CN102897779A - Preparation method of transparent silicon dioxide aerogel - Google Patents
Preparation method of transparent silicon dioxide aerogel Download PDFInfo
- Publication number
- CN102897779A CN102897779A CN2012104396704A CN201210439670A CN102897779A CN 102897779 A CN102897779 A CN 102897779A CN 2012104396704 A CN2012104396704 A CN 2012104396704A CN 201210439670 A CN201210439670 A CN 201210439670A CN 102897779 A CN102897779 A CN 102897779A
- Authority
- CN
- China
- Prior art keywords
- gel
- preparation
- silicon dioxide
- solution
- aerogel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to aerogel and provides a preparation method of transparent silicon dioxide aerogel, which has the advantages of low cost, simple process, short production period, controllable reacting process and continuous production and adopts secondary modification process and normal-pressure drying steps. The preparation method comprises the following steps: 1) solution preparation and silicon source co-precursor hydrolysis; 2) ion exchange and silicon dioxide hydrogel preparation by using gel; and 3) aging, alcoholizing, modifying and normal-pressure drying of the silicon dioxide gel.
Description
Technical field
The present invention relates to a kind of aerogel, especially relate to take service water glass as raw material, adopt twice-modified method also by quick solvent replacing, the preparation method of a kind of transparent silicon dioxide aerogel of constant pressure and dry.
Background technology
Silicon-dioxide (SiO
2) aerogel is a kind of solid-phase particle, the particle pore size is the novel porous functional materials of nanometer scale, and continuous three-dimensional net structure can and be cut out in nanoscale control.Because it has translucency and ultra-light-weight, aerosil is also sometimes referred to as " solid-state cigarette " or " frost smoke ".Aerosil has the performance of many uniquenesses, and such as high-specific surface area, high porosity, high thermal insulation, low density, ultralow dielectric and low specific refraction etc., performance can be along with the control of its structure is had continuous adjustability.The excellent properties that aerosil has makes it to have broad application prospects in fields such as heat-insulation and heat-preservation, thermal isolation, catalysis, energy-conserving and environment-protective, petrochemical complex, drug release, aerospace.Aspect fundamental research, the fractal structure of aerogel, Growth kinetics mechanism, low temperature thermal property and network skeleton and Molecular interaction etc. have become the forward position of Condensed Matter Physics research, cause investigator's very big concern.
Rong Jiao – gel method is the main method of preparation aerosil at present, relates to the steps such as washing, the replacement of pure water, supercritical drying in the preparation process, and complex process poor efficiency, cycle, length, product purity were difficult to guarantee.Utilized afterwards estersil to pass through a step catalysis Rong Jiao – gel method at CO
2Prepare the lower aerosil of density under the supercritical drying, just make the research of aerogel further.At present the research emphasis of aerosil mainly concentrates in the optimization of adopting different silicon source presomas and synthesis path, with reach reduce cost, shortening cycle, experiment condition safer, promote the purpose that aerogel is commercially produced.
Through scholars' extensive work, reported at present under constant pressure and dry the aerosil take tetraethyl orthosilicate (TEOS) or positive quanmethyl silicate (TMOS) as silicon source presoma processability excellence.The aerosil specific surface area that obtains the constant pressure and dry preparation such as the applicant can reach 1000m
2/ g, density 0.1 ~ 0.2g/cm
3, hydrophobic angle reaches 157 °.But estersil eka-silicon source presoma price, and poisonous, the easy blinding of methyl silicate, so this preparation method exists environmental protection and safety problem.
The advantages such as that water glass has is cheap, material is easy to get are the first-selected starting material of realizing the suitability for industrialized production aerosil.Water glass claims again water glass, its purposes is very extensive, each department that almost spreads all over national economy, in chemical system, be used to prepare the basic raw material of the silicides such as silica gel, zeolite molecular sieve, silicon sol, sodium-potassium silicate, deep processing series product take water glass as raw material have reached tens kinds, and the research for preparing in recent years aerogel take water glass as silicon source material more and more comes into one's own.But, the aerosil of preparation generally is Powdered take water glass as the presoma constant pressure and dry at present, complex technical process, solvent-oil ratio is large in the building-up process, and the aerosil for preparing also has a certain distance with the aerosil that adopts the preparation of estersil class presoma in performance.
The main component of water glass is Na
2OmSiO
2In order to remove sodium ion to forming the impact of aerogel, at present mainly will by proportioning dilute good sodium silicate solution by strong-acid ion exchange resin with the preparation silicon sol, also have the method that adopts the deionized water wash gel to remove sodium ion in the gel hole etc.Publication number is that the Chinese patent of CN101538046A discloses a kind of method of using coal ash for manufacturing prepared silicon dioxide aerogel and zeolite.The method provides a kind of new way of high-efficiency resource recycling flyash, has also solved the discarded problem of environmental pollution that causes of flyash.In method one, use the sulfuric acid catalysis sodium silicate gel, soak silica dioxide gel with deionized water multiple timing in 72h again and remove wherein sodium ion, silica dioxide gel is carried out solvent replacing and surface modification treatment prepares aerogel.Also someone takes to wash for several times silica hydrogel with deionized water, but this method obviously is difficult to remove in a large number the sodium ion in the hydrogel, at final residue after the drying in aerosil, affect purity and the performance of aerogel, and increased the synthesis cycle of aerosil.
Prepare for constant pressure and dry in the research field of aerosil, can the quality of aerosil skeleton hydrophobically modified be obtain aerosil in the constant pressure and dry situation, and the important step that obtains the various performance quality of aerosil.At present the main organosilane that adopts carries out hydrophobically modified to aerogel, but the moisture in the silica hydrogel hole that water glass is silicon source presoma to be formed has material impact to the modifying process of gel.Since organosilane-modified dose with the reactive behavior of water than with the silica dioxide gel skeleton on the reactive behavior of Si-OH strong, therefore the large quantitative response of hole moisture in properties-correcting agent and the silica hydrogel, gel skeleton hydrophobically modified process lost efficacy, and used a large amount of properties-correcting agent can overcome this problem.Publication number be the Chinese patent of CN102179230A take water glass as raw material, constant pressure and dry has prepared a kind of aerosil of composing magnetic, the specific surface area 500m of aerogel
2/ g is with 110 ~ 120 ° of the contact angles of water.But in preparation process, adopted a large amount of organosilicon modifier (trimethylchlorosilane, hexamethyldisilazane, dimethyldichlorosilane(DMCS) etc.), so that the preparation cost of aerosil significantly improves.
At present the silica hydrogel alcoholization being formed the silicon-dioxide alcogel is the main method that overcomes this problem, replace the aqueous solution of skeleton in the hydrophilic silica hydrogel hole take dehydrated alcohol, often need to be soaked in gel in a large amount of ethanol solutions for a long time or use in a certain amount of dehydrated alcohol repeatedly the aqueous solution in the solvent replacing gel.As being that the Chinese patent of CN102020285A has been mentioned gel is placed in dehydrated alcohol or the Virahol and soaked 24h at publication number, with dehydrated alcohol or washed with isopropyl alcohol twice, the aerogel powder density that obtains at last is 0.1 ~ 0.18g/cm again
3, specific surface area 500 ~ 700m
2/ g, mean pore size 15 ~ 20nm.At publication number be the Chinese patent of 101164881A in order to prepare the aerosil microballoon, the hydrogel microsphere that gel is obtained is successively at V
Water: V
Dehydrated alcoholSoak respectively 28h in the ethanol solution of=1:1 and the dehydrated alcohol to obtain silicon-dioxide alcogel microballoon.Hydrogel after the people such as external A.Parvathy Rao also will wear out in the process of preparation aerogel is put into again 36h internal solvent exchange 3 times of ethanolic soln.
Be that the Chinese patent of CN101538046A discloses a kind of method of using coal ash for manufacturing prepared silicon dioxide aerogel and zeolite at publication number.Adopt synthetic water glass to prepare aerosil.One of method is to use the sulfuric acid catalysis sodium silicate gel, soaks silica dioxide gel with deionized water multiple timing in 72h again and removes wherein sodium ion, and silica dioxide gel is carried out solvent replacing and surface modification treatment prepares aerogel.The scholar of University of Science ﹠ Technology, Beijing also takes deionized water to wash for several times silica hydrogel, but this method obviously is difficult to remove in a large number the sodium ion in the hydrogel, remain in the aerosil after the final drying, affect purity and the performance of aerogel, increased the synthesis cycle of aerosil.Two of method is the hydrogel that the silicic acid after the ion-exchange forms is soaked 24h in dehydrated alcohol after, be modification in the mixing solutions of ethanol, trimethylchlorosilane and normal hexane of 2:3:30 in volume ratio, prepare aerosil finally by drying, the aerogel density that obtains is 0.12g/cm
3, specific surface area is 907m
2/ g, pore volume are 4.875cc/g.
Publication number be the Chinese patent of CN102179230A take water glass as raw material, constant pressure and dry has prepared a kind of aerosil of composing magnetic, the specific surface area 500m of aerogel
2/ g is with 110 ~ 120 ° of the contact angles of water.But adopted a large amount of organosilicon modifier (trimethylchlorosilane, hexamethyldisilazane, dimethyldichlorosilane(DMCS) etc.) in the preparation process, so that the preparation cost of aerosil significantly improves.Be that the required silane modifier consumption of aerosil of silicon source presoma preparation is 1 ~ 10 times of the silica wet gel volume consumption in the estersil class presoma preparation process by water glass at present.
Since 2006, external Sharad.D Bhagat adds multifunction surface properties-correcting agent in the gel formation process, prepare silicon dioxide aerogel powder take water glass as presoma under constant pressure and dry technique, specific surface area 473 ~ 776m
2/ g, density 0.1 ~ 0.309g/cm
3, the sample that the method obtains is opaque white powder, physical strength is relatively poor.But preparation time is short, and technique is simple, and the consumption of replacing solvent normal hexane and properties-correcting agent silane in the building-up process is also lower.
The applicant in Chinese patent CN101372337A, disclose a kind of with low cost, technique is simple, with short production cycle, reaction process is controlled, and the method for the preparing transparent silicon dioxide aerogel by co-precursor normal atmosphere drying that can be continuously produced.The co-precursor surface-modification method has been successfully applied to take tetraethyl orthosilicate (TEOS) as silicon source presoma and has prepared in the research of aerosil, prepares the technology of aerosil such as the normal pressure of the applicant's application.But how this method is applied to prepare rare research of aerosil with water glass.
At present, the research Main Problems for preparing aerosil take water glass as presoma comprises: synthesis cycle is long, and solution and organosilicon modifier consumption too much cause high cost in the building-up process; The aerogel over-all properties is relatively poor; There is a certain amount of residual impurity etc. in the aerogel hole.How simple and easy under constant pressure and dry, low-cost and rapidly the excellent aerosil of processability become the important bottleneck of this problem development.
Summary of the invention
The object of the present invention is to provide a kind of with low cost, technique is simple, with short production cycle, reaction process is controlled, and can be continuously produced, and adopts the preparation method of a kind of transparent silicon dioxide aerogel of twice-modified method constant pressure and dry.
The preparation method of a kind of transparent silicon dioxide aerogel of the present invention may further comprise the steps:
1) hydrolysis of the configuration of solution and silicon source co-precursor
Organoalkoxysilane, water glass solution and deionized water are mixed, organoalkoxysilane is hydrolyzed in deionized water, obtain solution A; In molar ratio, water glass: organoalkoxysilane: deionized water=1: (0.2 ~ 0.6): (30 ~ 40); Described organoalkoxysilane is Union carbide A-162 (MTES) or methyltrimethoxy silane (MTMS);
2) ion-exchange and gel prepare silica hydrogel
The solution A of step 1) preparation is added strongly acidic styrene's resin, leave standstill and carry out ion-exchange, then suction filtration obtains the solution of pH=2 ~ 3, adding ammoniacal liquor regulation system pH value is 8 ~ 8.5 again, obtain silicon dioxide gel, then silicon dioxide gel is transferred in the container and left standstill, namely make silica hydrogel; By volume, solution A: strongly acidic styrene's resin=1: (0.5 ~ 2);
3) aging, the alcoholization of silica dioxide gel, modification, constant pressure and dry
With step 2) silica hydrogel that obtains is immersed in the aging and alcoholization of carrying out gel in the ethanol solution, the gel of gained is immersed in the mixing solutions of trimethylchlorosilane (TMCS), dehydrated alcohol and normal hexane after will refining again, carry out surface modification, gel after the modification carries out constant pressure and dry, namely obtains block shape transparent silicon dioxide aerogel.
In step 2) in, described ion-exchange time of repose can be 5 ~ 20min; Describedly silicon dioxide gel is transferred to the time of repose that leaves standstill in the container can be 10～60min.
In step 3), the volume ratio of described dehydrated alcohol and silica hydrogel can be 1: (1.2 ~ 2); Described temperature aging and alcoholization can be 25 ~ 60 ℃, and the time aging and alcoholization can be 24 ~ 48h; The gel of gained is soaked in the mixing solutions of trimethylchlorosilane (TMCS), dehydrated alcohol and normal hexane after the described alcoholization, preferably under air-proof condition, soaked 1 ~ 2 day, by volume, trimethylchlorosilane (TMCS): dehydrated alcohol: normal hexane=1: (1 ~ 3): (6 ~ 8); The technical process of described constant pressure and dry is preferably: the gel after the described modification is at 45 ~ 50 ℃ of insulation 6 ~ 8h, then be warming up to 65 ~ 70 ℃, be incubated again 6 ~ 8h, be warming up to again 120 ℃, be incubated again 4 ~ 6h, be warming up at last 200 ℃, be incubated again 4 ~ 8h, stove is chilled to room temperature subsequently, and whole drying process heat-up rate is 1 ~ 5 ℃/min.
Compared with the prior art, the present invention has following outstanding advantages:
The preparation method of transparent silicon dioxide aerogel of the present invention is in air atmosphere, and the atmospheric low-temperature dry heat is carried out under processing.React by adding MTES or the MTMS silicic acid one after to ion-exchange in the sol-gel stage, carry out the preliminary modification in surface, in the process that the aging skeleton of gel strengthens, can carry out the quick alcoholization of gel simultaneously, namely one go on foot solvent replacing, use the water in the dehydrated alcohol replacement gel nano aperture, adopt again TMCS to carry out twice-modified.The last surface for preparing under constant pressure and dry is with the aerosil of hydrophobic group, and aerogel shows as hydrophobicity.The aerosil of preparation becomes piece better, and pore size distribution is relatively concentrated, and (0 ~ 50nm), size evenly.Aerosil is nano-porous structure, density 0.1 ~ 0.2g/cm
3, porosity 90% ~ 96%, specific surface area 650 ~ 850m
2/ g, hydrophobic angle is about 145 °.
The preparation method of transparent silicon dioxide aerogel of the present invention provide a kind of simple and easy, fast, the preparation method of transparent cake aerosil cheaply, the novelty of this method is, introduce a small amount of MTES with hydrophobic grouping or MTMS etc. as co-precursor properties-correcting agent in the ion-exchange stage of water glass, and the hydrolysis time of control co-precursor properties-correcting agent, could successfully synthesize transparent uniform gel.After forming gel; carry out the quick solvent replacing gel alcoholization of the aging of gel and a step; main the playing of co-precursor properties-correcting agent discharged hole moisture, makes the fast effect of alcoholization of gel, and the introducing of co-precursor also helps the hole protection of aerosil constant pressure and dry.In addition, in order to make synthetic aerosil performance more excellent, it is namely twice-modified that the present invention has introduced the gel surface derivatization method in a creative way, makes the residual Si-OH group of gel polycondensation fully by Si-CH
3Replace, simultaneously the alcoholic solution in the gel hole is replaced with the less normal hexane of coefficient of surface tension, last constant pressure and dry just can obtain the aerosil of excellent properties.
The present silica hydrogel that forms of the silicate solution of water glass after by ion-exchange, inner bore surface is with a large amount of Si-OH group of polycondensation remnants, so that gel is wetting ability.Be immersed in the process that ethanol solution carries out solvent replacing at silica hydrogel, only rely on the concentration difference of gel and outside soaking solution slowly to spread, cause the gel alcoholization often to need repeatedly multi-solvent consumption and long-time solvent replacing.Modifying function by co-precursor silane in present method is so that the silica hydrogel inner bore surface is with-CH
3Hydrophobic grouping, silicon dioxide skeleton possess certain hydrophobicity.In the aging process of gel, make the hydrogel alcoholization by solvent replacing simultaneously, because in the gel hole-CH
3Hydrophobic grouping has certain repulsive interaction to the aqueous solution in the hole, thereby moisture content in the hydrogel hole and the solvent replacing of soaking solution dehydrated alcohol have been promoted, so that silica hydrogel hole water content reduces in a large number, also avoided simultaneously owing to the synthesis cycle of repeatedly solvent replacing generation and the problem of solvent consumption increase.On the basis of co-precursor method modification, because the gel water content reduces in a large number, so that the consumption of hydrophobically modified organosilane commonly used significantly reduces, secondly, in the modifying process of organosilane, the aqueous solution of remnants and reaction and the aqueous solution of silane are carried out simultaneously by the discharge in the gel hole in the gel hole.At present, the aqueous solution mostly is modified silane reaction and discharges on a small quantity outside the gelling system in the general modifying process, the present invention is because the hydrophobicity of gel skeleton has but been accelerated the eliminating of modifying process water, also further reduced the consumption of organosilane, thereby the synthetic cost of aerosil is further reduced.
The present invention has avoided the use of expensive silicon source presoma, has adopted the water glass solution of scale operation in industrialization, has solved to prepare on a large scale at present one of main problem of aerosil with constant pressure and dry.Reduced simultaneously the consumption of all kinds of SOLVENTS and expensive silane modifier in preparation process, hydrogel is aging and alcoholization simultaneously, overcome the hydrogel taked aging first after the alcoholization process increase the problem of synthesis cycle.The replacement solvent dehydrated alcohol consumption (a little more than the hydrogel volume) of alcoholization process also is far smaller than the consumption in the most building-up process, and a step can reach gel alcoholization effect, overcome many unfavorable factors that a large amount of solvent demands of a step or multistep solvent replacing are brought, be conducive to commercialization and prepare on a large scale aerosil.The consumption of silane modifier has been that modification consumption in the precursor synthesis process is consistent with tetraethyl orthosilicate in present method, overcome the shortcoming of constant pressure and dry water glass synthetic silica aerogel costliness and silane modifier high flow rate amount, and also having very excellent physics and structure properties by the aerosil that present method prepares, fundamental performance parameter can compare favourably with the aerogel for preparing with expensive presoma TEOS.Because the adding of MTES or MTMS, so that-CH
3More be evenly distributed on the inside and outside skeleton of aerogel, it is block that aerosil is, and also having overcome with water glass is the shortcoming that aerogel that presoma obtains mostly is greatly powder.
Description of drawings
Fig. 1 is the synthetic sample photo of the aerosil of the embodiment of the invention 1 preparation.
Fig. 2 is the N of the aerosil of the embodiment of the invention 1 and comparative example 1 preparation
2Adsorption desorption isothermal curve figure.In Fig. 2, X-coordinate is relative pressure (P/P
0); Ordinate zou is adsorption volume (cm
3/ g).Curve 1 is take water glass as presoma, and MTES is the N of the aerosil of co-precursor preparation
2Adsorption desorption isothermal curve figure; Curve 2 is the N of the aerosil of preparation take water glass as presoma only
2Adsorption desorption isothermal curve figure;
Fig. 3 is the graph of pore diameter distribution of the aerosil of the embodiment of the invention 1 and comparative example 1 preparation.In Fig. 3, X-coordinate is aperture (nm); Ordinate zou is pore volume (cm
3/ g).Curve 1 is take water glass as presoma, and MTES is the graph of pore diameter distribution of the aerosil of co-precursor preparation; Curve 2 is the graph of pore diameter distribution of the aerosil of preparation take water glass as presoma only;
Fig. 4 is the infrared spectrogram of the aerosil of the embodiment of the invention 1 preparation.In Fig. 4, X-coordinate is wave number (cm
-1); Ordinate zou is transmitance (%).The chemical bond that marks from left to right is followed successively by-CH
3,-CH
2, Si-O-Si, Si-C, Si-O-Si, Si-O-Si.
Fig. 5 is the scanning electron microscope (SEM) photograph of the aerosil of the embodiment of the invention 1 preparation.
Fig. 6 is the contact angle figure of the aerosil of the embodiment of the invention 1 preparation.
Embodiment
The invention will be further described below by embodiment and accompanying drawing.
Material molar ratio is: water glass: MTES: water=1: 0.3: 35, MTES with 1.7ml, the deionized water mix and blend 48h of the water glass solution of 5ml and 12.5ml, again mixing solutions is passed in strongly acidic styrene's resin of 25ml, suction filtration obtains the silicon sol of pH=2 ~ 3 behind the 10min, add while stirring a certain amount of ammoniacal liquor, make the final pH value of system 8.0.Stop behind the 10min stirring, with SiO
2Colloidal sol leaves standstill 24h, treats the sample gel.Place ethanol solution to wear out and solvent replacing gel, aging temperature is 30 ℃, after aging gel sample is immersed in the solution batch volume than being trimethylchlorosilane (TMCS): dehydrated alcohol: normal hexane=1(4ml): modification is 2 days in 1: 8 the mixing solutions, with normal hexane flush away modification liquid, sample is immersed in the drying that heats up under the normal pressure in the normal hexane.
Drying process is: gel sample is at 45 ~ 50 ℃ of lower insulation 6h, speed with 1 ℃/min is warming up to 65 ℃ again, insulation 7h, speed with 1 ℃/min is warming up to 120 ℃ again, and insulation 5h, the speed with 1 ℃/min is warming up to 200 ℃ at last, insulation 6h, with being chilled to room temperature, namely obtain transparent silicon dioxide aerogel subsequently.
Fig. 1～5 are the correlated results of the present embodiment sample, and other performance perameter sees Table 1.
For MTES relatively adds impact on the aerosil preparation, the pure silicon colloidal sol that the below obtains after with water glass ion-exchange also prepares aerosil under identical synthesis condition, and the performance perameter of aerosil relatively:
Material molar ratio is: water glass: water=1: 35, with the water glass solution of 5ml and the deionized water mix and blend 48h of 12.5ml, remix solution passes in strongly acidic styrene's resin of 25ml, suction filtration obtains the silicon sol of pH=2 ~ 3 behind the 10min, add while stirring a certain amount of ammoniacal liquor, make the final pH value of system about 8.0.Stop behind the 10min stirring, with SiO
2Colloidal sol leaves standstill 24h, treats the sample gel.After wearing out gel sample is immersed in the solution batch volume than being TMCS: dehydrated alcohol: normal hexane=1(4ml): modification is 2 days in 1: 8 the mixing solutions, with normal hexane flush away modification liquid, sample is immersed in the drying that heats up under the normal pressure in the normal hexane.Drying process is: gel sample is at 45 ~ 50 ℃ of lower insulation 6h, speed with 1 ℃/min is warming up to 65 ℃ again, insulation 7h, speed with 1 ℃/min is warming up to 120 ℃ again, and insulation 5h, the speed with 1 ℃/min is warming up to 200 ℃ at last, insulation 6h, with being chilled to room temperature, namely obtain transparent silicon dioxide aerogel subsequently.The correlated performance parameter sees Table 1.
Table 1
| The properties of sample parameter | Numerical value (pure silicon colloidal sol) | Numerical value (MTES co-precursor) |
| Specific surface area (m 2/g) | 971.2±14.5 | 706.0±13.3 |
| Mean pore size (nm) | 5.7 | 11.8 |
| Pore volume (cm 3/g) | 1.4 | 2.9 |
| Density (g/cm 3) | 0.45 | 0.12 |
| Porosity (%) | 80 | 94.5 |
| Transparency | Transparent | Transparent |
| Hydrophobic angle (°) | 118 | 146 |
| Shape | Chunky shape | Block |
Material molar ratio is: water glass: MTMS: water=1: 0.3: 38, MTMS with 1.7ml, the deionized water mix and blend 24h of the water glass solution of 5ml and 13.5ml, again mixing solutions is passed in strongly acidic styrene's resin of 25ml, suction filtration obtains the silicon sol of pH=2 ~ 3 behind the 10min, add while stirring a certain amount of ammoniacal liquor, make the final pH value of system about 8.0.Stop behind the 10min stirring, with SiO
2Colloidal sol leaves standstill 24h, treats the sample gel.Place ethanol solution to wear out and solvent replacing gel, aging temperature is 30 ℃, after aging gel sample is immersed in the solution batch volume than being TMCS: dehydrated alcohol: normal hexane=1(4ml): modification is 2 days in 3: 6 the mixing solutions, with normal hexane flush away modification liquid, sample is immersed in the drying that heats up under the normal pressure in the normal hexane, and drying process is with embodiment 1.
The density of the aerosil of described preparation is 0.15g/cm
3, specific surface area is 625.2m
2/ g, mean pore size is 14.2nm, pore volume is 3.2cm
3/ g, hydrophobic angle is 144 °.
Embodiment 3
Material molar ratio is: water glass: MTES: water=1: 0.2: 40, MTES with 2.3ml, the deionized water mix and blend 24h of the water glass solution of 5ml and 14.3ml, remix solution passes in strongly acidic styrene's resin of 25ml, suction filtration obtains the silicon sol of pH=2 ~ 3 behind the 10min, add while stirring a certain amount of ammoniacal liquor, make the final pH value of system about 8.0.Stop behind the 10min stirring, with SiO
2Colloidal sol leaves standstill 24h, treats the sample gel.Place ethanol solution to wear out and solvent replacing gel, aging temperature is 30 ℃, after aging gel sample is immersed in the solution batch volume than being TMCS: dehydrated alcohol: normal hexane=1(4ml): modification is 2 days in 1: 8 the mixing solutions, with normal hexane flush away modification liquid, sample is immersed in the drying that heats up under the normal pressure in the normal hexane, and drying process is with embodiment 1.
The density of the aerosil of preparation is 0.15g/cm
3, specific surface area is 684.4m
2/ g, mean pore size is 10.1nm, pore volume is 2.7cm
3/ g, hydrophobic angle is 142 °.
Embodiment 4
Material molar ratio is: water glass: MTES: water=1: 0.6: 30, MTES with 3.4ml, the deionized water mix and blend 24h of the water glass solution of 5ml and 10ml, remix solution passes in strongly acidic styrene's resin of 25ml, suction filtration obtains the silicon sol of pH=2 ~ 3 behind the 10min, add while stirring a certain amount of ammoniacal liquor, make the final pH value of system about 8.0.Stop behind the 10min stirring, with SiO
2Colloidal sol leaves standstill 24h, treats the sample gel.Place ethanol solution to wear out and solvent replacing gel, aging temperature is 30 ℃, after aging gel sample is immersed in the solution batch volume than being TMCS: dehydrated alcohol: modification is 2 days in the mixing solutions of normal hexane=1: 3: 6, with normal hexane flush away modification liquid, sample is immersed in the drying that heats up under the normal pressure in the normal hexane, and drying process is with embodiment 1.
The density of the aerosil of preparation is 0.20g/cm
3, specific surface area is 702.2m
2/ g, mean pore size is 9.5nm, pore volume is 1.71cm
3/ g, hydrophobic angle is 145 °.
Embodiment 5
Similar to Example 1, difference only is: when placing ethanol solution to wear out with solvent replacing gel, aging temperature is 60 ℃.
The density of the aerosil of preparation is 0.11g/cm
3, specific surface area is 525.2m
2/ g, mean pore size is 17.2nm, pore volume is 2.31cm
3/ g, hydrophobic angle is 143 °.
Embodiment 6
Similar to Example 1, difference only is: after aging gel sample is immersed in the solution batch volume than being TMCS: dehydrated alcohol: normal hexane=1(4ml): modification is 1 day in 1: 8 the mixing solutions.
The density of the aerosil of preparation is 0.24g/cm
3, specific surface area is 750.2m
2/ g, mean pore size is 9.2nm, pore volume is 1.72cm
3/ g, hydrophobic angle is 140 °.
Embodiment 7
Similar to Example 2, difference only is: with material molar ratio be: water glass: MTMS: the mixing solutions of water=1: 0.5: 33 gained passes in strongly acidic styrene's resin of 40ml.
The density of the aerosil of preparation is 0.19g/cm
3, specific surface area is 690.5m
2/ g, mean pore size is 10.3nm, pore volume is 1.80cm
3/ g, hydrophobic angle is 144 °.
Claims (7)
1. the preparation method of a transparent silicon dioxide aerogel is characterized in that may further comprise the steps:
1) hydrolysis of the configuration of solution and silicon source co-precursor
Organoalkoxysilane, water glass solution and deionized water are mixed, organoalkoxysilane is hydrolyzed in deionized water, obtain solution A; In molar ratio, water glass: organoalkoxysilane: deionized water=1: (0.2 ~ 0.6): (30 ~ 40); Described organoalkoxysilane is Union carbide A-162 or methyltrimethoxy silane;
2) ion-exchange and gel prepare silica hydrogel
The solution A of step 1) preparation is added strongly acidic styrene's resin, leave standstill and carry out ion-exchange, then suction filtration obtains the solution of pH=2 ~ 3, adding ammoniacal liquor regulation system pH value is 8 ~ 8.5 again, obtain silicon dioxide gel, then silicon dioxide gel is transferred in the container and left standstill, namely make silica hydrogel; By volume, solution A: strongly acidic styrene's resin=1: (0.5 ~ 2);
3) aging, the alcoholization of silica dioxide gel, modification, constant pressure and dry
With step 2) silica hydrogel that obtains is immersed in the aging and alcoholization of carrying out gel in the ethanol solution, the gel of gained is immersed in the mixing solutions of trimethylchlorosilane, dehydrated alcohol and normal hexane after will refining again, carry out surface modification, gel after the modification carries out constant pressure and dry, namely obtains block shape transparent silicon dioxide aerogel.
2. the preparation method of a kind of transparent silicon dioxide aerogel as claimed in claim 1 is characterized in that in step 2) in, described ion-exchange time of repose is 5 ~ 20min; It is described that silicon dioxide gel is transferred to the time of repose that leaves standstill in the container is 10～60min.
3. the preparation method of a kind of transparent silicon dioxide aerogel as claimed in claim 1 is characterized in that in step 3), and the volume ratio of described dehydrated alcohol and silica hydrogel is 1: (1.2 ~ 2).
4. the preparation method of a kind of transparent silicon dioxide aerogel as claimed in claim 1 is characterized in that in step 3), and described temperature aging and alcoholization is 25 ~ 60 ℃, and the time aging and alcoholization is 24 ~ 48h.
5. the preparation method of a kind of transparent silicon dioxide aerogel as claimed in claim 1, it is characterized in that in step 3), the gel of gained is soaked in the mixing solutions of trimethylchlorosilane, dehydrated alcohol and normal hexane after the described alcoholization, under air-proof condition, to soak 1 ~ 2 day, by volume, trimethylchlorosilane: dehydrated alcohol: normal hexane=1: (1 ~ 3): (6 ~ 8).
6. the preparation method of a kind of transparent silicon dioxide aerogel as claimed in claim 1, it is characterized in that in step 3), the technical process of described constant pressure and dry is: the gel after the modification is at 45 ~ 50 ℃ of insulation 6 ~ 8h, then be warming up to 65 ~ 70 ℃ the 1st time, be incubated again 6 ~ 8h, be warming up to 120 ℃ the 2nd time again, be incubated again 4 ~ 6h, be warming up to 200 ℃ last the 3rd time, be incubated 4 ~ 8h again, stove is chilled to room temperature subsequently.
7. the preparation method of a kind of transparent silicon dioxide aerogel as claimed in claim 6 is characterized in that described the 1st intensification, the 2nd intensification and the heat-up rate that heats up for the 3rd time are 1 ~ 5 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210439670.4A CN102897779B (en) | 2012-11-06 | 2012-11-06 | Preparation method of transparent silicon dioxide aerogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210439670.4A CN102897779B (en) | 2012-11-06 | 2012-11-06 | Preparation method of transparent silicon dioxide aerogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102897779A true CN102897779A (en) | 2013-01-30 |
| CN102897779B CN102897779B (en) | 2014-08-06 |
Family
ID=47570315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210439670.4A Active CN102897779B (en) | 2012-11-06 | 2012-11-06 | Preparation method of transparent silicon dioxide aerogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102897779B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396086A (en) * | 2013-08-08 | 2013-11-20 | 厦门大学 | Preparation method for glass fiber-reinforced water glass-based silica composite aerogel |
| CN104071797A (en) * | 2014-05-21 | 2014-10-01 | 合肥科斯孚安全科技有限公司 | Method for preparing silicon dioxide aerogel coating with low density and large specific surface area by water glass at normal pressure and room temperature |
| CN104740797A (en) * | 2013-12-31 | 2015-07-01 | 镇江新元素医药科技有限公司 | Respirator capable of filtering PM (particulate matters) 2.5 effectively |
| CN105110340A (en) * | 2015-06-23 | 2015-12-02 | 北京建工新型建材有限责任公司 | Preparation method for elastic transparent silica aerogel |
| CN105236929A (en) * | 2014-07-09 | 2016-01-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | SiO2 aerogel with bactericidal function and preparation method therefor |
| CN105271263A (en) * | 2015-09-18 | 2016-01-27 | 四川鑫炬矿业资源开发股份有限公司 | Low-density transparent silica aerogel and preparation method |
| WO2016173911A1 (en) | 2015-04-29 | 2016-11-03 | Wacker Chemie Ag | Process for producing organically modified aerogels |
| EP3147261A1 (en) * | 2014-05-22 | 2017-03-29 | Panasonic Intellectual Property Management Co., Ltd. | Process for producing silica aerogel |
| CN106587081A (en) * | 2016-12-01 | 2017-04-26 | 伊科纳诺（北京）科技发展有限公司 | Method for preparing hydrophobic hybrid aerosil |
| CN106746692A (en) * | 2016-12-01 | 2017-05-31 | 湖北硅金凝节能减排科技有限公司 | Aeroge is in absorption and seals the application on heavy metal up for safekeeping |
| KR20180113818A (en) * | 2017-04-07 | 2018-10-17 | 주식회사 엘지화학 | Method for preparing transparent silica hydrogel |
| CN109012517A (en) * | 2018-08-28 | 2018-12-18 | 浙江工业大学 | A method of compound silica-based aerogel is prepared by raw material of iron tailings |
| CN111484021A (en) * | 2020-05-08 | 2020-08-04 | 厦门大学 | Preparation method of silicon dioxide aerogel |
| CN112978737A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Preparation method of nano silicon oxide particles with uniform particle size |
| CN113015697A (en) * | 2018-11-13 | 2021-06-22 | 弗劳恩霍夫应用研究促进协会 | Method for producing aerogels and aerogels obtained using said method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101164881A (en) * | 2007-10-11 | 2008-04-23 | 北京科技大学 | Low cost method for preparing SiO2 aerogel micro-sphere |
| CN101691227A (en) * | 2009-10-13 | 2010-04-07 | 厦门大学 | Method for preparing silica aerogel material |
| CN102659120A (en) * | 2012-04-18 | 2012-09-12 | 同济大学 | Preparation method for hydrophobic large-size bulk nanometer porous SiO2 aerogel |
-
2012
- 2012-11-06 CN CN201210439670.4A patent/CN102897779B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101164881A (en) * | 2007-10-11 | 2008-04-23 | 北京科技大学 | Low cost method for preparing SiO2 aerogel micro-sphere |
| CN101691227A (en) * | 2009-10-13 | 2010-04-07 | 厦门大学 | Method for preparing silica aerogel material |
| CN102659120A (en) * | 2012-04-18 | 2012-09-12 | 同济大学 | Preparation method for hydrophobic large-size bulk nanometer porous SiO2 aerogel |
Non-Patent Citations (3)
| Title |
|---|
| SHARAD D. BHAGAT等: "A cost-effective and fast synthesis of nanoporous SiO2 aerogel powders using water-glass via ambient pressure drying route", 《SOLID STATE SCIENCES》 * |
| SHARAD D. BHAGAT等: "Superhydrophobic silica aerogel powders with simultaneous surface modification, solvent exchange and sodium ion removal from hydrogels", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| SHARAD D. BHAGAT等: "Superhydrophobic silica aerogel powders with simultaneous surface modification, solvent exchange and sodium ion removal from hydrogels", 《MICROPOROUS AND MESOPOROUS MATERIALS》, vol. 112, 30 October 2008 (2008-10-30) * |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396086A (en) * | 2013-08-08 | 2013-11-20 | 厦门大学 | Preparation method for glass fiber-reinforced water glass-based silica composite aerogel |
| CN104740797A (en) * | 2013-12-31 | 2015-07-01 | 镇江新元素医药科技有限公司 | Respirator capable of filtering PM (particulate matters) 2.5 effectively |
| CN104740797B (en) * | 2013-12-31 | 2018-09-04 | 镇江新元素医药科技有限公司 | A kind of mask that can effectively filter PM2.5 |
| CN104071797A (en) * | 2014-05-21 | 2014-10-01 | 合肥科斯孚安全科技有限公司 | Method for preparing silicon dioxide aerogel coating with low density and large specific surface area by water glass at normal pressure and room temperature |
| CN104071797B (en) * | 2014-05-21 | 2015-12-09 | 合肥科斯孚安全科技有限公司 | A kind of method preparing low density bigger serface aerosil coating with water glass atmospheric pressure at room |
| EP3147261A1 (en) * | 2014-05-22 | 2017-03-29 | Panasonic Intellectual Property Management Co., Ltd. | Process for producing silica aerogel |
| US10077193B2 (en) | 2014-05-22 | 2018-09-18 | Panasonic Intellectual Property Management Co., Ltd. | Method for producing silica aerogel |
| EP3147261A4 (en) * | 2014-05-22 | 2017-03-29 | Panasonic Intellectual Property Management Co., Ltd. | Process for producing silica aerogel |
| CN105236929A (en) * | 2014-07-09 | 2016-01-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | SiO2 aerogel with bactericidal function and preparation method therefor |
| WO2016173911A1 (en) | 2015-04-29 | 2016-11-03 | Wacker Chemie Ag | Process for producing organically modified aerogels |
| DE102015207939A1 (en) | 2015-04-29 | 2016-11-03 | Wacker Chemie Ag | Process for the preparation of organically modified aerogels |
| US10618815B2 (en) | 2015-04-29 | 2020-04-14 | Wacker Chemie Ag | Process for producing organically modified aerogels |
| CN105110340B (en) * | 2015-06-23 | 2019-03-26 | 北京建工新型建材有限责任公司 | A kind of preparation method of elasticity transparent silicon dioxide aerogel |
| CN105110340A (en) * | 2015-06-23 | 2015-12-02 | 北京建工新型建材有限责任公司 | Preparation method for elastic transparent silica aerogel |
| CN105271263A (en) * | 2015-09-18 | 2016-01-27 | 四川鑫炬矿业资源开发股份有限公司 | Low-density transparent silica aerogel and preparation method |
| CN106746692A (en) * | 2016-12-01 | 2017-05-31 | 湖北硅金凝节能减排科技有限公司 | Aeroge is in absorption and seals the application on heavy metal up for safekeeping |
| CN106587081A (en) * | 2016-12-01 | 2017-04-26 | 伊科纳诺（北京）科技发展有限公司 | Method for preparing hydrophobic hybrid aerosil |
| KR20180113818A (en) * | 2017-04-07 | 2018-10-17 | 주식회사 엘지화학 | Method for preparing transparent silica hydrogel |
| KR102358445B1 (en) * | 2017-04-07 | 2022-02-04 | 주식회사 엘지화학 | Method for preparing transparent silica hydrogel |
| CN109012517A (en) * | 2018-08-28 | 2018-12-18 | 浙江工业大学 | A method of compound silica-based aerogel is prepared by raw material of iron tailings |
| CN109012517B (en) * | 2018-08-28 | 2020-09-29 | 浙江工业大学 | Method for preparing composite silicon-based aerogel by taking iron tailings as raw materials |
| CN113015697A (en) * | 2018-11-13 | 2021-06-22 | 弗劳恩霍夫应用研究促进协会 | Method for producing aerogels and aerogels obtained using said method |
| CN112978737A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Preparation method of nano silicon oxide particles with uniform particle size |
| CN111484021A (en) * | 2020-05-08 | 2020-08-04 | 厦门大学 | Preparation method of silicon dioxide aerogel |
| CN111484021B (en) * | 2020-05-08 | 2021-11-09 | 福建蓝烟新材料有限公司 | Preparation method of silicon dioxide aerogel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102897779B (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102897779B (en) | Preparation method of transparent silicon dioxide aerogel | |
| CN101691227B (en) | Method for preparing silica aerogel material | |
| CN101372337B (en) | Method for preparing transparent silicon dioxide aerogel by co-precursor normal atmosphere drying | |
| CN106629750B (en) | A kind of atmospheric preparation method of transparent silicon dioxide block aeroge | |
| CN102642841B (en) | A kind of normal pressure prepares low density and high performance SiO2The method of aeroge | |
| KR100924781B1 (en) | Method for Preparing Surface-Modified Transparent Bead Type Aerogel and Aerogel Prepared Therefrom | |
| CN103396086A (en) | Preparation method for glass fiber-reinforced water glass-based silica composite aerogel | |
| CN106867019A (en) | One kettle way prepares SiO2The method of cellulose composite aerogel material | |
| CN103708476A (en) | Preparation method of flexible silica aerogel | |
| CN102351507B (en) | Method for preparing fiber-reinforced SiO2 aerogel from rice husk ash as raw material | |
| CN103043673B (en) | A kind of preparation method of aerosil | |
| KR100796253B1 (en) | Method of fabricating superhydrophobic silica chain powders | |
| KR20100010350A (en) | Preparation method of silica aerogel powders | |
| CN102167337A (en) | Silicon dioxide aerogel and preparation method thereof | |
| CN110339790A (en) | Spherical amino modified silica aerogel and preparation method | |
| CN103936018A (en) | Method for preparing hydrophobic SiO2 aerogel by virtue of normal pressure drying | |
| CN101259964A (en) | Constant pressure and dry preparation method for high-performance silicon dioxide aerogel by using rice husk ash as raw material | |
| CN109133072A (en) | A method of hydrophobic silica aerogel is prepared using iron tailings as raw material is supper-fast | |
| TW201641544A (en) | Aerogel granule and preparation method thereof | |
| CN106430219A (en) | Method for preparing silicon oxide aerogel with low cost | |
| CN104909375A (en) | Method for rapidly preparing hydrophobicsilica aerogel by carbon dioxidesubcritical drying method | |
| Xia et al. | Synthesis and physicochemical characterization of silica aerogels by rapid seed growth method | |
| CN112138612A (en) | Preparation method of graphene-organic silicon composite aerogel | |
| CN101125655A (en) | Method for preparing nanometer silicon dioxide | |
| CN107759143B (en) | Mesoporous methyl silsesquioxane aerogel block with high specific surface area and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200116 Address after: Room 605, unit 1, floor 6, No. 20, Gongti East Road, Chaoyang District, Beijing 100020 Patentee after: Zhongke Runzi Technology Co.,Ltd. Address before: Xiamen City, Fujian Province, 361005 South Siming Road No. 422 Patentee before: Xiamen University |
|
| TR01 | Transfer of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of transparent silicon dioxide aerogel Effective date of registration: 20200409 Granted publication date: 20140806 Pledgee: Chongqing Hechuan Xuhui Venture Capital Co.,Ltd. Pledgor: Zhongke Runzi Technology Co.,Ltd. Registration number: Y2020500000003 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230307 Address after: 401120 Office Building, No. 1148, Gaoyang Road, Nanjin Street Sub-district Office, Hechuan District, Chongqing Patentee after: Zhongke Runzi (Chongqing) energy saving Technology Co.,Ltd. Address before: 100020 605, unit 1, 6 / F, 20 Gongti East Road, Chaoyang District, Beijing Patentee before: Zhongke Runzi Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right |