CN105271260A - Method for preparing hydrophobic silica aerogel through normal-pressure drying process - Google Patents
Method for preparing hydrophobic silica aerogel through normal-pressure drying process Download PDFInfo
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- CN105271260A CN105271260A CN201410256475.7A CN201410256475A CN105271260A CN 105271260 A CN105271260 A CN 105271260A CN 201410256475 A CN201410256475 A CN 201410256475A CN 105271260 A CN105271260 A CN 105271260A
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- silica aerogel
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000004965 Silica aerogel Substances 0.000 title claims abstract description 28
- 238000001035 drying Methods 0.000 title claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 70
- 150000002576 ketones Chemical class 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000004964 aerogel Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- -1 silicate ester Chemical class 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 239000005051 trimethylchlorosilane Substances 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
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000001186 cumulative effect Effects 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
- 238000001291 vacuum drying Methods 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
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 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
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-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
- 239000011148 porous material Substances 0.000 claims description 2
- XQMTUIZTZJXUFM-UHFFFAOYSA-N tetraethoxy silicate Chemical group CCOO[Si](OOCC)(OOCC)OOCC XQMTUIZTZJXUFM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 125000003158 alcohol group Chemical group 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 44
- 239000007863 gel particle Substances 0.000 description 24
- 229920002545 silicone oil Polymers 0.000 description 17
- 230000004048 modification Effects 0.000 description 13
- 238000012986 modification Methods 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000011240 wet gel Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000000352 supercritical drying Methods 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 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
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 230000032683 aging Effects 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
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 238000001179 sorption measurement Methods 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
A disclosed method for preparing hydrophobic silica aerogel through a normal-pressure drying process comprises: (1) partially hydrolyzing an orthosilicate, so as to form a poly(alkoxysiloxane) with different polymerization degrees; (2) uniformly mixing the poly(alkoxysiloxane) with an alcohol or ketone and a base catalyst, and standing to form an alcohol or ketone gel; (3) breaking the alcohol/ketone gel through stirring, mixing with a liquid alkane or fluoroalkane with stirring, so as to displace the alcohol or ketone in the alcohol/ketone gel and obtain an alkane gel; (4) mixing the alkane gel with a mixed solution of a hydrophobic agent and a liquid alkane with stirring, so as to obtain a hydrophobic alkane gel; and (5) performing normal-pressure drying on the hydrophobic alkane gel, so as to obtain the target product. The method realizes continuous production of the hydrophobic silica aerogel without water washing and alcohol exchange operation, is short in production period, less in energy consumption, small in environment influence, energy-saving and environment-friendly, and also the obtained product possesses excellent performances such as low thermal conductivity, high specific surface area, low density and the like.
Description
Technical field
The present invention be more particularly directed to a kind of method that constant pressure and dry technology obtains hydrophobic silica aerogel powder, belong to nano-porous materials technical field.
Background technology
Aerogel is a kind of highly porous nano material, usually adopt special process that the liquid displacement in wet gel is become gas and significantly do not change gel network structure to prepare aerogel.First aerogel products is aerosil in the world, is prepared in 1931 by professor Kistler of California, USA Pacific Ocean university by agglutinating nature yeast and supercritical drying.Because aerosil has high-specific surface area (400 ~ 1500m
2/ g), high porosity (80 ~ 99.8%), low density (0.003 ~ 0.6g/cm
3) and the feature such as lower thermal conductivity (0.012 ~ 0.038W/mk), make aerosil have boundless application prospect in fields such as high temperature resistant heat insulation material, extremely-low density material, specific acoustic resistance coupling material, gas adsorption and filtering material, catalyst support material, drug carrier materials, and cause huge research interest that is academic and industrial community thus.But, the aerogel products of current excellent performance is all prepared by supercritical drying, such as CN102583407A and CN102642842B discloses the method using supercritical drying to prepare aerogel, it displaces the solvent in wet gel by supercutical fluid, can be good at keeping the original structure of gel after final drying.Usual supercritical drying needs to use special equipment, operates under high pressure-temperature, and make apparatus expensive, operational difficulty on the one hand, cost is high; There is great potential safety hazard on the other hand.Therefore aerogel products and being applied in domesticly is not popularized.
In order to reduce the production cost of aerogel, improve security, CN103073008A, CN101691227B and CN103043673A disclose the method using constant pressure and dry to prepare aerogel, comprise: by repeatedly exchanging with multi-solvents the solvent fluid exchange in gel duct being become low surface tension, as normal hexane etc., again by the surface in duct by hydrophilically modified be hydrophobicity, substantially reduce the capillary force in gel duct, thus the contraction of gel is very little in the process of drying, substantially original form can be kept.Because constant pressure and dry needs gel duct exchange of solvent repeatedly and surface-hydrophobicized process, preparation cycle is long, complex operation, is difficult to realize industrialization production.Document 1 (Solidstatesciences2008,10:1113-1116) with document 2 (Powdertechnology2010,197:288-294) report serialization, in enormous quantities normal pressure respectively and prepare the method for silicon dioxide aerogel powder, because document all adopts relatively inexpensive water glass to be silicon source, need in preparation process to remove sodium ion by ion exchange method or massive laundering method, and multiple step such as alcohol displacement, alkane displacement, hydrophobically modified, preparation cycle is long, complex operation, the impact caused environment is also larger.
Summary of the invention
The object of the invention is to propose that a kind of technique is simple, with short production cycle, cost is low, and the constant pressure and dry only needing simple device to implement prepares the method for hydrophobic silica aerogel, thus overcome defect of the prior art.
For achieving the above object, present invention employs following technical scheme:
Constant pressure and dry prepares a method for hydrophobic silica aerogel, comprises the steps:
(1) positive silicate ester portion is hydrolyzed, is formed poly-(oxyalkylsiloxane) with different polymerization degree;
(2) described poly-(oxyalkylsiloxane) and alcohol or ketone, alkaline catalysts are mixed, leave standstill formation alcohol or ketone gel;
(3) described alcohol/ketone gel is blended to powder or particulate state, with liquid alkane or fluoroalkane mix and blend, thus displace the alcohol/ketone in described alcohol/ketone gel, obtain alkane gel;
(4) by the mixing solutions mix and blend of described alkane gel and hydrophobizing agent and liquid alkane, hydrophobic alkane gel is obtained;
(5) by described hydrophobic alkane gel constant pressure and dry, the hydrophobized silica aerogel of powder shaped is obtained.
Among a comparatively preferred embodiment, step (1) can comprise: be that positive silicon ester and the water of 1:0.1 ~ 1:5.0 mixes with organic solvent by mol ratio, and add hydrolyst formation hybrid reaction system, under hydrolysis temperature, react more than 0.1h, obtain described poly-(oxyalkylsiloxane).
Further, described positive silicon ester can be selected but be not limited to tetraethoxy or methyl silicate.
Further, described organic solvent can be selected but be not limited to alcohol or ketone.
Further, described hydrolyst comprises mineral acid or organic acid.
Further, described hydrolysis temperature is the reflux temperature of room temperature to described organic solvent.
Preferably, in hybrid reaction system described in step (1) concentration of hydrolyst 10
-1within mol/L.
Among a comparatively preferred embodiment, step (2) can comprise:
Volume ratio is mixed with alkaline catalysts at the alcohol of 50:1 ~ 0.01:1 or ketone and poly-(oxyalkylsiloxane), leaves standstill formation alcohol or ketone gel;
Further, described alcohol preferably adopts carbonatoms to be less than the small molecular alcohol of 8.
Further, described ketone preferably adopts carbonatoms to be less than the ketone of 8.
Preferably, the consumption of alkaline catalysts described in step (2) is within 15% of described alcohol or ketone gel cumulative volume.
Among a comparatively preferred embodiment, step (3) comprising: liquid alkane or fluoroalkane and alcogel mixed by the volume ratio of 50:1 ~ 1:100 and stir, wherein stirring velocity is 10 ~ 8000rpm, whipping temp is room temperature ~ alkane boiling temperature, churning time is more than 0.1h, thus the alcohol/ketone displaced in described alcohol/ketone gel, obtain alkane gel.
Further, described liquid alkane or fluoroalkane preferably adopt liquid alkane or the fluoroalkane of carbonatoms≤8.
Among a comparatively preferred embodiment, step (4) comprising: be the hydrophobizing agent of 50:1 ~ 1:100 and the mixing solutions of liquid alkane and alkane gel mix and blend by volume ratio, stirring velocity is 10 ~ 8000rpm, whipping temp is room temperature ~ alkane boiling temperature, churning time is more than 0.1h, obtains described hydrophobic alkane gel.
Further, in the mixing solutions of described hydrophobizing agent and liquid alkane, the volume percent content of hydrophobizing agent is preferably 0.5% ~ 50%.
Among a comparatively preferred embodiment, in step (5), the mode of constant pressure and dry comprises forced air drying, naturally dries or vacuum-drying, and drying temperature is room temperature ~ 300 DEG C, and time of drying is at more than 0.1h.
Compared with prior art, positively effect of the present invention comprises: (1) eliminates water displacement, and the alcohol displacement needed for existing atmosphere pressure desiccation, substantially reduces preparation cycle, has saved resource; (2) because not needing alcohol to replace, also can avoid a large amount of uses of alcohol, reduce further cost, and reduce the impact on environment; (3) product that obtains has the excellent properties such as lower thermal conductivity, high-specific surface area, low density.
Accompanying drawing explanation
Fig. 1 is by being obtained hydrophobic aerogel isothermal nitrogen adsorption desorption graphic representation in the embodiment of the present invention 1.
Fig. 2 is by being obtained hydrophobic aerogel isothermal nitrogen adsorption desorption graphic representation in the embodiment of the present invention 2.
Fig. 3 is by being obtained hydrophobic aerogel isothermal nitrogen adsorption desorption graphic representation in the embodiment of the present invention 3.
Fig. 4 is by being obtained hydrophobic aerogel isothermal nitrogen adsorption desorption graphic representation in the embodiment of the present invention 4.
Fig. 5 is by being obtained hydrophobic aerogel isothermal nitrogen adsorption desorption graphic representation in the embodiment of the present invention 5.
Fig. 6 is by being obtained hydrophobic aerogel isothermal nitrogen adsorption desorption graphic representation 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 putting into practice in a large number, propose technical scheme of the present invention, it is mainly using poly-(oxyalkylsiloxane) of positive silicon ester various polymerization degree for raw material is prepared into as silicon source, again by silicon source, alcohol/ketone and alkaline catalysts are mixed, after leaving standstill gel, wet gel is blended, and with the liquid alkane of low surface tension or fluoroalkane displacement, and use hydrophobizing agent modification, drier acquisition hydrophobic silica aerogel powder.
By technical scheme of the present invention, the continuous prodution of hydrophobic silica aerogel can be realized, avoid the steps such as washing, alcohol exchange, with short production cycle, energy consumption is few, little to environmental influence, and the hydrophobic silica aerogel that obtains has nano-porous structure, and density is 0.030 ~ 0.160g/cm
3, thermal conductivity is between 0.0130 ~ 0.0400W/mK, and specific surface area is at 600 ~ 1000m
2between/g, mean pore size is less than 50nm.
As follows more specifically explanation is explained to technical scheme of the present invention.
The method that a kind of constant pressure and dry of the present invention prepares hydrophobic silica aerogel mainly comprises:
(1) positive silicate ester portion is hydrolyzed into poly-(oxyalkylsiloxane) (also can referred to as CS silicone oil) of the multiple polymerization degree, for subsequent use as self-control silicon source;
(2) described CS silicone oil, alcohol or ketone, alkaline catalysts are mixed, leave standstill and form alcohol or ketone gel;
(3) obtained alcohol/ketone gel is blended to powder or particulate state, then by this gel and liquid alkane or fluoroalkane mix and blend, displace the alcohol/ketone in gel, finally adopt and to filter or the mode such as centrifugal obtains alkane gel;
(4) by obtained alkane gel and containing the hydrophobizing agent of certain volume mark and the mixing solutions mix and blend of liquid alkane, the modes such as filtration are then adopted by reactant to be separated to obtain hydrophobic alkane gel;
(5) by obtained hydrophobic alkane gel constant pressure and dry, hydrophobized silica aerogel powder is obtained.
Wherein, among one comparatively specific embodiment, the method that this constant pressure and dry prepares hydrophobic silica aerogel can comprise:
(1) by positive silicon ester, hydrolyst, alcohol or ketone (such as acetone) mixing and stirring, backflow for some time, such as 8-20 hour, form the CS silicone oil of the various polymerization degree, store for future use, its quality guaranteed period is more than 1 year;
(2) described silicone oil, alcohol or ketone, alkaline catalysts are mixed, leave standstill and form gel, in room temperature to reflux temperature (such as 60 DEG C) aging for some time of alcohol or ketone, such as 1 ~ 5 hour;
(3) by obtained alcohol or ketone gel mechanical disintegration, and with liquid alkane or fluoroalkane mix and blend, be then alkane gel and liquid alkane or fluoroalkane by obtained gel-alkane pulp separation;
(4) by the mixing solutions of obtained alkane gel and hydrophobizing agent and liquid alkane at room temperature or heated and stirred, subsequently obtained gel mixture is separated into hydrophobic alkane gel, alkane and hydrophobic reactant thing;
(5) by obtained hydrophobic alkane gel constant pressure and dry, hydrophobized silica aerogel is obtained.
Among a better embodiment, the silicon ester adopted in step (1) is preferably tetraethoxy or methyl esters etc., and the mol ratio of itself and water arranges and preferably controls at 1:0.1 ~ 1:5.0; Solvent for use can be alcohol or ketone (such as acetone), and it is 0.1:1 ~ 1:0.1 that consumption preferably controls in the volume ratio with positive silicon ester; Described hydrolyst comprises the organic acid such as the mineral acids such as dilute hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or acetic acid, oxalic acid, citric acid, and its concentration in hydrolysis reaction system preferably controls 10
-1within mol/L; And hydrolysis temperature is preferably the reflux temperature of room temperature to solvent for use; Hydrolysis time is preferably at 0.1-50 hour.
Among a better embodiment, in step (2), alcohol used comprises methyl alcohol, ethanol, propyl alcohol, the trimethyl carbinol, propyl carbinol or other alcohol (preferably, in alcohol molecule, carbonatoms is not more than 8), ketone used is that acetone, butanone or other ketone solvent are (preferred, in ketone molecule, carbonatoms is not more than 8), consumption and CS silicone oil volume ratio are between 50:1 ~ 0.01:1; Wherein alkaline catalysts used comprises sodium hydroxide, potassium hydroxide, urea, ammoniacal liquor, triethylamine etc., and consumption is preferably within 15% of gel cumulative volume.
Among a better embodiment, broken or mechanical stirring crumbling method manually in step (3), can be adopted to blend described alcohol/ketone gel to powder or particulate state.
Among a better embodiment, step (3) can also comprise: to be mixed with alcogel by liquid alkane by the volume ratio of 50:1 ~ 1:100 and stir, stirring velocity is 10 ~ 8000rpm, whipping temp is room temperature ~ alkane boiling temperature, churning time is 0.1 ~ 100 hour, wherein said alkane comprises various liquid alkane or fluoroalkane, and especially preferably carbonatoms is not more than liquid alkane or the fluoroalkane of 8.
Among a better embodiment, step (4) can comprise: the liquid alkane-hydrophobizing agent mixed solution and the alkane gel mix and blend that by volume ratio are 50:1 ~ 1:100, stirring velocity is 10 ~ 8000rpm, and whipping temp is room temperature ~ alkane boiling temperature, and churning time is 0.1 ~ 100 hour.
Further, the volume percent content of hydrophobizing agent described in step (4) in the mixing solutions of hydrophobizing agent and liquid alkane is 0.5% ~ 50%.
Wherein, described hydrophobizing agent can be selected but be not limited to methyltrimethoxy silane, trimethylmethoxysilane, dimethyldichlorosilane(DMCS), trimethylchlorosilane or hexamethyl two silicon nitrogen (amine) alkane etc.
Among a better embodiment, constant pressure and dry mode in step (5) can be selected but be not limited to forced air drying, naturally dries or vacuum-drying etc., and drying temperature is preferably room temperature ~ 300 DEG C, time of drying is preferably more than 0.1h, and particularly 0.01 is little of 300 hours.
Below in conjunction with the technical solution of the present invention is further explained the explanation of some preferred embodiments and accompanying drawing.
Embodiment 1
(1) preparation of CS silicone oil: by the dilute acid soln (concentration 10 of 1 mole of tetraethoxy, 0.8 mole of water
-4mol/L), ethanol (160ml) mixing, reflux for subsequent use after 16 hours.
(2) synthesis of gel: get 10 parts of CS silicone oil and 12 parts of ethanol in stirring tank, stirs lower instillation 50 microlitre ammoniacal liquor, stirring velocity 50rpm, stirs after 5 minutes and leaves standstill formation water white transparency alcogel.
(3) gel particle solvent exchange and hydrophobization process: add normal hexane 60ml after being pulverized by alcogel, stir after 4 hours and filter, again gel particle is placed in the middle of 60ml normal hexane, and slowly add 10ml trimethylchlorosilane, stir 2 hours, filter the alkane gel particle obtaining surface-hydrophobicized modification.
(4) drying of wet gel particle: the gel particle of surface-hydrophobicized modification is dry in blast drier, temperature controls at 100 DEG C, obtain hydrophobic aerogel powder after 60 minutes, the thin desorption curve figure of isothermal of this aerogel powder can consult Fig. 1, and other parameters see table 1.
Embodiment 2
(1) preparation of CS silicone oil: by the dilute acid soln (10 of 1 mole of methyl silicate, 1.3 mole of water
-3mol/L), ethanol (180ml) mixing, reflux for subsequent use after 10 hours.
(2) synthesis of gel: get 10 parts of CS silicone oil and 10 parts of ethanol in stirring tank, stir lower instillation 60 microlitre ammoniacal liquor, stirring velocity 600rpm, stirred after 5 minutes, left standstill the transparent alcogel of formation.
(3) gel particle solvent exchange and hydrophobization process: add normal hexane 100ml after being pulverized by alcogel, stir after 4 hours and filter, again gel particle is placed in the middle of 100ml normal hexane, and slowly add 10ml trimethylchlorosilane, stir 2 hours, filter the alkane gel particle obtaining surface-hydrophobicized modification.
(4) drying of wet gel particle: the gel particle of surface-hydrophobicized modification is dry in blast drier, temperature controls at 80 DEG C, obtain hydrophobic aerogel powder after 120 minutes, the thin desorption curve figure of isothermal of this aerogel powder is shown in Fig. 2, and other parameters see table 1.
Embodiment 3
(1) preparation of CS silicone oil: by the dilute acid soln (10 of 1 mole of tetraethoxy, 1.3 mole of water
-2mol/L), ethanol (180ml) mixing, reflux for subsequent use after 15 hours.
(2) synthesis of gel: get 10 parts of CS silicone oil, 12 parts of ethanol in stirring tank, stir lower instillation 40 microlitre ammoniacal liquor, stirring velocity 1000rpm, stirred after 5 minutes, left standstill and formed transparent alcogel.
(3) gel particle solvent exchange and hydrophobization process: add normal hexane 100ml after being pulverized by alcogel, stir after 4 hours and filter, again gel particle is placed in the middle of 100ml normal hexane, and slowly add 12ml trimethylchlorosilane, stir 2 hours, filter the alkane gel particle obtaining surface-hydrophobicized modification.
(4) drying of wet gel particle: the gel particle of surface-hydrophobicized modification is dry in blast drier, temperature controls at 150 DEG C, obtain hydrophobic aerogel powder after 30 minutes, the thin desorption curve of this aerogel powder isothermal can consult Fig. 3, and other parameters see in table 1.
Embodiment 4
(1) preparation of CS silicone oil: by the dilute acid soln (10 of 1 mole of tetraethoxy, 1.6 mole of water
-5mol/L), ethanol (100ml) mixing, reflux for subsequent use after 8 hours.
(2) synthesis of gel: get 10 parts of CS silicone oil, 15 parts of ethanol in stirring tank, stir lower instillation 60 microlitre ammoniacal liquor, stirring velocity 2000rpm, stirred after 5 minutes, left standstill and formed alcogel.
(3) gel particle solvent exchange and hydrophobization process: add normal hexane 80ml after being pulverized by alcogel, stir after 4 hours and filter, again gel particle is placed in the middle of 80ml normal hexane, and slowly add 10ml trimethylchlorosilane, stir 2 hours, filter the alkane gel particle obtaining surface-hydrophobicized modification.
(4) drying of wet gel particle: the gel particle of surface-hydrophobicized modification is dry in blast drier, temperature controls at 150 DEG C, obtain hydrophobic aerogel powder after 30 minutes, the thin desorption curve of this aerogel powder isothermal refers to Fig. 4, and other parameters see in table 1.
Embodiment 5
(1) preparation of CS silicone oil: by the dilute acid soln (10 of 1 mole of tetraethoxy, 1.0 mole of water
-3mol/L), ethanol (180ml) mixing, reflux for subsequent use after 15 hours.
(2) synthesis of gel: get 10 parts of CS silicone oil, 10 parts of ethanol in stirring tank, stir lower instillation 60 microlitre ammoniacal liquor, stirring velocity 4000rpm, stirred after 5 minutes, left standstill and formed alcogel.
(3) gel particle solvent exchange and hydrophobization process: add normal hexane 100ml after being pulverized by alcogel, stir after 4 hours and filter, again gel particle is placed in the middle of 100ml normal hexane, and slowly add 12ml hexamethyldisilazane, stir 2 hours, filter the alkane gel particle obtaining surface-hydrophobicized modification.
(4) drying of wet gel particle: the gel particle of surface-hydrophobicized modification is dry in blast drier, temperature controls at 150 DEG C, obtain hydrophobic aerogel powder after 30 minutes, the thin desorption curve of isothermal of this aerogel powder refers to Fig. 5, and other parameters see in table 1.
Embodiment 6
(1) preparation of CS silicone oil: by the dilute acid soln (10 of 1 mole of tetraethoxy, 1.6 mole of water
-3mol/L), ethanol (180ml) mixing, reflux for subsequent use after 15 hours.
(2) synthesis of gel: get 10 parts of CS silicone oil, 8 parts of ethanol in stirring tank, stir lower instillation 80 microlitre ammoniacal liquor, stirring velocity 5000rpm, stirred after 5 minutes, left standstill and formed alcogel.
(3) gel particle solvent exchange and hydrophobization process: add normal hexane 100ml after being pulverized by alcogel, stir after 4 hours and filter, again gel particle is placed in the middle of 100ml normal hexane, and slowly add 8ml trimethylchlorosilane, stir 2 hours, filter the alkane gel particle obtaining surface-hydrophobicized modification.
(4) drying of wet gel particle: gel particle natural air drying in stink cupboard of surface-hydrophobicized modification, atmospheric pressure at room is placed, obtain hydrophobic aerogel powder after 24 hours, the thin desorption curve of isothermal of this aerogel powder refers to Fig. 6, and other parameters see in table 1.
In table 1. embodiment 1-6 obtain the structure and performance parameters of hydrophobic aerogel powder
Should be appreciated that above explanation and on drawing shown in embodiment can not resolve the design philosophy surely of the present invention that is limited.Hold in technical field of the present invention identical know the knowledgeable can by technical thought of the present invention with various form improvement change, such improvement and change, be interpreted as belonging in protection scope of the present invention.
Claims (11)
1. constant pressure and dry prepares a method for hydrophobic silica aerogel, it is characterized in that comprising the steps:
(1) positive silicate ester portion is hydrolyzed, is formed poly-(oxyalkylsiloxane) with different polymerization degree;
(2) described poly-(oxyalkylsiloxane) and alcohol or ketone, alkaline catalysts are mixed, leave standstill formation alcohol or ketone gel;
(3) described alcohol/ketone gel is blended to powder or particulate state, with liquid alkane or fluoroalkane mix and blend, displace the alcohol/ketone in described alcohol/ketone gel, thus obtain alkane gel;
(4) by the mixing solutions mix and blend of described alkane gel and hydrophobizing agent and liquid alkane, hydrophobic alkane gel is obtained;
(5) by described hydrophobic alkane gel constant pressure and dry, the hydrophobized silica aerogel of powder shaped is obtained.
2. constant pressure and dry prepares the method for hydrophobic silica aerogel according to claim 1, it is characterized in that step (1) comprising: be that positive silicon ester and the water of 1:0.1 ~ 1:5.0 mixes with organic solvent by mol ratio, and add hydrolyst formation hybrid reaction system, under hydrolysis temperature, react more than 0.1h, obtain described poly-(oxyalkylsiloxane);
Wherein, described positive silicon ester comprises tetraethoxy or methyl silicate,
Described organic solvent comprises alcohol or ketone,
Described hydrolyst comprises mineral acid or organic acid, and described mineral acid comprises hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid, and described organic acid comprises acetic acid, oxalic acid or citric acid,
Described hydrolysis temperature is the reflux temperature of room temperature to described organic solvent.
3. according to claim 1 or 2, constant pressure and dry prepares the method for hydrophobic silica aerogel, it is characterized in that the concentration of hydrolyst in hybrid reaction system described in step (1) is 10
-1within mol/L.
4. constant pressure and dry prepares the method for hydrophobic silica aerogel according to claim 1, it is characterized in that step (2) comprising:
Volume ratio is mixed with alkaline catalysts at the alcohol of 50:1 ~ 0.01:1 or ketone and poly-(oxyalkylsiloxane), leaves standstill formation alcohol or ketone gel;
Wherein, described alcohol adopts carbonatoms to be less than the small molecular alcohol of 8,
Described ketone adopts carbonatoms to be less than the ketone of 8,
Described alkaline catalysts comprises sodium hydroxide, potassium hydroxide, urea, ammoniacal liquor or triethylamine.
5. according to claim 1 or 4, constant pressure and dry prepares the method for hydrophobic silica aerogel, it is characterized in that the consumption of alkaline catalysts described in step (2) is within 15% of described alcohol or ketone gel cumulative volume.
6. constant pressure and dry prepares the method for hydrophobic silica aerogel according to claim 1, it is characterized in that step (3) comprising: liquid alkane or fluoroalkane and alcogel mixed by the volume ratio of 50:1 ~ 1:100 and stir, wherein stirring velocity is 10 ~ 8000rpm, whipping temp is room temperature ~ alkane boiling temperature, churning time is more than 0.1h, thus the alcohol/ketone displaced in described alcohol/ketone gel, obtain alkane gel;
Described liquid alkane or fluoroalkane adopt liquid alkane or the fluoroalkane of carbonatoms≤8.
7. constant pressure and dry prepares the method for hydrophobic silica aerogel according to claim 1, it is characterized in that step (4) comprising: be the hydrophobizing agent of 50:1 ~ 1:100 and the mixing solutions of liquid alkane and alkane gel mix and blend by volume ratio, stirring velocity is 10 ~ 8000rpm, whipping temp is room temperature ~ alkane boiling temperature, churning time is more than 0.1h, obtains described hydrophobic alkane gel.
8. according to claim 1 or 7, constant pressure and dry prepares the method for hydrophobic silica aerogel, it is characterized in that the volume percent content of hydrophobizing agent in the mixing solutions of described hydrophobizing agent and liquid alkane is 0.5% ~ 50%.
9. according to claim 1 or 7, constant pressure and dry prepares the method for hydrophobic silica aerogel, it is characterized in that described hydrophobizing agent comprises methyltrimethoxy silane, trimethylmethoxysilane, dimethyldichlorosilane(DMCS), trimethylchlorosilane or hexamethyl two silicon nitrogen (amine) alkane.
10. constant pressure and dry prepares the method for hydrophobic silica aerogel according to claim 1, it is characterized in that the mode of constant pressure and dry in step (5) comprises forced air drying, naturally dries or vacuum-drying, drying temperature is room temperature ~ 300 DEG C, and time of drying is at more than 0.1h.
11. according to any one of claim 1-10 constant pressure and dry prepare the method for hydrophobic silica aerogel, it is characterized in that described hydrophobic silica aerogel has nano-porous structure, and the density of described aerogel is 0.030 ~ 0.160g/cm
3, thermal conductivity is between 0.0130 ~ 0.0400W/mK, and specific surface area is at 600 ~ 1000m
2between/g, mean pore size is less than 50nm.
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| CN111005231A (en) * | 2019-11-20 | 2020-04-14 | 上海工程技术大学 | Preparation method of durable photocatalytic self-repairing super-amphiphobic ultraviolet-proof textile |
| 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 |
| CN117680059A (en) * | 2023-12-21 | 2024-03-12 | 浙江岩谷科技有限公司 | Method for continuously preparing hydrophobic aerogel powder by double-fluid atomization |
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