CN105271260B - A kind of method that constant pressure and dry prepares hydrophobic silica aerogel - Google Patents
A kind of method that constant pressure and dry prepares hydrophobic silica aerogel Download PDFInfo
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- CN105271260B CN105271260B CN201410256475.7A CN201410256475A CN105271260B CN 105271260 B CN105271260 B CN 105271260B CN 201410256475 A CN201410256475 A CN 201410256475A CN 105271260 B CN105271260 B CN 105271260B
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000004965 Silica aerogel Substances 0.000 title claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 66
- 150000002576 ketones Chemical class 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 241001502050 Acis Species 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 230000001186 cumulative effect Effects 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000005815 base catalysis Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- -1 silicate ester Chemical class 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 44
- 239000007863 gel particle Substances 0.000 description 24
- 239000004964 aerogel Substances 0.000 description 23
- 229920002545 silicone oil Polymers 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 238000006073 displacement reaction Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000004048 modification Effects 0.000 description 12
- 238000012986 modification Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 9
- 239000011240 wet gel Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- 238000002336 sorption--desorption measurement Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000000352 supercritical drying Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a kind of method that constant pressure and dry prepares hydrophobic silica aerogel, including：（1）Positive silicate ester portion is hydrolyzed, formed poly- (oxyalkylsiloxane) with different polymerization degree；（2）Poly- (oxyalkylsiloxane) is well mixed with alcohol or ketone, base catalyst, standing forms alcohol or ketone gel；（3）After the alcohol/ketone gel is blended, mixed with liquid alkane or fluoroalkane, so as to displace alcohol/ketone in the alcohol/ketone gel, obtain alkane gel；（4）The mixed solution of the alkane gel and water-repelling agent and liquid alkane is mixed, hydrophobic alkane gel is obtained；（5）By the hydrophobic alkane gel constant pressure and dry, target product is obtained.The present invention can realize the continuous production of hydrophobic silica aerogel, with short production cycle without washing and alcohol swap operation, energy resource consumption is few, influence to environment is small, energy-conserving and environment-protective, and obtained product has the excellent properties such as lower thermal conductivity, high-specific surface area, low-density.
Description
Technical field
The present invention is more particularly directed to a kind of method that constant pressure and dry technology obtains hydrophobic silica aerogel powder, belong to and receive
Rice porous material technical field.
Background technology
Aeroge is a kind of highly porous nano material, generally using special process the liquid displacement in wet gel
Into gas aeroge is prepared without significantly changing the network structure of gel.First aerogel products are silica gas in the world
Gel, is prepared in professor Kistler by California, USA Pacific Ocean university in 1931 by agglutinating nature yeast and supercritical drying
Out.Because aerosil has high-specific surface area (400~1500m2/ g), high porosity (80~99.8%),
Low-density (0.003~0.6g/cm3) and the features such as lower thermal conductivity (0.012~0.038W/mk) so that aerosil
In high temperature resistant heat insulation material, extremely-low density material, acoustic impedance coupling material, gas absorption and filtering material, catalyst carrier material
The fields such as material, drug carrier material have boundless application prospect, and thus cause the huge research of academic and industrial circle
Interest.But, the aerogel products of current excellent performance are all prepared by supercritical drying, for example
CN102583407A and CN102642842B disclose the method that aeroge is prepared using supercritical drying, and it passes through shooting flow
Body displaces the solvent in wet gel, can be good at keeping the original structure of gel after finally drying.Usual supercritical drying
Need to use special equipment, operated under high pressure-temperature, on the one hand cause equipment expensive, operating difficulties, cost is high；The opposing party
There is great potential safety hazard in face.Therefore popularization is not got up at home for aerogel products and its application.
In order to reduce the production cost of aeroge, improve security, CN103073008A, CN101691227B and
CN103043673A discloses the method that aeroge is prepared using constant pressure and dry, including：Being exchanged by multiple and multi-solvents will
Fluid exchange in gel duct turns into the solvent of low surface tension, such as n-hexane, then the surface in duct is changed by hydrophily
Property is hydrophobicity, substantially reduces the capillary force in gel duct, thus during drying gel contraction very little, base
Original form can be kept on this.Because constant pressure and dry needs multiple gel duct exchange of solvent and surface-hydrophobicized processing,
Long preparation period, it is cumbersome, it is difficult to realize industrialization production.(the Solid state sciences2008,10 of document 1:
1113-1116) with (the Powder technology2010,197 of document 2:Serialization, high-volume 288-294) are reported respectively often
The method for suppressing prepared silicon dioxide aerogel powder, because document all uses relatively inexpensive waterglass for silicon source, preparation process
In need to remove multiple steps such as sodium ion, and alcohol displacement, alkane displacement, hydrophobically modified by ion-exchange or massive laundering method
Suddenly, long preparation period, cumbersome, the influence caused to environment is also larger.
The content of the invention
It is an object of the invention to propose that a kind of technique is simple, with short production cycle, cost is low, and only need simple device
The constant pressure and dry of execution prepares the method for hydrophobic silica aerogel, so as to overcome defect of the prior art.
For achieving the above object, present invention employs following technical scheme：
A kind of method that constant pressure and dry prepares hydrophobic silica aerogel, comprises the following steps：
(1) positive silicate ester portion is hydrolyzed, formed poly- (oxyalkylsiloxane) with different polymerization degree；
(2) poly- (oxyalkylsiloxane) is well mixed with alcohol or ketone, base catalyst, standing forms alcohol or ketone is solidifying
Glue；
(3) alcohol/ketone gel is blended to powder or graininess, mixed with liquid alkane or fluoroalkane, so that
Alcohol/ketone in the alcohol/ketone gel is displaced, alkane gel is obtained；
(4) mixed solution of the alkane gel and water-repelling agent and liquid alkane is mixed, obtains hydrophobic alkane gel；
(5) by the hydrophobic alkane gel constant pressure and dry, the hydrophobized silica aeroge of powder shaped is obtained.
Among one more preferred embodiment, step (1) can include：It is 1 by mol ratio:0.1~1:5.0 just
Esters of silicon acis and water are mixed with organic solvent, and add hydrolyst formation hybrid reaction system, are reacted under hydrolysis temperature
More than 0.1h, is obtained poly- (oxyalkylsiloxane).
Further, the positive esters of silicon acis can select but be not limited to tetraethyl orthosilicate or methyl silicate.
Further, the organic solvent can select but be not limited to alcohol or ketone.
Further, the hydrolyst includes inorganic acid or organic acid.
Further, the hydrolysis temperature is reflux temperature of the room temperature to the organic solvent.
It is preferred that, described in step (1) in hybrid reaction system the concentration of hydrolyst 10-1Within mol/L.
Among one more preferred embodiment, step (2) can include：
By volume ratio 50:1~0.01:1 alcohol or ketone and poly- (oxyalkylsiloxane) are well mixed with base catalyst, quiet
Put to form alcohol or ketone gel；
Further, the alcohol is preferred to use the small molecular alcohol that carbon number is less than 8.
Further, the ketone is preferred to use the ketone that carbon number is less than 8.
It is preferred that, the consumption of base catalyst described in step (2) is within the 15% of the alcohol or ketone gel cumulative volume.
Among one more preferred embodiment, step (3) includes：Liquid alkane or fluoroalkane are pressed 50 with alcogel:1
~1:100 volume ratio is mixed and stirred for, and wherein mixing speed is 10~8000rpm, and whipping temp is room temperature~alkane boiling point temperature
Degree, mixing time is more than 0.1h, so as to displace alcohol/ketone in the alcohol/ketone gel, obtains alkane gel.
Further, the liquid alkane or fluoroalkane are preferred to use the liquid alkane or fluoroalkane of carbon number≤8.
Among one more preferred embodiment, step (4) includes：It is 50 by volume ratio:1~1:100 water-repelling agent
Mixed with the mixed solution of liquid alkane with alkane gel, mixing speed is 10~8000rpm, whipping temp is room temperature~alkane boiling
Point temperature, mixing time is more than 0.1h, obtains the hydrophobic alkane gel.
Further, the volume percent content of water-repelling agent is preferably in the mixed solution of the water-repelling agent and liquid alkane
0.5%~50%.
Among one more preferred embodiment, the mode of constant pressure and dry includes forced air drying, dried in the air naturally in step (5)
Dry or vacuum drying, drying temperature is room temperature~300 DEG C, and drying time is in more than 0.1h.
Compared with prior art, the positive effect of the present invention includes：(1) water displacement, and existing constant pressure and dry are eliminated
Alcohol displacement needed for method, substantially reduces manufacturing cycle, has saved resource；(2) because not needing alcohol displacement, the big of alcohol can also be avoided
Amount is used, and reduce further cost, and reduce the influence to environment；(3) obtaining product has lower thermal conductivity, high-ratio surface
The excellent properties such as product, low-density.
Brief description of the drawings
Fig. 1 is by obtaining hydrophobic aerogel isothermal nitrogen adsorption desorption curve map in the embodiment of the present invention 1.
Fig. 2 is by obtaining hydrophobic aerogel isothermal nitrogen adsorption desorption curve map in the embodiment of the present invention 2.
Fig. 3 is by obtaining hydrophobic aerogel isothermal nitrogen adsorption desorption curve map in the embodiment of the present invention 3.
Fig. 4 is by obtaining hydrophobic aerogel isothermal nitrogen adsorption desorption curve map in the embodiment of the present invention 4.
Fig. 5 is by obtaining hydrophobic aerogel isothermal nitrogen adsorption desorption curve map in the embodiment of the present invention 5.
Fig. 6 is by obtaining hydrophobic aerogel isothermal nitrogen adsorption desorption curve map in the embodiment of the present invention 6.
Embodiment
In view of many defects of the prior art, inventor is through studying for a long period of time and largely putting into practice, it is proposed that the present invention
Technical scheme, it is mainly prepared into poly- (oxyalkylsiloxane) of the various degree of polymerization by raw material of positive esters of silicon acis and is used as silicon
Source, then by the way that silicon source, alcohol/ketone and base catalyst are well mixed, stand after gel, wet gel is blended, and with low surface
Liquid alkane or the fluoroalkane displacement of tension force, and be modified using water-repelling agent, re-dry obtains hydrophobic silica aerogel powder.
By technical scheme, it is possible to achieve the continuous production of hydrophobic silica aerogel, it is to avoid washing,
The steps such as alcohol exchange, with short production cycle, energy resource consumption is few, and effect on environment is small, and obtained hydrophobic silica aerogel has
There is nano-porous structure, density is 0.030~0.160g/cm3, thermal conductivity compares surface between 0.0130~0.0400W/mK
Product is in 600~1000m2Between/g, average pore size is less than 50nm.
Technical scheme is more specifically illustrated as follows.
The method that a kind of constant pressure and dry of the present invention prepares hydrophobic silica aerogel mainly includes：
(1) poly- (oxyalkylsiloxane) that positive silicate ester portion is hydrolyzed into a variety of degree of polymerization (may be also referred to simply as CS silicon
Oil), it is standby as self-control silicon source；
(2) the CS silicone oil, alcohol or ketone, base catalyst are well mixed, standing forms alcohol or ketone gel；
(3) obtained alcohol/ketone gel is blended to powder or graininess, then the gel is mixed with liquid alkane or fluoroalkane
Stirring, displaces alcohol/ketone in gel, finally obtains alkane gel using the mode such as filtering or centrifugation；
(4) mixed solution of obtained alkane gel and the water-repelling agent containing certain volume fraction and liquid alkane is mixed,
Reactant is then separated into obtain hydrophobic alkane gel using modes such as filterings；
(5) by obtained hydrophobic alkane gel constant pressure and dry, hydrophobized silica aerogel powder is obtained.
Wherein, among one more specific embodiment, the constant pressure and dry prepares the side of hydrophobic silica aerogel
Method can include：
(1) positive esters of silicon acis, hydrolyst, alcohol or ketone (such as acetone) are mixed evenly, backflow a period of time, example
Such as 8-20 hours, the CS silicone oil of the various degree of polymerization is formed, is stored for future use, its shelf-life is more than 1 year；
(2) silicone oil, alcohol or ketone, base catalyst are well mixed, standing forms gel, in time of room temperature to alcohol or ketone
Flow temperature (such as 60 DEG C) aging for a period of time, such as 1~5 hour；
(3) by obtained alcohol or ketone gel mechanical crushing, and mixed with liquid alkane or fluoroalkane, then will be obtained solidifying
Glue-alkane pulp separation is alkane gel and liquid alkane or fluoroalkane；
(4) by the mixed solution of obtained alkane gel and water-repelling agent and liquid alkane at room temperature or heating stirring, then by institute
Obtain gel mixture and be separated into hydrophobic alkane gel, alkane and hydrophobic reactant thing；
(5) by obtained hydrophobic alkane gel constant pressure and dry, hydrophobized silica aeroge is obtained.
Among a preferred embodiment, the esters of silicon acis employed in step (1) is preferably tetraethyl orthosilicate or methyl esters etc.,
The mol ratio row of itself and water are preferably controlled in 1:0.1~1:5.0；Solvent for use can be alcohol or ketone (such as acetone), and consumption is excellent
Selected control system is being 0.1 with the volume ratio of positive esters of silicon acis:1~1:0.1；The hydrolyst include watery hydrochloric acid, sulfuric acid, phosphoric acid,
The organic acid such as the inorganic acids such as nitric acid or acetic acid, oxalic acid, citric acid, its concentration in hydrolysis reaction system is preferably controlled in 10- 1Within mol/L；And hydrolysis temperature is preferably reflux temperature of the room temperature to solvent for use；Hydrolysis time is preferably at 0.1-50 hours.
Among a preferred embodiment, alcohol used includes methanol, ethanol, propyl alcohol, the tert-butyl alcohol, n-butanol in step (2)
Or (preferably, 8) carbon number is not more than other alcohol in alcohol molecule, and ketone used is that acetone, butanone or other ketone solvents are (excellent
Choosing, 8) carbon number is not more than in ketone molecule, and consumption is with CS silicone oil volume ratios 50:1~0.01:Between 1；Alkali wherein used
Catalyst includes sodium hydroxide, potassium hydroxide, urea, ammoniacal liquor, triethylamine etc., consumption preferably gel cumulative volume 15% with
It is interior.
, can be using manually broken or mechanical agitation crumbling method in step (3) among a preferred embodiment
The alcohol/ketone gel is blended to powder or graininess.
Among a preferred embodiment, step (3) can also include：By 50:1~1:100 volume ratio is by liquid alkane
It is mixed and stirred for alcogel, mixing speed is 10~8000rpm, whipping temp is room temperature~alkane boiling temperature, mixing time
For 0.1~100 hour, wherein the alkane includes various liquid alkane or fluoroalkane, particularly preferred carbon number was not more than 8 liquid
Alkane or fluoroalkane.
Among a preferred embodiment, step (4) can include：It is 50 by volume ratio:1~1:100 liquid alkane-dredge
Aqua mixed liquor is mixed with alkane gel, and mixing speed is 10~8000rpm, and whipping temp is room temperature~alkane boiling temperature,
Mixing time is 0.1~100 hour.
Further, percent by volume of the water-repelling agent in the mixed solution of water-repelling agent and liquid alkane described in step (4)
Content is 0.5%~50%.
Wherein, the water-repelling agent can select but be not limited to MTMS, trimethylmethoxysilane, dimethyl
Dichlorosilane, trim,ethylchlorosilane or hexamethyl two silicon nitrogen (amine) alkane etc..
Among a preferred embodiment, the constant pressure and dry mode in step (5) can select but be not limited to forced air drying, certainly
So dry or be dried in vacuo, and drying temperature is preferably room temperature~300 DEG C, drying time is preferably more than 0.1h, especially
It is 0.01 hour to 300 hours.
Below in conjunction with some preferred embodiments and accompanying drawing the technical solution of the present invention is further explained explanation.
Embodiment 1
(1) preparation of CS silicone oil：By 1 mole of tetraethyl orthosilicate, the dilute acid soln (concentration 10 of 0.8 mole of water-4mol/L)、
Ethanol (160ml) is mixed, standby after flowing back 16 hours.
(2) synthesis of gel：10 parts of CS silicone oil and 12 parts of ethanol are taken in stirred tank, stirring is lower to instill 50 microlitres of ammoniacal liquor, stirs
Speed 50rpm is mixed, stirring stands after 5 minutes and forms water white transparency alcogel.
(3) displacement of gel particle solvent and silicic acid anhydride：N-hexane 60ml is added after alcogel is crushed, stirring 4 is small
When after filter, then gel particle is placed among 60ml n-hexanes, and be slowly added to 10ml trim,ethylchlorosilanes, stirred 2 hours,
It is filtrated to get the alkane gel particle of surface-hydrophobicized modification.
(4) drying of wet gel particle：The gel particle of surface-hydrophobicized modification is dried in blast drier, temperature control
System obtains hydrophobic aerogel powder after 100 DEG C, 60 minutes, and the thin desorption curve figure of isothermal of the aerogel powder see Fig. 1,
Other specification sees table 1.
Embodiment 2
(1) preparation of CS silicone oil：By 1 mole of methyl silicate, the dilute acid soln (10 of 1.3 mole of water-3Mol/L), ethanol
(180ml) is mixed, standby after flowing back 10 hours.
(2) synthesis of gel：10 parts of CS silicone oil and 10 parts of ethanol are taken in stirred tank, stirring is lower to instill 60 microlitres of ammoniacal liquor, stirs
Speed 600rpm is mixed, after stirring 5 minutes, standing forms transparent alcogel.
(3) displacement of gel particle solvent and silicic acid anhydride：N-hexane 100ml is added after alcogel is crushed, stirring 4 is small
When after filter, then gel particle is placed among 100ml n-hexanes, and be slowly added to 10ml trim,ethylchlorosilanes, stirring 2 is small
When, it is filtrated to get the alkane gel particle of surface-hydrophobicized modification.
(4) drying of wet gel particle：The gel particle of surface-hydrophobicized modification is dried in blast drier, temperature control
System obtains hydrophobic aerogel powder after 80 DEG C, 120 minutes, and the thin desorption curve figure of isothermal of the aerogel powder is shown in Fig. 2, other
Parameter sees table 1.
Embodiment 3
(1) preparation of CS silicone oil：By 1 mole of tetraethyl orthosilicate, the dilute acid soln (10 of 1.3 mole of water-2Mol/L), ethanol
(180ml) is mixed, standby after flowing back 15 hours.
(2) synthesis of gel：10 parts of CS silicone oil, 12 parts of ethanol are taken in stirred tank, stirring is lower to instill 40 microlitres of ammoniacal liquor, stirring
Speed 1000rpm, after stirring 5 minutes, standing forms transparent alcogel.
(3) displacement of gel particle solvent and silicic acid anhydride：N-hexane 100ml is added after alcogel is crushed, stirring 4 is small
When after filter, then gel particle is placed among 100ml n-hexanes, and be slowly added to 12ml trim,ethylchlorosilanes, stirring 2 is small
When, it is filtrated to get the alkane gel particle of surface-hydrophobicized modification.
(4) drying of wet gel particle：The gel particle of surface-hydrophobicized modification is dried in blast drier, temperature control
System obtains hydrophobic aerogel powder after 150 DEG C, 30 minutes, and the thin desorption curve of aerogel powder isothermal see Fig. 3, other
Parameter is seen in table 1.
Embodiment 4
(1) preparation of CS silicone oil：By 1 mole of tetraethyl orthosilicate, the dilute acid soln (10 of 1.6 mole of water-5Mol/L), ethanol
(100ml) is mixed, standby after flowing back 8 hours.
(2) synthesis of gel：10 parts of CS silicone oil, 15 parts of ethanol are taken in stirred tank, stirring is lower to instill 60 microlitres of ammoniacal liquor, stirring
Speed 2000rpm, after stirring 5 minutes, standing forms alcogel.
(3) displacement of gel particle solvent and silicic acid anhydride：N-hexane 80ml is added after alcogel is crushed, stirring 4 is small
When after filter, then gel particle is placed among 80ml n-hexanes, and be slowly added to 10ml trim,ethylchlorosilanes, stirred 2 hours,
It is filtrated to get the alkane gel particle of surface-hydrophobicized modification.
(4) drying of wet gel particle：The gel particle of surface-hydrophobicized modification is dried in blast drier, temperature control
System hydrophobic aerogel powder is obtained after 150 DEG C, 30 minutes, the thin desorption curve of aerogel powder isothermal referring to Fig. 4, other
Parameter is seen in table 1.
Embodiment 5
(1) preparation of CS silicone oil：By 1 mole of tetraethyl orthosilicate, the dilute acid soln (10 of 1.0 mole of water-3Mol/L), ethanol
(180ml) is mixed, standby after flowing back 15 hours.
(2) synthesis of gel：10 parts of CS silicone oil, 10 parts of ethanol are taken in stirred tank, stirring is lower to instill 60 microlitres of ammoniacal liquor, stirring
Speed 4000rpm, after stirring 5 minutes, standing forms alcogel.
(3) displacement of gel particle solvent and silicic acid anhydride：N-hexane 100ml is added after alcogel is crushed, stirring 4 is small
When after filter, then gel particle is placed among 100ml n-hexanes, and be slowly added to 12ml HMDSs, stirring 2 is small
When, it is filtrated to get the alkane gel particle of surface-hydrophobicized modification.
(4) drying of wet gel particle：The gel particle of surface-hydrophobicized modification is dried in blast drier, temperature control
System obtains hydrophobic aerogel powder after 150 DEG C, 30 minutes, the thin desorption curve of isothermal of the aerogel powder referring to Fig. 5, its
His parameter is seen in table 1.
Embodiment 6
(1) preparation of CS silicone oil：By 1 mole of tetraethyl orthosilicate, the dilute acid soln (10 of 1.6 mole of water-3Mol/L), ethanol
(180ml) is mixed, standby after flowing back 15 hours.
(2) synthesis of gel：10 parts of CS silicone oil, 8 parts of ethanol are taken in stirred tank, stirring is lower to instill 80 microlitres of ammoniacal liquor, stirring
Speed 5000rpm, after stirring 5 minutes, standing forms alcogel.
(3) displacement of gel particle solvent and silicic acid anhydride：N-hexane 100ml is added after alcogel is crushed, stirring 4 is small
When after filter, then gel particle is placed among 100ml n-hexanes, and be slowly added to 8ml trim,ethylchlorosilanes, stirred 2 hours,
It is filtrated to get the alkane gel particle of surface-hydrophobicized modification.
(4) drying of wet gel particle：The gel particle of surface-hydrophobicized modification natural air drying in fume hood, atmospheric chamber
Temperature is placed, and obtains hydrophobic aerogel powder after 24 hours, the thin desorption curve of isothermal of the aerogel powder referring to Fig. 6, other
Parameter is seen in table 1.
The structure and performance parameters of hydrophobic aerogel powder are obtained in the embodiment 1-6 of table 1.
It should be appreciated that described above and can not parse the fixed design of the invention that is limited in the embodiment shown on drawing and think
Think.Holding identical skill in the technical field of the present invention can be improved the technical thought of the present invention with various form
Change, such improvement and change, it is thus understood that belong in protection scope of the present invention.
Claims (10)
1. a kind of method that constant pressure and dry prepares hydrophobic silica aerogel, it is characterised in that comprise the following steps：
(1) positive esters of silicon acis and water are mixed with organic solvent, and adds hydrolyst formation hybrid reaction system, in hydrolysis temperature
The lower reaction 0.1h~50h of degree, obtains poly- (oxyalkylsiloxane) with different polymerization degree, mole of the positive esters of silicon acis and water
Than for 1:0.1~1:5.0, the hydrolysis temperature is reflux temperature of the room temperature to the organic solvent；
(2) alcohol or ketone and poly- (oxyalkylsiloxane) are well mixed with base catalyst, standing forms alcohol or ketone gel, the alcohol
Or the volume ratio of ketone and poly- (oxyalkylsiloxane) is 50:1~0.01:1, the consumption of the base catalyst is solidifying in the alcohol or ketone
Within the 15% of glue cumulative volume；
(3) alcohol/ketone gel is blended to powder or graininess, then liquid alkane or fluoroalkane and alcogel is pressed 50:1~
1:100 volume ratio is mixed, and mixing speed is 10~8000rpm, and whipping temp is room temperature~alkane boiling temperature, during stirring
Between be 0.1h~100h, alcohol/ketone in the alcohol/ketone gel is displaced, so as to obtain alkane gel；
(4) mixed solution of the alkane gel and water-repelling agent and liquid alkane is mixed, mixing speed is 10~8000rpm,
Whipping temp is room temperature~alkane boiling temperature, and mixing time is 0.1h~100h, obtains hydrophobic alkane gel, the mixed solution with
The volume ratio of alkane gel is 50:1~1:100；
(5) by the hydrophobic alkane gel constant pressure and dry, the hydrophobized silica aeroge of powder shaped is obtained.
2. the method that constant pressure and dry prepares hydrophobic silica aerogel according to claim 1, it is characterised in that：Step
(1) the positive esters of silicon acis described in includes tetraethyl orthosilicate or methyl silicate,
The organic solvent includes alcohol or ketone, and the hydrolyst includes inorganic acid or organic acid.
3. the method that constant pressure and dry prepares hydrophobic silica aerogel according to claim 2, it is characterised in that：Step
(1) inorganic acid described in includes hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid, and the organic acid includes acetic acid, oxalic acid or citric acid.
4. the method that constant pressure and dry prepares hydrophobic silica aerogel according to claim 1, it is characterised in that：Step
(1) concentration of hydrolyst is 10 in hybrid reaction system described in-1Within mol/L.
5. the method that constant pressure and dry prepares hydrophobic silica aerogel according to claim 1, it is characterised in that：Step
(2) alcohol described in is less than 8 small molecular alcohol using carbon number, and the ketone is less than 8 ketone, the base catalysis using carbon number
Agent includes sodium hydroxide, potassium hydroxide, urea, ammoniacal liquor or triethylamine.
6. the method that constant pressure and dry prepares hydrophobic silica aerogel according to claim 1, it is characterised in that：Step
(3) liquid alkane described in or fluoroalkane use the liquid alkane or fluoroalkane of carbon number≤8.
7. the method that constant pressure and dry prepares hydrophobic silica aerogel according to claim 1, it is characterised in that：It is described to dredge
The volume percent content of water-repelling agent is 0.5%~50% in the mixed solution of aqua and liquid alkane.
8. the method that constant pressure and dry prepares hydrophobic silica aerogel according to claim 1, it is characterised in that：It is described to dredge
Aqua includes MTMS, trimethylmethoxysilane, dimethyldichlorosilane, trim,ethylchlorosilane or hexamethyl
Two silicon nitrogen (amine) alkane.
9. the method that constant pressure and dry prepares hydrophobic silica aerogel according to claim 1, it is characterised in that：Step
(5) mode of constant pressure and dry includes forced air drying, dries or be dried in vacuo naturally in, and drying temperature is room temperature~300 DEG C, is done
The dry time is in more than 0.1h.
10. the method that the constant pressure and dry according to any one of claim 1-9 prepares hydrophobic silica aerogel, its feature
It is：The hydrophobic silica aerogel has a nano-porous structure, and the density of the aeroge for 0.030~
0.160g/cm3, thermal conductivity is between 0.0130~0.0400W/mK, and specific surface area is in 600~1000m2Between/g, average pore size
Less than 50nm.
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| CN110339787B (en) * | 2018-04-08 | 2021-09-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Gas-solid-liquid three-phase gel, preparation method and application thereof |
| CN111005231B (en) * | 2019-11-20 | 2022-08-26 | 上海工程技术大学 | Preparation method of durable photocatalytic self-repairing super-amphiphobic ultraviolet-proof textile |
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