, with the impurity element (as: Cl in the ethanolic soln exchange gel for preparing
-, NO
3 -) repeatedly, till the impurity element exchange finishes, can adopt silver nitrate solution to detect in the gelating soln whether also contain Cl
-Existence, if the solution that cleans out is through AgNO
3White precipitate appears in detection, then also needs further to clean.Remove SiO
2Behind the wet gel microballoon intermediate ion, use SiO
2Wet gel microballoon and ethanol volume ratio are cleaned 4 times for the 120:120 milliliter, each 2 days at interval, remove the water in the system;
(5) SiO
2The outside wetting ability of wet gel microballoon is handled: come microsphere surface is carried out the wetting ability processing with silane coupling agent 3-aminopropyl ortho-siliformic acid, wherein 3 milliliters of 3-aminopropyl ortho-siliformic acids with join 120 milliliters of SiO after 17 milliliters of ethanol mix
2The wet gel microballoon, modification 3 days;
(6) SiO
2The drying of wet gel microballoon: with resulting SiO
2Wet gel microballoon supercritical CO
2Drying obtains SiO
2Aerogel microball;
(7) with SiO
2Aerogel microball joins in the water-borne coatings, preparation compound heat-insulation coating: 30%SiO by volume
2Aerogel microball joins in the pure acrylic emulsion, obtains composite coating.In order to improve the ability of thermal radiation resistant, add the TiO of 2% volume
2As opalizer.
Embodiment 2
(1) SiO2 colloidal sol preparation: positive silicon methyl esters (TMOS), dehydrated alcohol, distilled water are calculated with the mole proportioning of 1:8:4, then the quality of TMOS, dehydrated alcohol, distilled water is respectively 152g, 368g, 72g, 3 milliliters in nitric acid (mass percent concentration is 63%), water-bath is 3 hours under 60 ℃ of conditions;
(2) preparation of SiO2 wet gel microballoon: connect atomisation unit, adopt the atomizer of 0.1mm, atomizing pressure is 15Mpa, so that to spray sol solutions tiny, intensive, evenly, it is in the silicone oil of 100 μ pa.s that colloidal sol is evenly sprayed into 500 milliliters the viscous modulus that is positioned in the whipping appts that rotating speed is 700r/min, spraying in per 5 seconds 1 time, the spraying number of times is 50 times, continues stir about 10min, beginning 1 milliliter of dropping ammonia (concentration is 2%), stirring velocity is adjusted in dropping ammonia about 400 r/m, proceeds stir about 5 minutes; The mixing solutions that obtains microballoon and silicone oil is sealed with preservative film, aging 5 days, filter out oil after, obtain SiO2 wet gel microballoon;
(3) exchange of solvent: after the gel of generation leaves standstill 10 hours, gel micro-ball will be sunken to beaker bottom, this moment, available rubber suction bulb was drawn the mixing solutions that floats on gel surface, when drawing, note to make gel micro-ball to be exposed in the air, must guarantee that existing liquid level exceeds gel micro-ball in the beaker, get 60 milliliters of microspheres prepared, clean with dehydrated alcohol, with the water in the flush away collosol and gel, add-on is higher than SiO2 wet gel microballoon and gets final product, clean 3 times according to above method, each 5 hours timed intervals are in order to carrying out the surface modified use of SiO2 collosol and gel;
(4) SiO
2Wet gel microballoon hydrophobicity is handled: the volume ratio by trimethylchlorosilane and ethanol is 12 milliliters of 1:4 preparation mixing solutionss, and mixing solutions accounts for SiO
2Wet gel microsphere volume 20% adds above-mentioned cleaned SiO with this solution
2In the wet gel microballoon, carry out surface modification with the above-mentioned decorating liquid for preparing, modification 3 days;
(5) SiO
2The outside wetting ability of wet gel microballoon is handled: come microsphere surface is carried out the wetting ability processing with silane coupling agent 3-aminopropyl ortho-siliformic acid, wherein 1 milliliter of 3-aminopropyl ortho-siliformic acid with join 60 milliliters of SiO after 10 milliliters of ethanol mix
2The wet gel microballoon, modification 3 days;
(6) SiO
2The drying of wet gel microballoon: with resulting SiO
2Wet gel microballoon Supercritical Ethanol drying obtains SiO
2Aerogel microball;
(7) with SiO
2Aerogel microball joins in the water-borne coatings, preparation compound heat-insulation coating: 70%SiO by volume
2Aerogel microball joins in the benzene emulsion, obtains composite coating.
Embodiment 3
(1) SiO
2Colloidal sol preparation: acidic silicasol (mass concentration 35%, Na
+Concentration is less than 80ppm), dehydrated alcohol, distilled water calculate with the mole proportioning of 1:2:4, then the quality of acidic silicasol, dehydrated alcohol, distilled water is respectively 2 milliliters of 171g, 92g, 72g, acetic acid;
(2) SiO
2The preparation of wet gel microballoon: connect atomisation unit, adopt the atomizer of 0.3mm, atomizing pressure is 15Mpa, so that to spray sol solutions tiny, intensive, evenly, it is in the silicone oil of 200 μ pa.s that colloidal sol is evenly sprayed into 500 milliliters the viscous modulus that is positioned in the whipping appts that rotating speed is 900r/min, spraying in per 20 seconds 1 time, the spraying number of times is 70 times, continues stir about 10min, beginning 5 milliliters of dropping ammonia (concentration is 2%), stirring velocity is adjusted in dropping ammonia about 450 r/m, proceeds stir about 6 minutes; The microballoon that obtains and the mixing solutions of peanut oil are sealed with preservative film, aging 3 days, filter out oil after, obtain SiO
2The wet gel microballoon;
(3) exchange of solvent: after the gel of generation leaves standstill 20 hours, gel micro-ball will be sunken to beaker bottom, this moment, available rubber suction bulb was drawn the mixing solutions that floats on gel surface, when drawing, note to make gel micro-ball to be exposed in the air, must guarantee that existing liquid level exceeds gel micro-ball in the beaker, get 200 milliliters of microspheres prepared, then with the water in the normal hexane exchange gel, clean 3 times each 6 hours at interval according to above method.In order to carrying out the surface modified use of SiO2 collosol and gel;
(4) SiO
2Wet gel microballoon hydrophobicity is handled: the volume ratio by trimethylchlorosilane and ethanol is 80 milliliters of 1:7 preparation mixing solutionss, and mixing solutions accounts for SiO
2Wet gel microsphere volume 40% adds above-mentioned cleaned SiO with this solution
2In the wet gel microballoon, carry out surface modification with the above-mentioned decorating liquid for preparing, modification 5 days is used SiO
2Wet gel microballoon and ethanol volume ratio are 200:150 milliliter exchange 5 times, each 3 days at interval, remove the water in the system;
(5) SiO
2The outside wetting ability of wet gel microballoon is handled: come that with silane coupling agent 3-aminopropyl ortho-siliformic acid microsphere surface is carried out wetting ability and handle, wherein 3 milliliters of 3-aminopropyl ortho-siliformic acids with join 120 milliliters of SiO2 wet gel microballoons, modification 3 days after 17 milliliters of ethanol mix;
(6) SiO
2The drying of wet gel microballoon: with resulting SiO
2Wet gel microballoon constant pressure and dry, its method is (as document Pradip B. Sarawade, Jong-Kil Kim, Askwar Hilonga, Hee Taik Kim, Production of low-density sodium silicate-based hydrophobic silica aerogel beads by a novel fast gelation process and ambient pressure drying process, Solid State Sciences, 2010,5,911-918), obtain SiO
2Aerogel microball;
(7) with SiO
2Aerogel microball joins in the water-borne coatings, and preparation compound heat-insulation coating: the 50%SiO2 aerogel microball joins in the pure acrylic emulsion by volume.
Embodiment 4
(1) SiO
2Colloidal sol preparation: positive silicon ethyl ester (TEOS), Union carbide A-162 (MTES), dehydrated alcohol, distilled water are calculated with the mole proportioning of 1:1:5:4, then the quality of TEOS, dehydrated alcohol, distilled water is respectively 208.33g, 178.30g, 230.35g, 72.04g, 4 milliliters in nitric acid (mass percent concentration is 63%), water-bath is 3 hours under 60 ℃ of conditions;
(2) SiO
2The preparation of wet gel microballoon: connect atomisation unit, adopt the atomizer of 0.1mm, atomizing pressure is 20Mpa, so that sol solutions is sprayed in institute is tiny, intensive, even; Colloidal sol is evenly sprayed in 500 milliliters the tori seed oil that is positioned in the whipping appts that rotating speed is 900r/min, and spraying is 20 times continuously, continues stir about 10min, beginning 1 milliliter of dropping ammonia (concentration is 2%).Stirring velocity is adjusted in dropping ammonia about 500 r/m, proceeds stir about 5 minutes; The mixing solutions that obtains microballoon and tori seed oil is sealed with preservative film, aging 3 days, filter out oil after, obtain SiO
2The wet gel microballoon;
(3) SiO
2The outside wetting ability of wet gel microballoon is handled: come microsphere surface is carried out the wetting ability processing with silane coupling agent 3-aminopropyl ortho-siliformic acid, wherein 3 milliliters of 3-aminopropyl ortho-siliformic acids with join 120 milliliters of SiO after 17 milliliters of ethanol mix
2The wet gel microballoon, modification 3 days;
(4) SiO
2The drying of wet gel microballoon: with resulting SiO
2Wet gel microballoon supercritical CO
2Drying obtains SiO
2Aerogel microball;
(5) with SiO
2Aerogel microball joins in the water-borne coatings, and preparation compound heat-insulation coating: the 30%SiO2 aerogel microball joins in the organic silicon-acrylate copolymer emulsion by volume, obtains composite coating.
Claims (1)
1. the preparation method of an aerosil water-borne heat-insulating coating is characterized in that: described preparation method adopts following step to realize:
A, SiO
2Colloidal sol preparation: with SiO
2Silicon source, Union carbide A-162, dehydrated alcohol and deionized water evenly mix, and add nitric acid again and form silicon sol, and its mol ratio is: SiO
2Silicon source: Union carbide A-162: dehydrated alcohol: deionized water: nitric acid=1:0-10:1-30:1-10:0.0005-0.08; The silicon sol of preparation is sent in the water-bath water-bath 0-30 hour under temperature 20-70 ℃ condition, and set aside for use at room temperature; Described SiO
2Any one in tetraethoxy TEOS, methyl silicate TMOS, the acidic silicasol taken from the silicon source; The mass percent concentration of described nitric acid is 63%;
B, SiO
2The preparation of wet gel microballoon: step a gained sol solutions is passed through atomisation unit, be under the condition of 5-30Mpa at atomizing pressure, colloidal sol is evenly sprayed in the oil phase that is positioned in the whipping appts that rotating speed is 400-3000r/min, spraying in per 10 seconds 1 time, spray 3-100 time altogether, after the end to be atomized, continue stir about 1-60min, begin to drip the ammoniacal liquor that concentration is 0.1-5%, drip quantity by silicon sol: the ammoniacal liquor mole ratio is 1:10
-6-10
-2Ratio adds; Stirring velocity is adjusted in dropping ammonia about 400-3000 r/m, proceeds stir about 1-60 minute; The microballoon that the obtains mixing solutions with oil is sealed with preservative film, aging 1-5 days, filter out oil after, obtain SiO
2Wet gel microballoon, the size of resultant microballoon are 1 micron-1000 microns; Described oil phase is taken from peanut oil, tori seed oil, and silicone oil or other oil phase can form in the water-in-oil system any one with silicon sol, and the consumption of described oil phase is 82 ~ 87% of sol solutions weight;
C, exchange of solvent: after the generation gel leaves standstill 10-72 hour, after treating that gel micro-ball is sunken to container bottom, absorption floats on the mixing solutions of gel surface, when drawing, note to make gel micro-ball to be exposed in the air, must guarantee that existing liquid level is higher than gel micro-ball in the container, get 120 milliliters of microspheres prepared, then with the water in the normal hexane exchange gel, clean 3～7 times each 6～72 hours timed intervals according to above method; In order to carrying out SiO
2The surface modified use of collosol and gel;
D, SiO
2Wet gel microballoon hydrophobicity is handled: the volume ratio by trimethylchlorosilane and ethanol is 1:5 preparation mixing solutions, and mixing solutions accounts for SiO
2Wet gel microsphere volume 20% adds above-mentioned cleaned SiO with this solution
2In the wet gel microballoon, carry out surface modification with the above-mentioned decorating liquid for preparing, modification 2～5 days; Use the mixing solutions of dehydrated alcohol: water=5:1 to clean then, the impurity element in exchange gel 3-10 time is till the impurity element exchange finishes; Adopt silver nitrate solution to detect in the gelating soln whether also contain the existence of Cl-, if the solution that cleans out is through AgNO
3White precipitate appears in detection, then also needs further to clean; Owing to be to carry out finishing with organosilane or organochlorosilane, the SiO that obtains
2The grafting of wet gel microballoon hole surface has a large amount of alkyl or alkoxyl group and is hydrophobic, removes SiO
2Behind the wet gel microballoon intermediate ion, use SiO
2Wet gel microballoon and ethanol volume ratio are 1:1 exchange 3-6 time, each 1-5 days at interval, remove the water in the system;
E, be that 1:1-10 mixes as the silicon source with the mol ratio of Union carbide A-162 MTES:TEOS, prepare SiO by atomizing or other method
2Wet gel hydrophobicity microballoon;
F, SiO
2The outside wetting ability of wet gel microballoon is handled: come microsphere surface is carried out the wetting ability processing with silane coupling agent 3-aminopropyl ortho-siliformic acid, wherein 3 milliliters of 3-aminopropyl ortho-siliformic acids with join 100 milliliters of SiO after 17 milliliters of ethanol mix
2The wet gel microballoon, modification 1-5 days;
G, SiO
2The drying of wet gel microballoon: with resulting SiO
2Wet gel microballoon supercritical CO
2Drying obtains SiO
2Aerogel microball;
H, with SiO
2Aerogel microball joins in the water-borne coatings, preparation compound heat-insulation coating, and the ratio of 5%:95% is with SiO by volume
2Aerogel microball joins in the pure acrylic emulsion, obtains composite coating; In order to improve the ability of thermal radiation resistant, add the TiO of 0-10% volume
2As opalizer.
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