CN105110341B - A kind of preparation method of nanometer titanium dioxide silica aerogel - Google Patents
A kind of preparation method of nanometer titanium dioxide silica aerogel Download PDFInfo
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- CN105110341B CN105110341B CN201510553903.7A CN201510553903A CN105110341B CN 105110341 B CN105110341 B CN 105110341B CN 201510553903 A CN201510553903 A CN 201510553903A CN 105110341 B CN105110341 B CN 105110341B
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Abstract
The present invention discloses a kind of preparation method of nanometer titanium dioxide silica aerogel, with organic material methane-siliconic acid and inorganic material metallic silicon power as raw material, after first passing through steam activation, again with alkali reaction, adjust pH value, add secondary solvent to form silicon dioxide gel, be subsequently adding that auxiliary agent is aged, surface modified, after solvent displacement, finally carry out at ambient pressure nanometer titanium dioxide silica aerogel being obtained after classification is dried.The inventive method process is simple, safety, without the need for complicated, expensive device, process is easily controlled, and product quality is stable, and excellent performance, especially insulation, hydrophobicity are projected, and are easy to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of nanometer titanium dioxide silica aerogel.
Background technology
Aerosil is a kind of light material with nanoporous, in the side such as mechanics, acoustics, calorifics, optics
Face is respectively provided with the performance of uniqueness.Aerosil hole ratio is up to 80%-99.8%, and bore hole size is about 1nm-100nm, than
Surface area is up to 200m2/g-1000m2/ g, variable density is up to 3kg/m3-500kg/m3, heat-proof quality low with heat conductivity
It is good, and suction performance it is strong the advantages of.
In prior art, the preparation of aerosil typically adopts traditional high-temperature supercritical drying process, high temperature
Supercritical drying requires to carry out in high temperature, environment under high pressure, high energy consumption, high-risk, complex process equipment and costliness, is unfavorable for big
Scale is continuously produced.Generally to tetraethyl orthosilicate（TEOS）For silicon source, prepared by the aerosil of supercritical drying
Journey is complicated, and time-consuming, and efficiency is low, cost intensive.And conventional normal temperature and pressure dry technology research is still short of, the titanium dioxide prepared
Silica aerogel structural behaviour still can not be compared with aerosil prepared by supercritical drying, while unmodified SiO2
Aeroge has hydrophilic.The problem limits current SiO2The industrial applications of aerogel material.
The content of the invention
It is an object of the invention to provide a kind of preparation method of nanometer titanium dioxide silica aerogel, the method process is simple,
Reduce raw material and production equipment cost, prepared nanometer titanium dioxide silica aerogel excellent performance.
To reach above-mentioned purpose, the solution of the present invention is：
A kind of preparation method of nanometer titanium dioxide silica aerogel, comprises the following steps：
The first step, by metallic silicon power and methane-siliconic acid 15-50 in mass ratio:1 mixing, is ground to particle diameter less than 45 microns
Afterwards, 0.5-2 hours are activated under water vapor conditions of the quality for 8-20 times of metallic silicon power quality, being then dividedly in some parts quality is
The aqueous slkali of silica flour and methane-siliconic acid gross mass 4%, reacts 2-4 hours, is filtered；
Second step, adds acid to be neutralized reaction in the filtrate after filtration, after pH value reaches 2-5, add volume for filter
Liquid accumulates 0.5-1 times of secondary solvent and is sufficiently stirred for 5-30 minutes, then is added thereto to quality for silicon dioxide gel quality
0.5-2% drying aids, stand 0.5-1.5 hours and form silica hydrogel；
3rd step, silica hydrogel is aged at 40-70 DEG C, and digestion time is 4-72 hours；
4th step, is going for 1-6 times of silica hydrogel quality by the silica hydrogel quality after ageing
Ion water washing 1-3 time, time are 1-4 hours；Silane coupler and organic solvent mixing are subsequently adding, surface are carried out and is modified,
After reacting 6-24 hours at 30-70 DEG C, then using azeotropic distillation device replacement solvent；
5th step, silica hydrogel obtained in step 4 is carried out at ambient pressure to obtain nano-silica after classification is dried
SiClx aeroge, baking temperature are dried from 60,80,100,120,150 DEG C, and time interval is 1-2 hours.
Further, in step one, aqueous slkali is sodium hydroxide, potassium hydroxide, sodium carbonate, the one kind in ammonia spirit, its matter
Amount fraction is 1.0-3.0%.
Further, in step one, aqueous slkali is preferably the oxyammonia solution that mass fraction is 1.5%.Further, step 2
In acid be hydrochloric acid, sulphuric acid, phosphoric acid, the one kind in oxalic acid, its mass fraction is 1-15%.
Further, the acid in step 2 is preferably the sulfuric acid solution that mass fraction is 8%.
Further, secondary solvent is methanol, ethanol, isopropanol, the one kind in n-butyl alcohol.
Further, drying aids be dimethylformamide, acetamide, the one kind in Methanamide.
Further, the silane coupler in step 4 is isobutyl triethoxy silane, gamma-aminopropyl-triethoxy silicon
One kind in alkane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, 1-5% of its consumption for hydrogel quality.
Further, the silane coupler in step 4 is preferably the isobutyl triethoxy silane that mass fraction is 2%.
Further, the organic solvent in step 4 be methanol, ethanol, acetone, n-butyl alcohol, normal heptane, Ketohexamethylene, chloroform,
One kind in dichloromethane, 1-2.5 times for hydrogel quality of its consumption.
After such scheme, organic material methane-siliconic acid and inorganic material metallic silicon power are raw material by the present invention, first Jing
After crossing steam activation, then with alkali reaction, adjust pH value, add secondary solvent formed silicon dioxide gel, be subsequently adding auxiliary agent
Aged, surface is modified, after solvent displacement, finally carry out at ambient pressure obtaining nanometer titanium dioxide silica aerogel after classification is dried.
The nanometer titanium dioxide silica aerogel prepared by the method has advantages below：
One, using organic material methane-siliconic acid and inorganic material metallic silicon power different material basigamy, under steam activation
A kind of three dimensional skeletal structure of hybrid inorganic-organic is prepared with hybridization technique and modification technology.Therefore, its hydrophobicity is dashed forward
Go out, heat insulating effect it is notable.
Two, drying is classified using normal pressure, it is to avoid using supercritical fluid drying technique, this technique has simply, without needs
The low advantage of complex device, cost of investment, and avoid the high temperature needed for dry run, condition of high voltage there is high cost and peace
The shortcomings of hidden danger is big entirely.
Three, the loose structure with lightweight, comprcssive strength are high, and coefficient of thermal conductivity is less than 0.02W/ (m.K), heat-insulation and heat-preservation effect
It is really good, and density is low, water proof fire retardant, environmental protection, anti-soda acid is corrosion-resistant, non-aging, long service life.
Specific embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment one
A kind of preparation method of nanometer titanium dioxide silica aerogel, comprises the following steps：
The first step, weighs 15g metallic silicon powers and the mixing of 1.0g methane-siliconic acids, and Jing ball millings are machined to particle diameter less than 45 microns
Afterwards, it is placed in 2000ml there-necked flasks, then passes to 320g steam activations 0.5 hour, is then dividedly in some parts 42.66g mass
Fraction is 1.5% Dilute Ammonia Solution, reacts 2 hours, is filtered；
Second step, adds the sulfuric acid solution that mass fraction is 8% to be neutralized reaction, when pH value reaches in the filtrate after filtration
To after 2.0, add the secondary solvent methanol of 260ml to be simultaneously sufficiently stirred for 30 minutes, then plus 2.6g dimethylformamides make drying and help
Agent, stands 0.5 hour and forms silica hydrogel；
3rd step, silica hydrogel obtained in above-mentioned steps two is aged at 40 DEG C, and digestion time is 48
Hour；
4th step, the 800ml deionized water wash of the silica hydrogel after ageing is washed 2 times, and the time is 1 little
When；900ml n-butyl alcohol and 8.0g isobutyl triethoxy silanes are subsequently adding, surface are carried out and is modified, react 6 hours at 70 DEG C
Afterwards, then using azeotropic distillation device replacement solvent；
5th step, hydrogel obtained in step 4 is carried out at ambient pressure to obtain nano silicon airsetting after classification is dried
Glue, baking temperature are dried from 60,80,100,120,150 DEG C, and time interval is 2 hours.
Embodiment two
A kind of preparation method of nanometer titanium dioxide silica aerogel, comprises the following steps：
The first step, weighs 50g metallic silicon powers and the mixing of 1.0g methane-siliconic acids, and Jing ball millings are machined to particle diameter less than 45 microns
Afterwards, it is placed in 2000ml there-necked flasks, then passes to 408g steam activations 2 hours, is then dividedly in some parts 68.0g mass fractions
For 1.0% sodium hydroxide solution, react 2 hours, filtered；
Second step, adds the hydrochloric acid solution that mass fraction is 15.0% to be neutralized reaction, works as pH value in the filtrate after filtration
After reaching 5.0, add the secondary solvent ethanol of 527ml to be simultaneously sufficiently stirred for 5 minutes, then plus 10.54g acetamides make drying aids,
Stand 1.5 hours and form silica hydrogel；
3rd step, silica hydrogel obtained in above-mentioned steps two is aged at 70 DEG C, and digestion time is 72
Hour；
4th step, the 1200ml deionized water wash of the silica hydrogel after ageing is washed 3 times, and the time is 4 little
When；2000ml ethanol and 10.64g gamma-aminopropyl-triethoxy-silanes are subsequently adding, and are carried out surface and are modified, 24 are reacted at 30 DEG C
After hour, then using azeotropic distillation device replacement solvent；
5th step, hydrogel obtained in step 4 is carried out at ambient pressure to obtain nano silicon airsetting after classification is dried
Glue, baking temperature are dried from 60,80,100,120,150 DEG C, and time interval is 2 hours.
Embodiment three
A kind of preparation method of nanometer titanium dioxide silica aerogel, comprises the following steps：
The first step, weighs 20g metallic silicon powers and the mixing of 1.0g methane-siliconic acids, and Jing ball millings are machined to particle diameter less than 45 microns
Afterwards, it is placed in 2000ml there-necked flasks, then passes to 210g steam activations 1 hour, is then dividedly in some parts 28.0g mass fractions
For 3.0% potassium hydroxide solution, react 1 hour, filtered；
Second step, adds the oxalic acid solution that mass fraction is 10.0% to be neutralized reaction, works as pH value in the filtrate after filtration
After reaching 3.0, add the secondary solvent n-butyl alcohol of 250ml to be simultaneously sufficiently stirred for 20 minutes, then plus 5.0g Methanamides make drying aids,
Stand 1.0 hours and form silica hydrogel；
3rd step, silica hydrogel obtained in above-mentioned steps two is aged at 50 DEG C, and digestion time is 36
Hour；
4th step, the 560ml deionized water wash of the silica hydrogel after ageing is washed 1 time, and the time is 1 little
When；800ml n-butyl alcohol and 13.75g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane are subsequently adding, surface are carried out and is modified,
After 60 DEG C of reactions 12 hours, then using azeotropic distillation device replacement solvent；
5th step, hydrogel obtained in step 4 is carried out at ambient pressure to obtain nano silicon airsetting after classification is dried
Glue, baking temperature are dried from 60,80,100,120,150 DEG C, and time interval is 2 hours.
Example IV
A kind of preparation method of nanometer titanium dioxide silica aerogel, comprises the following steps：
The first step, weighs 30g metallic silicon powers and the mixing of 1.0g methane-siliconic acids, and Jing ball millings are machined to particle diameter less than 45 microns
Afterwards, it is placed in 2000ml there-necked flasks, then passes to 248g steam activations 1.5 hours, is then dividedly in some parts 62.0g mass point
Number is 2.0% sodium carbonate liquor, reacts 3 hours, is filtered；
Second step, adds the phosphoric acid solution that mass fraction is 12.0% to be neutralized reaction, works as pH value in the filtrate after filtration
After reaching 4.0, add the secondary solvent isopropanol of 160ml and be sufficiently stirred for 15 minutes, then plus 3.2g dimethylformamides amine work
Drying aids, stand 1.5 hours and form silica hydrogel；
3rd step, silica hydrogel obtained in above-mentioned steps two is aged at 60 DEG C, and digestion time is 72
Hour；
4th step, the 1440ml deionized water wash of the silica hydrogel after ageing is washed 3 times, and the time is 4 little
When；480ml normal heptane and 12.0g gamma-aminopropyl-triethoxy-silanes are subsequently adding, and are carried out surface and are modified, 18 are reacted at 50 DEG C
After hour, then using azeotropic distillation device replacement solvent；
5th step, hydrogel obtained in step 4 is carried out at ambient pressure to obtain nano silicon airsetting after classification is dried
Glue, baking temperature are dried from 60,80,100,120,150 DEG C, and time interval is 2 hours.
In all of above embodiment, it is all needed for chemical drugss, reagent and prepare solution needed for chemical drugss,
Reagent is the pure above purity of analysis, and water used is deionized water.
The preferred embodiments of the present invention are the foregoing is only, not the restriction to this case, what all keys according to this case were done
Equivalent variations, each fall within the protection domain of this case.
Claims (7)
1. a kind of preparation method of nanometer titanium dioxide silica aerogel, it is characterised in that comprise the following steps：
The first step, by metallic silicon power and methane-siliconic acid 15-50 in mass ratio:1 mixing, after being ground to particle diameter less than 45 microns,
Then quality is dividedly in some parts quality for silica flour to activate 0.5-2 hours under 8-20 times of metallic silicon power quality of water vapor conditions
With the aqueous slkali of methane-siliconic acid gross mass 4%, 2-4 hours are reacted, is filtered；
Second step, adds acid to be neutralized reaction in the filtrate after filtration, after pH value reaches 2-5, addition volume is filtrate body
The secondary solvent of 0.5-1 times of product is simultaneously sufficiently stirred for 5-30 minutes, then is added thereto to quality for silicon dioxide gel quality
The drying aids of 0.5-2%, stand 0.5-1.5 hours and form silica hydrogel；
3rd step, silica hydrogel is aged at 40-70 DEG C, and digestion time is 4-72 hours；
4th step, by the deionization that the silica hydrogel quality after ageing is 1-6 times of silica hydrogel quality
Water washing 1-3 time, time are 1-4 hours；Silane coupler and organic solvent mixing are subsequently adding, surface are carried out and is modified, in 30-
After 70 DEG C of reaction 6-24 hours, then using azeotropic distillation device replacement solvent；
5th step, silica hydrogel obtained in step 4 is carried out at ambient pressure to obtain nano silicon after classification is dried
Aeroge, baking temperature are dried from 60,80,100,120,150 DEG C, and time interval is 1-2 hours.
2. a kind of preparation method of nanometer titanium dioxide silica aerogel as claimed in claim 1, it is characterised in that alkali in step one
Solution is sodium hydroxide, potassium hydroxide, sodium carbonate, the one kind in ammonia spirit, and its mass fraction is 1.0-3.0%.
3. a kind of preparation method of nanometer titanium dioxide silica aerogel as claimed in claim 1, it is characterised in that in step 2
Sour one kind in hydrochloric acid, sulphuric acid, phosphoric acid, oxalic acid, its mass fraction are 1-15%.
4. a kind of preparation method of nanometer titanium dioxide silica aerogel as claimed in claim 1, it is characterised in that secondary solvent is
One kind in methanol, ethanol, isopropanol, n-butyl alcohol.
5. a kind of preparation method of nanometer titanium dioxide silica aerogel as claimed in claim 1, it is characterised in that drying aids are
One kind in dimethylformamide, acetamide, Methanamide.
6. a kind of preparation method of nanometer titanium dioxide silica aerogel as claimed in claim 1, it is characterised in that in step 4
Silane coupler is isobutyl triethoxy silane, gamma-aminopropyl-triethoxy-silane, γ-(the third oxygen of 2,3- epoxies) propyl group three
One kind in methoxy silane, 1-5% of its quality for hydrogel quality.
7. a kind of preparation method of nanometer titanium dioxide silica aerogel as claimed in claim 1, it is characterised in that in step 4
Organic solvent is methanol, ethanol, acetone, n-butyl alcohol, normal heptane, Ketohexamethylene, chloroform, the one kind in dichloromethane, and its consumption is
1-2.5 times of hydrogel quality.
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