CN104475059B - A kind of preparation method of sponge silica aerogel composite - Google Patents
A kind of preparation method of sponge silica aerogel composite Download PDFInfo
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- CN104475059B CN104475059B CN201410701719.8A CN201410701719A CN104475059B CN 104475059 B CN104475059 B CN 104475059B CN 201410701719 A CN201410701719 A CN 201410701719A CN 104475059 B CN104475059 B CN 104475059B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/44—Materials comprising a mixture of organic materials
- B01J2220/445—Materials comprising a mixture of organic materials comprising a mixture of polymers
Abstract
The present invention provides a kind of preparation method of sponge silica aerogel composite, and silicon source and solvent are mixed and added into formation silicon source solution after deionized water is stirred；Acidic catalyst, base catalyst and drying control chemical additive are successively added in silicon source solution, stirring obtains the Ludox of pH=5 7；It is poured into again in the container for filling sponge, gel is formed after standing；Add polar solvent to carry out aging, exchange, then add the polar solvent that non-polar solven is swapped out in gel；Finally it is soaked in the mixed liquor of silane coupler and non-polar solven to gel surface modification after carrying out classification drying under condition of normal pressure, obtain that hydrophobicity is strong and the strong sponge silica aerogel composite of adsorptivity, its hydrophobic oleophilic oil, it is high to the organic solvent such as n-hexane, gasoline, kerosene, benzene adsorption rate, adsorption capacity has very strong application value up to more than the 95% of itself volume, in municipal sewage treatment or petroleum pollution in ocean etc..
Description
Technical field
The invention belongs to technical field of macromolecules, and in particular to a kind of sponge of super hydrophobic and high adsorption-silicon airsetting
The preparation method of glue composite.
Background technology
Sponge is a kind of porous material, has good water imbibition, but its hole is larger, and water storage capacity is weaker, water
Uptake is little；Aeroge is then a kind of nano-porous materials of bigger serface, and density is smaller（About 0.1g/cm3）；And
Though being handled through surface hydrophobicity, silica-aeroge of constant pressure and dry can largely adsorb organic matter, moisture is not absorbed completely.
In view of the condition that supercritical drying prepares aerosil is very harsh, and the requirement to equipment is very high, mesh
The preparation method of preceding constant pressure and dry turns into the research emphasis of people.Such as Ni Xingyuan（Chinese patent, application number
200810042222.4）Disclose and use rice-straw ash as raw material, be modified, prepared at ambient pressure hydrophobic by exchange of solvent, surface
The method of type aerosil.Cao Xu light etc.（Chinese patent, application number 200910042159.5）Disclose with organosilicon
Oxygen alkane is replaced through microwave irradiation, solvent, the method for preparing aerosil at ambient pressure.Jiang Faxing, Lin Fen etc.（It is Chinese special
Profit, application number 201210123519.X）It is raw material that one kind, which is disclosed, with acidic silicasol, is replaced through solvent, surface silicyl
After change, pass through the method for the obtained aerosil of overcritical or constant pressure and dry.Chinese patent CN201210121968.0,
CN201210114691.9 is prepared, by ion exchange, with positive silicic acid four using sodium metasilicate as raw material using collosol and gel two-step method
The ethanol solution aging of ethyl ester, most obtains aeroge through exchange of solvent and modification, constant pressure and dry afterwards.Liu Guangwu of Tongji University etc.
Using waterglass as silicon source, after being replaced by alcohol solvent, the table of hexamethyldisiloxane and hydrochloric acid mixed solution to wet gel is directly used
Face is group modified, and constant pressure and dry goes out hydrophobic SiO2Aeroge, the dosage of modifying agent are big.The Lv Pengpeng of University of Science ＆ Technology, Beijing is equal
Sample is using waterglass as silicon source, and using ethylene glycol, formamide as solvent, silicon is obtained with exchanging last air drying by the agings of 7 days
Aeroge, preparation time are longer.Ni Wen etc. is modified one-step method using waterglass as silicon source, using exchange of solvent and surface and prepares silicon gas
Gel.
The pure silicon dioxide aerogel particle prepared above by constant pressure and dry method is smaller, in irregular shape, is using
During easily cracking situation, so as to limit its application, actually pure silicon dioxide aeroge is also seldom direct
Utilize.
In addition, Chinese patent（Application number CN103073008A）Using tetraethyl orthosilicate as silicon source, through collosol and gel, always
The steps such as change, exchange of solvent, surface modification, have been prepared aerosil, it was prepared under the conditions of constant pressure and dry
Journey is more complicated, and absorption property is bad.Cui Sheng, all pellets etc.（Chinese patent, application number 201310675505.3）Utilize positive silicic acid four
Ethyl ester etc. is that silicon source has prepared hydrophilic aerogel/sponge by sol-gel process under CO 2 supercritical drying condition
Composite, it utilizes supercritical drying process, and the danger of operation, cost etc. greatly improve, and the compound secondly prepared is
Hydrophilic, it is bad to the assimilation effect of greasy dirt in water.Bian Zhaoyong, Wang Hui etc.（Chinese patent, application number 201310271648.8）
It is prepared for being prepared for silica aerogel under the conditions of constant pressure and dry using the alkoxysilane mixture of functional group substitution as presoma
Oil suction sponge, although preparation process is simple, the alkoxy silane of the functional group substitution used in it is expensive, is not suitable for
A large amount of productions.
The content of the invention
It is an object of the invention to characteristics such as the bigger serface using aerosil, super hydrophobics, with sponge
For skeleton, through gel, exchange, surface is modified and classification is dried and prepares sponge-silicon dioxide silica aerogel composite material.The material can
Specific shape is made as needed, there is very strong organic matter adsorption capacity, while hydrophobicity is strong（Hydrophobic angle about 161
Degree）, and the unfavorable factor such as contraction, cracking occurred in prepared by normal pressure is avoided, therefore in municipal sewage treatment or offshore oil
Pollution etc. has very strong application value.
Technical scheme is as follows：
A kind of preparation method of sponge-silica aerogel composite, comprises the following steps：
（1）Silicon source and solvent are mixed and added into formation silicon source solution after deionized water is stirred；
（2）Acidic catalyst regulation pH value of solution=3-4 is first added in silicon source solution；Add drying control chemistry addition
Heating water bath is carried out after agent stirring, base catalyst is eventually adding and stirs to obtain pH=5-7 Ludox；
（3）Ludox is poured into the container for filling sponge, gel is formed after standing；
（4）Under 40-60 DEG C of water-bath, polar solvent progress aging is added into gel, and be swapped out the moisture in gel；
（5）Add non-polar solven and carry out exchange of solvent, to be swapped out the polar solvent in gel；
（6）The soak after polar solvent will be swapped out in the mixed liquor of silane coupler and non-polar solven to solidifying
Glue surface is modified；
（7）Classification drying is carried out in atmospheric conditions to modified gel, obtains hydrophobic, absorbent-type sponge-silicon airsetting
Glue composite.
Further preferred scheme, the step（1）Middle silicon source is tetraethyl orthosilicate or positive quanmethyl silicate, and solvent is first
Alcohol or ethanol；The silicon source and the volume ratio of solvent are 1:1.5-5, silicon source and be 1 with the amount ratio of the material of deionized water:2-6.
The step（2）Middle acidic catalyst is aqueous hydrochloric acid solution or ammonium fluoride solution, and its concentration is 0.1-0.5mol/L；
The drying control chemical additive is N, N- dimethylformamides, N, N- dimethyl acetamides or ethylene glycol, the drying
It is 0.5-2 to control the amount of chemical addition agent and the material of silicon source ratio, and the heating water bath time is 6-10h.
The step（2）Neutral and alkali catalyst is ammonia spirit or ethanolamine solutions, and its concentration is 0.5-2mol/L.
The step（3）The middle container for containing sponge is shaped as cylindricality or square, and its bottom surface area is more than sponge
Planimetric area；
The addition of the Ludox is defined by flooding sponge；
After Ludox to be poured into the container for filling sponge, then pressing sponge is stood with fully discharging its internal air
30min-2h。
Further, the step（4）Middle polar solvent is at least one in methanol, ethanol, acetone, ethylene glycol and isopropanol
Kind；
The addition of the polar solvent is defined by submerging all gels；
The number of the exchange is 1-3 times, is exchanged once per 6-10h.
The step（5）Middle non-polar solven is one kind in n-hexane, hexamethylene, normal heptane；
The addition of the non-polar solven is defined by submerging all gels；
The exchange of solvent number is 2-3 times, is exchanged once per 6-10h.
Further, the step（6）The mixed liquor of middle silane coupler and non-polar solven is with both percents by volume
Mixed for 10-25%, its addition is defined by submerging all gels；
The silane coupler is trim,ethylchlorosilane, HMDS, HMDO, 3- aminopropyls
One kind in triethoxysilane；
The non-polar solven is from one kind in n-hexane, hexamethylene, normal heptane.
Further, the step（6）Middle surface, which is modified, to be carried out in 40-60 DEG C of water bath, time 12-36h.
Further, the step（7）It is middle classification dryings be first by modified gel as at 40-60 DEG C drying 3-6h,
Then it is placed at 90-150 DEG C and dries 6-10h.
The present invention utilizes the characteristics such as the bigger serface of aerosil, super hydrophobic, using sponge as skeleton, through solidifying
Glue, exchange, surface is modified and classification is dried and prepares sponge-silicon dioxide silica aerogel composite material.The material can be made as needed
Into specific shape, there is very strong organic matter adsorption capacity, while hydrophobicity is high, and avoid what is occurred in prepared by normal pressure
Shrink, the unfavorable factor such as cracking, therefore there is very strong application value in municipal sewage treatment or petroleum pollution in ocean etc..
So the present invention has the advantages that relative to prior art：
（1）The present invention prepares sponge-silica aerogel composite using constant pressure and dry method, and it is relative to supercritical drying
For dry preparation method, the energy is saved, and it is low for equipment requirements.
（2）The present invention fixes aerogel particles using macroporous structure therein, can be made into by the use of sponge as skeleton
The sponge silica aerogel composite of large scale, regular shape, avoiding that pure silicon aeroge low intensity, shape are random can not be into
The defects of block, small particle, be not in shrink in use, situations such as cracking, be easy to practical application.
（3）Sponge prepared by the present invention-silica aerogel composite has hydrophobic oleophilic oil performance, and its absorption property is high, right
The organic solvent such as n-hexane, gasoline, kerosene, benzene adsorption rate is high, adsorption capacity up to itself volume more than 95%.
（4）Drying control chemical additive is added in the present invention to control the pore structure of gel, makes the hole of gel
Distribution is more uniform, improves its absorption property.
Embodiment
Specific embodiment is further described to the present invention below.
Embodiment one：
（1）Formed after 69ml tetraethyl orthosilicates are mixed and added into 24ml deionized waters stirring 30min with 180ml ethanol
Silicon source solution；
（2）0.1mol/L aqueous hydrochloric acid solutions are first added in silicon source solution, pH value of solution=3 is adjusted, adds 6ml N, N-
Dimethylformamide, stirring carry out 45 DEG C of heating water bath 6h after 5 minutes；0.5mol/L ammonia spirits are eventually adding to stir 2 minutes,
Obtain the Ludox of pH=6；
（3）Ludox is poured into the cylindricality for filling sponge or square container, extruding sponge is quiet to remove air therein
Gel is formed after putting 30min；
（4）Ethanol is added into gel to be defined to submerge topmost gel, carries out aging under 45 DEG C of water bath conditions, and hand over
The moisture to swap out in gel, exchange 1 time, time 10h；
（5）N-hexane is added into gel to be defined to submerge topmost gel, carries out exchange of solvent 2 times, and one is exchanged per 6h
It is secondary, to be swapped out the ethanol in gel；
（6）It is 10% by both percents by volume that the soak of ethanol, which will be swapped out, in trim,ethylchlorosilane and n-hexane
In the mixed liquor mixed, it is defined by submerging all gels, 12h is modified to gel surface in 45 DEG C of water baths；
（7）Classification drying is carried out in atmospheric conditions to modified gel, prior to 60 DEG C at dry 3h, at 90 DEG C
6h is dried, obtains sponge-silica aerogel composite.
Thermal conductivity 0.0257w/mk, the density 0.148g/cm of gained composite3, 162 ° of hydrophobic angle.
Embodiment two：
（1）Silicon is formed after the positive quanmethyl silicates of 23ml and 40ml methanol are mixed and added into 8ml deionized waters stirring 20min
Source solution；
（2）The ammonium fluoride solution that concentration is 0.1mol/L is first added in silicon source solution, pH value of solution=3 is adjusted, adds
4ml N, N- dimethyl acetamides, stirring carry out 45 DEG C of heating water bath 10h after 5 minutes, it is molten to be eventually adding 0.5mol/L monoethanolamines
Liquid stirs 2 minutes, must adjust the Ludox of pH=7；
（3）By step（2）In obtained Ludox pour into the cylindricality for filling sponge or square container, extruding sponge with except
Air therein is removed, gel is formed after standing 2h；
（4）Methanol is added into gel, is defined by submerging topmost gel, and aging is carried out under 60 DEG C of water bath conditions, and
Exchange 2 times, exchanged once per 10h, the moisture being swapped out in gel；
（5）N-hexane is added into gel to be defined to submerge topmost gel, carries out exchange of solvent 2 times, and one is exchanged per 8h
It is secondary, to be swapped out the methanol in gel；
（6）It is 25% by both percents by volume that the soak of methanol, which will be swapped out, in trim,ethylchlorosilane and n-hexane
In the mixed liquor mixed, it is defined by submerging all gels, 12h is modified to gel surface in 60 DEG C of water baths；
（7）Classification drying is carried out in atmospheric conditions to modified gel, prior to 50 DEG C at dry 3h, at 90 DEG C
6h is dried, obtains sponge-silica aerogel composite.
Thermal conductivity 0.0274w/mk, the density 0.152g/cm of gained composite3, 160 ° of hydrophobic angle.
Embodiment three：
（1）Silicon is formed after 23ml tetraethyl orthosilicates and 60ml ethanol are mixed and added into 6ml deionized waters stirring 20min
Source solution；
（2）0.1mol/L aqueous hydrochloric acid solutions are first added in silicon source solution, pH value of solution=3 is adjusted, adds 8ml N, N-
Dimethylformamide, stir 5 minutes, carry out 45 DEG C of heating water bath 6h afterwards；0.5mol/L ammonia spirits are added to stir 2 minutes,
Obtain the Ludox of pH=5；
（3）By step（2）In obtained Ludox pour into the cylindricality for filling sponge or square container, extruding sponge with except
Air therein is removed, gel is formed after standing 1h；
（4）Acetone is added into gel to be defined to submerge topmost gel, carries out aging under 40 DEG C of water bath conditions, and hand over
The moisture to swap out in gel, time 6h；
（5）Hexamethylene is added into gel to be defined to submerge topmost gel, carries out exchange of solvent 2 times, and one is exchanged per 6h
It is secondary, to be swapped out the acetone in gel；
（6）It is 10% by both percents by volume that the soak of acetone, which will be swapped out, in trim,ethylchlorosilane and n-hexane
In the mixed liquor mixed, it is defined by submerging all gels, 20h is modified to gel surface in 50 DEG C of water baths；
（7）Classification drying is carried out in atmospheric conditions to modified gel, prior to 60 DEG C at dry 3h, then at 150 DEG C
Lower dry 6h, obtain sponge-silica aerogel composite.
Thermal conductivity 0.0265w/mk, the density 0.158g/cm of gained composite3, 159 ° of hydrophobic angle.
Example IV：
（1）Formed after 11.5ml tetraethyl orthosilicates are mixed and added into 4ml deionized waters stirring 25min with 40ml methanol
Silicon source solution；
（2）0.5mol/L aqueous hydrochloric acid solutions are first added in silicon source solution, pH value of solution=4 is adjusted, adds 3ml ethylene glycol,
Stirring 5 minutes, 45 DEG C of heating water bath 6h are carried out afterwards；1mol/L ammonia spirits are added afterwards to mix 2 minutes, obtain the Ludox of pH=6；
（3）By step（2）In obtained Ludox pour into the cylindricality for filling sponge or square container, extruding sponge with except
Air therein is removed, gel is formed after standing 1.5 h；
（4）Methanol is added into gel, is defined by submerging topmost gel, and aging is carried out under 45 DEG C of water bath conditions, and
The moisture being swapped out in gel, time 10h；
（5）Normal heptane is added into gel to be defined to submerge topmost gel, carries out exchange of solvent 2 times, and one is exchanged per 8h
It is secondary, to be swapped out the ethanol in gel；
（6）The soak after polar solvent will be swapped out in APTES and normal heptane by both
Percent by volume is in 15% mixed liquor mixed, is defined by submerging all gels, to gel table in 40 DEG C of water baths
Face is modified 36h；
（7）Classification drying is carried out in atmospheric conditions to modified gel, prior to 40 DEG C at dry 6h, at 90 DEG C
10h is dried, obtains sponge-silica aerogel composite.
Thermal conductivity 0.0349w/mk, the density 0.147g/cm of gained composite3, 161 ° of hydrophobic angle.
Embodiment five：
（1）Formed after 11.5ml tetraethyl orthosilicates are mixed and added into 4ml deionized waters stirring 20min with 50ml ethanol
Silicon source solution；
（2）0.2mol/L aqueous hydrochloric acid solutions are first added in silicon source solution, pH value of solution=3 is adjusted, adds 3ml N, N-
Dimethyl acetamide, stir 5 minutes, carry out 45 DEG C of heating water bath 6h afterwards；2mol/L ammonia spirits are added to stir 2 minutes, pH=
6 Ludox；
（3）By step（2）In obtained Ludox pour into the cylindricality for filling sponge or square container, extruding sponge with except
Air therein is removed, gel is formed after standing 72min；
（4）Ethylene glycol is added into gel, is defined by submerging topmost gel, and aging is carried out under 60 DEG C of water bath conditions,
And the moisture in gel is swapped out, time 8h；
（5）Normal heptane is added into gel to be defined to submerge topmost gel, carries out exchange of solvent 3 times, and one is exchanged per 8h
It is secondary, to be swapped out the ethylene glycol in gel；
（6）The soak of ethylene glycol will be swapped out in hexamethyl HMDS and n-hexane by both volumes hundred
Divide than being in 20% mixed liquor mixed, be defined by submerging all gels, gel surface is modified in 60 DEG C of water baths
12h；
（7）Classification drying is carried out in atmospheric conditions to modified gel, prior to 60 DEG C at dry 3h, then at 120 DEG C
Lower dry 6h, obtain sponge-silica aerogel composite.
Thermal conductivity 0.0399w/mk, the density 0.157g/cm of gained composite3, 158 ° of hydrophobic angle.
Sponge-silica aerogel composite prepared by the embodiment of the present invention one-five detects according to related detecting method respectively
Its thermal conductivity（The hot food texture measurements of Hot Disk TPS2500s, room temperature）, density（GB/T 1933-2009）, hydrophobic angle（KSV
The contact angle measurements of CAM 200 (Helsinki, Finland), room temperature）, shown in table 1 specific as follows：
| Thermal conductivity | Density | Hydrophobic angle | |
| Embodiment one | 0.0257w/mk | 0.148g/cm3 | 162° |
| Embodiment two | 0.0274w/mk | 0.152g/cm3 | 160° |
| Embodiment three | 0.0265w/mk | 0.158g/cm3 | 159° |
| Example IV | 0.0349w/mk | 0.147g/cm3 | 161° |
| Embodiment five | 0.0399w/mk | 0.157g/cm3 | 158° |
It can be seen that from upper table 1, the thermal conductivity of sponge-silica aerogel composite prepared by the present invention is very low, for heat not
Good conductor；Density is 0.147-0.157g/cm3, illustrate that composite density is small, i.e., its porosity is big；Hydrophobic angle is 158-
162 °, illustrate that the composite hydrophobicity of the present invention is strong.
In addition, sponge-silica aerogel composite prepared by the present invention can repeatedly use, specifically made with embodiment one
Illustrated exemplified by standby sponge-silica aerogel composite, its adsorbance and the absorption number relation such as institute of table 2 to normal hexane
Show, and its adsorbance is also bigger than the adsorbance of pure aeroge, specific adsorbance is as shown in table 3.
Wherein adsorbance is relative to sorbing material volume itself, i.e. adsorbance=V (volume of adsorbed material)/V（Inhale
The volume of enclosure material）；Research of the adsorpting data of pure aeroge from Gurav et al..The adsorption test method of this material has no
In domestic standard, a foreign literature of reference（Zheng, Q., Z. Cai, and S. Gong, Journal of
Materials Chemistry A. 2 (2014) 3110.）
Adsorbance and the relation of absorption number of 2 sponges of the table-silica aerogel composite to n-hexane
| Adsorption desorption cycle-index | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Adsorbance（ml/cm3） | 0.91 | 0.90 | 0.91 | 0.89 | 0.88 | 0.89 | 0.91 | 0.90 | 0.92 | 0.90 |
The absorption property of table 3 compares（Adsorbance unit is ml/cm3）
As can be known from the above table, sponge-silica aerogel composite that prepared by the present invention can repeatedly use, as shown in table 2,
After normal hexane progress circulation absorption 10 times, its adsorbance remains to reach 0.90 ml/cm3。
As shown in table 3, sponge-silica aerogel composite that prepared by the present invention is to normal hexane, normal heptane, gasoline and kerosene
Adsorbance reach 0.91ml/cm3More than.And suction of the pure silicon dioxide aeroge to normal hexane, normal heptane, gasoline and kerosene
Attached amount is respectively 0.61,0.78,0.91,0.89ml/cm3, it is below the absorption of sponge-silica aerogel composite of the present invention
Amount.
Above example is not limited only to protection scope of the present invention, all to be modified based on the basic thought of invention
Or what is changed belongs to protection scope of the present invention.
Claims (9)
- A kind of 1. preparation method of sponge-silica aerogel composite, it is characterised in that：Comprise the following steps：（1）Silicon source and solvent are mixed and added into formation silicon source solution after deionized water is stirred；（2）Acidic catalyst regulation pH value of solution=3-4 is first added in silicon source solution；Drying control chemical additive is added to stir Heating water bath is carried out after mixing, base catalyst is eventually adding and stirs to obtain pH=5-7 Ludox；The drying control chemistry adds Agent is added to be N, N- dimethylformamides, N, N- dimethyl acetamides or ethylene glycol, the drying control chemical additive and silicon The amount ratio of the material in source is 0.5-2, and the heating water bath time is 6-10h；（3）Ludox is poured into the container for filling sponge, gel is formed after standing；（4）Under 40-60 DEG C of water-bath, polar solvent progress aging is added into gel, and be swapped out the moisture in gel；（5）Add non-polar solven and carry out exchange of solvent, to be swapped out the polar solvent in gel；（6）The soak after polar solvent will be swapped out in the mixed liquor of silane coupler and non-polar solven to gel table Face is modified；（7）Classification drying is carried out in atmospheric conditions to modified gel, obtains that hydrophobic, absorbent-type sponge-silica aerogel is multiple Condensation material；The classification drying is that first modified gel is placed at 40-60 DEG C to dry 3-6h, is then placed on 90-150 6-10h is dried at DEG C.
- 2. preparation method according to claim 1, it is characterised in that：The step（1）Middle silicon source is tetraethyl orthosilicate Or positive quanmethyl silicate, solvent are methanol or ethanol；The silicon source and the volume ratio of solvent are 1:1.5-5, silicon source and with go from The amount ratio of the material of sub- water is 1:2-6.
- 3. preparation method according to claim 1, it is characterised in that：The step（2）Middle acidic catalyst is hydrochloric acid water Solution or ammonium fluoride solution, its concentration are 0.1-0.5mol/L.
- 4. preparation method according to claim 1, it is characterised in that：The step（2）Neutral and alkali catalyst is that ammoniacal liquor is molten Liquid or ethanolamine solutions, its concentration are 0.5-2mol/L.
- 5. preparation method according to claim 1, it is characterised in that：The step（3）The shape of the middle container for containing sponge Shape is cylindricality or square, and its bottom surface area is more than the planimetric area of sponge；The addition of the Ludox is defined by flooding sponge；After Ludox to be poured into the container for filling sponge, then pressing sponge is stood with fully discharging its internal air 30min-2h。
- 6. preparation method according to claim 1, it is characterised in that：The step（4）Middle polar solvent is methanol, second At least one of alcohol, acetone, ethylene glycol and isopropanol；The addition of the polar solvent is defined by submerging all gels；The number of the exchange is 1-3 times, is exchanged once per 6-10h.
- 7. preparation method according to claim 1, it is characterised in that：The step（5）Middle non-polar solven be n-hexane, One kind in hexamethylene, normal heptane；The addition of the non-polar solven is defined by submerging all gels；The exchange of solvent number is 2-3 times, is exchanged once per 6-10h.
- 8. preparation method according to claim 1, it is characterised in that：The step（6）Middle silane coupler with it is nonpolar The mixed liquor addition of solvent is defined by submerging all gels；The silane coupler is trim,ethylchlorosilane, HMDS, HMDO, the second of 3- aminopropyls three One kind in TMOS；The non-polar solven is from one kind in n-hexane, hexamethylene, normal heptane.
- 9. preparation method according to claim 1, it is characterised in that：The step（6）It is at 40-60 DEG C that middle surface, which is modified, Carried out in water bath, time 12-36h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410701719.8A CN104475059B (en) | 2014-11-28 | 2014-11-28 | A kind of preparation method of sponge silica aerogel composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410701719.8A CN104475059B (en) | 2014-11-28 | 2014-11-28 | A kind of preparation method of sponge silica aerogel composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104475059A CN104475059A (en) | 2015-04-01 |
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| CN104923177B (en) * | 2015-05-19 | 2017-05-10 | 合肥科斯孚安全科技有限公司 | Preparation method of hydrophobic lipophilic sponge aerogel composite material |
| CN106830870A (en) * | 2017-03-05 | 2017-06-13 | 江苏华盛节能科技有限公司 | A kind of aerosil insulation material and preparation method thereof |
| CN107151020A (en) * | 2017-06-22 | 2017-09-12 | 中国科学技术大学 | A kind of method that silicon dioxide silica aerogel composite material is prepared with freeze-drying method |
| CN108855013A (en) * | 2018-07-31 | 2018-11-23 | 李忠 | A kind of processing of oil spill is with sponge and preparation method thereof |
| CN111437794A (en) * | 2020-04-24 | 2020-07-24 | 长春工业大学 | SiO (silicon dioxide)2Preparation method of aerogel/activated carbon composite material adsorbent |
| CN111848114B (en) * | 2020-07-31 | 2022-04-29 | 航天海鹰(镇江)特种材料有限公司 | Super heat-insulating aerogel composite material and preparation process thereof |
| CN112915979B (en) * | 2021-01-25 | 2023-07-25 | 伯克利南京医学研究有限责任公司 | Aerogel sponge material and preparation method and application thereof |
| CN113797881B (en) * | 2021-08-24 | 2024-05-07 | 天津朗华科技发展有限公司 | Petroleum and petrochemical waste gas adsorbent and preparation method and application thereof |
| CN113694877B (en) * | 2021-08-24 | 2023-11-28 | 天津朗华科技发展有限公司 | Selective adsorbent for purifying gasoline and preparation method and application thereof |
| CN113813937A (en) * | 2021-11-03 | 2021-12-21 | 江苏大学 | Selective adsorption material and preparation method thereof |
| CN116199522A (en) * | 2023-01-17 | 2023-06-02 | 武汉中科先进材料科技有限公司 | PU sponge-based silicon aerogel felt and preparation method thereof |
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| KR100848856B1 (en) * | 2007-03-27 | 2008-07-29 | 주식회사 넵 | Method for preparing hydrophobic surface aerogel and hydrophobic surface aerogel therefrom |
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| 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 |
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