CN109650395A - The method that sublimed method prepares aerosil - Google Patents

The method that sublimed method prepares aerosil Download PDF

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Publication number
CN109650395A
CN109650395A CN201910151863.1A CN201910151863A CN109650395A CN 109650395 A CN109650395 A CN 109650395A CN 201910151863 A CN201910151863 A CN 201910151863A CN 109650395 A CN109650395 A CN 109650395A
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CN
China
Prior art keywords
gel
aerosil
sublimed
alcohol
sublimate
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201910151863.1A
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Chinese (zh)
Inventor
云山
陈全会
陈荣
郭探
张加栋
李彦兴
李华举
洪坤
陈静
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Huaiyin Institute of Technology
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Huaiyin Institute of Technology
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Priority to CN201910151863.1A priority Critical patent/CN109650395A/en
Publication of CN109650395A publication Critical patent/CN109650395A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/158—Purification; Drying; Dehydrating
    • C01B33/1585—Dehydration into aerogels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution

Abstract

The invention discloses a kind of methods that sublimed method prepares aerosil, comprising the following steps: (1) sublimate is dissolved in alcohol aqueous solvent and obtains clear solution；(2) silicon source and base catalyst are added in solution described in step (1) and are uniformly mixed, standing forms gel, by gel aging；(3) gel of step (2) aging is subjected to vacuum sublimation and removes sublimate, obtain aerosil.Sublimate of the present invention can take up the hole of gel, plays a part of enhancing to the network structure of gel, can reduce the contraction of gel；Preparation process does not need exchange of solvent and gel surface modifying process, saves a large amount of organic solvent and the preparation efficiency of aerosil is greatly improved.Aerosil prepared by the present invention has nano-pore structure, and pore-size distribution is 1 ~ 200 nm, and BET specific surface area is up to 300 ~ 1000 m2·g‑1, density is 0.05 ~ 0.65 gcm‑3, thermal conductivity is 0.01 ~ 0.08 Wm‑1·k‑1。

Description

The method that sublimed method prepares aerosil
Technical field
The invention belongs to nanoporous field of new material preparation, in particular to the sublimed method side for preparing aerosil Method.
Background technique
Aerosil is a kind of lightweight solid material with nanoporous network structure, has large specific surface area (300 ~ 1000 m2·g-1), low-density (3 ~ 500kgm-3), lower thermal conductivity (0.01 ~ 0.05Wm-1·K-1) etc. excellent physicals Property can be widely applied to the fields such as aerospace, petroleum pipeline, building, catalysis, sewage treatment.Aerosil Preparation is usually to prepare gel first with sol-gel method, and the solvent removed in gel pore is then dried again.For The aeroge of low-density, the method for generalling use supercritical drying are obtained, but supercritical drying equipment is expensive, maintenance cost Height causes aeroge expensive, limits the extensive use of aeroge.
For the drying cost for reducing aeroge, many reports existing at present are replaced overcritical using the method for constant pressure and dry Dry method.If China Patent Publication No. CN108423685A is using ethyl orthosilicate as silicon source, obtained by soda acid two-step catalysis To gel, exchange of solvent then is carried out to gel and surface is modified, finally carried out constant pressure and dry and obtain aerosil；In State patent publication No. CN107686117A is coagulated using the organosilicon containing organic group as presoma using sol-gel method Then gel is impregnated in organic solvent, and is modified to gel surface by glue, last constant pressure and dry obtains titanium dioxide Silica aerogel.But the atmosphere pressure desiccation for the use reported at present obtains in the step of aeroge and a large amount of solvent is needed to be handed over It changes, and hydrophobic treatment is carried out using surface of the surface modifier to gel, preparation process is cumbersome, and the period is long.
Therefore, there is still a need for a kind of easy, low in cost, easy to industrialized production method prepares silica airsetting Glue.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of sublimed methods to prepare aerosil Method is dried using the distillation of substance, to obtain the aeroge of low-density.
The present invention is achieved by the following technical solutions:
The method that sublimed method prepares aerosil, comprising the following steps:
(1) sublimate is dissolved in alcohol aqueous solvent and obtains clear solution；
(2) silicon source and base catalyst are added in solution described in step (1) and are uniformly mixed, standing forms gel, by gel Aging；
(3) gel of step (2) aging is subjected to vacuum sublimation and removes sublimate, obtain aerosil.
Further improvement of the present invention scheme are as follows:
The aging temperature of gel is 60 ~ 80 DEG C in step (2), and ageing time is 2 ~ 12 h.
Step carries out vacuum sublimation in (3) at 10 ~ 40 DEG C.
Further improvement project of the invention are as follows:
The sublimate, silicon source, alcohol, water, base catalyst molar ratio be 1:0.1 ~ 20:10 ~ 50:0.4 ~ 10:0.001 ~ 0.05。
The sublimate is one of naphthalene, benzoic acid, elemental iodine or two or more mixing.
The alcohol is one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol or two or more mixed It closes.
The silicon source is positive quanmethyl silicate, tetraethyl orthosilicate, multi-polysiloxane, methyltrimethoxysilane, methyl Triethoxysilane, ethyl trimethoxy silane, three second of ethyl triethoxysilane, vinyltrimethoxysilane or vinyl The mixing of one or more of oxysilane.
The base catalyst is one of sodium hydroxide, potassium hydroxide, urea, ammonium hydroxide, tetramethylammonium hydroxide or two Kind or more mixing.
The invention has the benefit that
(1) essence of traditional aeroge constant pressure and dry is solvent evaporation process, i.e., liquid is changed into gas, therefore in drying process In can generate huge capillary force, it is difficult to obtain the aeroge of low-density；And the present invention is totally different from existing normal pressure and does Dry, the present invention is dried using the distillation of substance, i.e., solid is changed into gas, and the capillary force of drying process subtracts significantly It is small, it is easy to get the aeroge of low-density.
(2) sublimate of the present invention can take up the hole of gel, play a part of enhancing, energy to the network structure of gel Enough reduce the contraction of gel.
(3) preparation process of the invention does not need exchange of solvent and gel surface modifying process, saves a large amount of organic molten Agent and the preparation efficiency that aerosil is greatly improved.
(4) aerosil prepared by the present invention has nano-pore structure, and pore-size distribution is 1 ~ 200 nm, BET ratio Surface area is up to 300 ~ 1000 m2·g-1, density is 0.05 ~ 0.65 gcm-3, thermal conductivity is 0.01 ~ 0.08 Wm-1·k-1。
Detailed description of the invention:
Fig. 1 is the micro-structure diagram of aerosil prepared by embodiment 1, it can be seen from the figure that silica airsetting Glue has three-dimensional manometer network porous structure.
Fig. 2 is aerosil graph of pore diameter distribution prepared by embodiment 2, and pore-size distribution is 2 ~ 80 nm.
Specific embodiment
Embodiment 1
Naphthalene is dissolved in methanol aqueous solvent and stirs to get clear solution, positive quanmethyl silicate, ammonium hydroxide are added in above-mentioned solution It stirs evenly, standing obtains gel；By gel at 60 DEG C 12 h of aging, then at 10 DEG C carry out vacuum sublimation remove gel Naphthalene in hole, obtains aerosil；Wherein naphthalene, positive quanmethyl silicate, methanol, water, ammonia molar ratio be 1:0.1: 10:0.4:0.001；
The density of the aerosil of preparation is 0.05 gcm-3, 1 ~ 200 is distributed as with nitrogen adsorption methods gaging hole diameter Nm, BET specific surface area are up to 1000 m2·g-1, it is 0.01 Wm that plane heat source method, which measures thermal conductivity,-1·k-1。
Embodiment 2
Naphthalene is dissolved in ethanol water solvent and stirs to get clear solution, tetraethyl orthosilicate, ammonium hydroxide are added in above-mentioned solution It stirs evenly, standing obtains gel；By gel at 80 DEG C 2 h of aging, then at 40 DEG C carry out vacuum sublimation remove gel Naphthalene in hole, obtains aerosil；Wherein naphthalene, positive quanmethyl silicate, ethyl alcohol, water, ammonia molar ratio be 1:20: 10:10:0.05；
The density of the aerosil of preparation is 0.65 gcm-3, 2 ~ 80 nm are distributed as with nitrogen adsorption methods gaging hole diameter, BET specific surface area is up to 300 m2·g-1, it is 0.08 Wm that plane heat source method, which measures thermal conductivity,-1·k-1。
Embodiment 3
Benzoic acid is dissolved in ethanol water solvent and stirs to get clear solution, multi-polysiloxane, urea are added to above-mentioned solution In stir evenly, standing obtain gel；By gel at 80 DEG C 4 h of aging, it is solidifying that vacuum sublimation removal is then carried out at 30 DEG C Benzoic acid in glue hole, obtains aerosil；Wherein mole of benzoic acid, multi-polysiloxane, ethyl alcohol, water, urea Than for 1:10:50:2:0.02；
The density of the aerosil of preparation is 0.15 gcm-3, 2 ~ 100 are distributed as with nitrogen adsorption methods gaging hole diameter Nm, BET specific surface area are up to 620 m2·g-1, it is 0.025 Wm that plane heat source method, which measures thermal conductivity,-1·k-1。
Embodiment 4
Iodine is dissolved in ethanol water solvent and stirs to get clear solution, multi-polysiloxane, urea are added in above-mentioned solution and stirred It mixes uniformly, standing obtains gel；By gel at 80 DEG C 4 h of aging, then at 30 DEG C carry out vacuum sublimation remove gel pore Iodine in gap, obtains aerosil；Wherein iodine, multi-polysiloxane, ethyl alcohol, water, urea molar ratio be 1:10:20: 5:0.04；
The density of the aerosil of preparation is 0.25 gcm-3, 1 ~ 150 is distributed as with nitrogen adsorption methods gaging hole diameter Nm, BET specific surface area are up to 530 m2·g-1, it is 0.035 Wm that plane heat source method, which measures thermal conductivity,-1·k-1。
Embodiment 5
Naphthalene is dissolved in isopropanol water solvent and stirs to get clear solution, by methyltriethoxysilane, tetramethylammonium hydroxide It is added in above-mentioned solution and stirs evenly, standing obtains gel；By gel at 60 DEG C 12 h of aging, then carried out at 10 DEG C Vacuum sublimation removes the naphthalene in gel pore, obtains aerosil；Wherein naphthalene, methyltriethoxysilane, isopropanol, Water, tetramethylammonium hydroxide molar ratio be 1:0.1:10:0.4:0.001；
The density of the aerosil of preparation is 0.08 gcm-3, 2 ~ 180 are distributed as with nitrogen adsorption methods gaging hole diameter Nm, BET specific surface area are up to 800 m2·g-1, it is 0.018 Wm that plane heat source method, which measures thermal conductivity,-1·k-1。

Claims (8)

1. the method that sublimed method prepares aerosil, which comprises the following steps:
(1) sublimate is dissolved in alcohol aqueous solvent and obtains clear solution；
(2) silicon source and base catalyst are added in solution described in step (1) and are uniformly mixed, standing forms gel, by gel Aging；
(3) gel of step (2) aging is subjected to vacuum sublimation and removes sublimate, obtain aerosil.
2. the method that sublimed method according to claim 1 prepares aerosil, it is characterised in that: in step (2) The aging temperature of gel is 60 ~ 80 DEG C, and ageing time is 2 ~ 12 h.
3. the method that sublimed method according to claim 1 prepares aerosil, it is characterised in that: in step (3) Vacuum sublimation is carried out at 10 ~ 40 DEG C.
4. the method that sublimed method according to claim 1 prepares aerosil, it is characterised in that: the distillation Substance, silicon source, alcohol, water, base catalyst molar ratio be 1:0.1 ~ 20:10 ~ 50:0.4 ~ 10:0.001 ~ 0.05.
5. the method that sublimed method according to claim 1 or 4 prepares aerosil, it is characterised in that: the liter Magnificent substance is one of naphthalene, benzoic acid, elemental iodine or two or more mixing.
6. the method that sublimed method according to claim 1 or 4 prepares aerosil, it is characterised in that: the alcohol For one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol or two or more mixing.
7. the method that sublimed method according to claim 1 or 4 prepares aerosil, it is characterised in that: the silicon Source is positive quanmethyl silicate, tetraethyl orthosilicate, multi-polysiloxane, methyltrimethoxysilane, methyltriethoxysilane, second One in base trimethoxy silane, ethyl triethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane Kind or two or more mixing.
8. the method that sublimed method according to claim 1 or 4 prepares aerosil, it is characterised in that: the alkali Catalyst is the mixing of one or more of sodium hydroxide, potassium hydroxide, urea, ammonium hydroxide, tetramethylammonium hydroxide.
CN201910151863.1A 2019-02-28 2019-02-28 The method that sublimed method prepares aerosil Withdrawn CN109650395A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110420667A (en) * 2019-07-19 2019-11-08 淮阴工学院 Aerogel composite and preparation method thereof for formaldehyde catalytic decomposition
CN114180582A (en) * 2021-12-27 2022-03-15 中国人民解放军海军工程大学 Hierarchical porous silica aerogel material and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101497444A (en) * 2009-03-04 2009-08-05 中国科学院广州能源研究所 Method for preparing nano polyporous material with large specific surface area by vacuum freeze-drying process
US20120152846A1 (en) * 2010-08-20 2012-06-21 Aerogel Technologies, LLC. Three-dimensional porous polyurea networks and methods of manufacture
CN102826514A (en) * 2012-09-06 2012-12-19 东南大学 Method for preparing inorganic oxide aerogel by dehydrating and drying organic solvent
CN104591301A (en) * 2015-01-12 2015-05-06 南京工业大学 Preparation method of porous nano CoFe2O4
CN109485905A (en) * 2018-11-26 2019-03-19 淮阴工学院 A kind of double cross-linked network silica-based aerogels and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101497444A (en) * 2009-03-04 2009-08-05 中国科学院广州能源研究所 Method for preparing nano polyporous material with large specific surface area by vacuum freeze-drying process
US20120152846A1 (en) * 2010-08-20 2012-06-21 Aerogel Technologies, LLC. Three-dimensional porous polyurea networks and methods of manufacture
CN102826514A (en) * 2012-09-06 2012-12-19 东南大学 Method for preparing inorganic oxide aerogel by dehydrating and drying organic solvent
CN104591301A (en) * 2015-01-12 2015-05-06 南京工业大学 Preparation method of porous nano CoFe2O4
CN109485905A (en) * 2018-11-26 2019-03-19 淮阴工学院 A kind of double cross-linked network silica-based aerogels and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110420667A (en) * 2019-07-19 2019-11-08 淮阴工学院 Aerogel composite and preparation method thereof for formaldehyde catalytic decomposition
CN114180582A (en) * 2021-12-27 2022-03-15 中国人民解放军海军工程大学 Hierarchical porous silica aerogel material and preparation method thereof
CN114180582B (en) * 2021-12-27 2023-07-21 中国人民解放军海军工程大学 Hierarchical porous silica aerogel material and preparation method thereof

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Application publication date: 20190419