CN101863480A - Preparation method for silicon dioxide aerogel - Google Patents
Preparation method for silicon dioxide aerogel Download PDFInfo
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- CN101863480A CN101863480A CN 201010217687 CN201010217687A CN101863480A CN 101863480 A CN101863480 A CN 101863480A CN 201010217687 CN201010217687 CN 201010217687 CN 201010217687 A CN201010217687 A CN 201010217687A CN 101863480 A CN101863480 A CN 101863480A
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Abstract
The invention relates to a preparation method for silicon dioxide aerogel. The method includes the following steps: (1) under the acidic condition that pH is equal to 3 to 5, stirring silicon tetrachloride and water for reaction, then adding ammonia water to regulate pH to 8 to 10, adding water and ethanol, and after hydrolytic polycondensation reaction, forming alcogel; (2) carrying out extraction, and removing water/alcohol mixture contained in the alcogel; taking gel solution, adding anhydrous methanol or ethanol, and replacing the water/alcohol mixture in gel pores with the anhydrous methanol or ethanol; (3) adding trimethyl chlorosilane and alkane to alkylate Si-OH on the surface of the gel skeleton, and after drying under the normal pressure, the SiO2 aerogel is produced. The invention has the following advantages that: (1) since the silicon tetrachloride as byproduct produced in a large amount by the organosilicon industry is used as raw material, the material cost in the process of production is greatly reduced; (2) compared with the conventional supercritical drying, the adopted normal-temperature drying can greatly reduce conditions needed by reaction; and (3) the invention cannot destroy the nanopore structure of the SiO2 aerogel, and can stably increase the reaction speed at the same time.
Description
Technical field
The present invention relates to a kind of preparation method of aerosil, specifically a kind of with silicon tetrachloride as starting raw material, with organic solvent with the Si-OH alkylation of gel skeleton surface, thereby carry out the method that drying prepares aerosil then.
Background technology
Aerosil has characteristics such as density is low, specific surface area is big, porosity height, is a kind of novel light nano-porous materials with bright prospects.Give full play to the excellent properties of aerogel, realize the cost degradation of raw material and preparation technology's simple and safe and cost degradation, making it can scale operation be the focus of studying at present.
In recent years, the research of silica aerogel mainly concentrates on German BASF, BESY company, the Los Alamos National Laboratories of the U.S., inferior National Laboratory of Lao Lunsili thing mole National Laboratory and mulberry ground, the investigation of materials center, Montpelier of France, the university of states such as Sweden LUND company and U.S., moral, day.At home, the research of silica aerogel starts from nineteen ninety-five Tongji University's ripple ear solid-state physics institute the earliest, it has taken the lead in setting up one and has overlapped the equipment of aerogel preparation and SOME PROPERTIES measurement, and and the German systematic study of tieing up Wurz fort College Physics institute cooperation development aerogel material.Colleges and universities such as University of Science ﹠ Technology, Beijing, Shanxi coalification institute of the Chinese Academy of Sciences also delivered relevant paper with scientific research institution in addition.But the research to silica aerogel is in the starting stage mostly, and also not having to form with the exploitation novel material is the action oriented research of purpose.
Also have difficult point restricting the scale operation and the application of product at present on the technology of preparing of this product.1. it is big to adopt supercritical drying to prepare the investment of silica aerogel needs, cost height, high-tension apparatus operational hazards.2. can run into the draw problem when adopting constant pressure and dry.Though handle and to address this problem by adopting means such as exchange of solvent/surface modification, when but constant pressure and dry technology is used for the scale operation aerogel, how stably to improve speed of response, the perviousness of accelerating modification liquid also needs further exploration.Number of patent application is that 200580015564 patent of invention adopts these class methods exactly.It is that tensio-active agent is dissolved in acidic aqueous solution, to wherein being added on the silicon compound that has water-disintegrable functional group and hydrophobic functional groups in the molecule reaction that is hydrolyzed, behind the gel solidification that generates, make described gel supercritical drying, can obtain the controlled aerosil of micro-pore diameter and micro-pore diameter distribution.Described tensio-active agent preferably uses any among nonionic surfactant, cationic surfactant and the anionic surfactant, perhaps mixes two or more uses.This method can't overcome above-mentioned defective.
Be different from traditional preparation method, the present invention adopts the starting material of polysilicon industry waste product silicon tetrachloride as silica aerogel.Not only solve the high murder by poisoning of high pollution byproduct emission problem in the polysilicon industry, and be translated into the functional novel material that fields such as can being widely used in optics, acoustics, mechanics, electricity has high added value.
Summary of the invention
Purpose of the present invention is exactly the defective at prior art, and a kind of preparation method of aerosil is provided, and it has solved SiO
2Draw and problem of slow response appear in aerogel easily when dry.
Preparation process of the present invention is as follows:
(1), under the acidic conditions of pH=3-5, add silicon tetrachloride and water stirring reaction, regulate pH=8-10 with ammoniacal liquor then, add entry and ethanol again, the polycondensation that is hydrolyzed forms alcogel;
(2), then the extraction, remove moisture/pure mixed solution in the alcogel; Get its coagulant liquid, add anhydrous methanol or ethanol, the water in the gel pore/pure mixed solution is replaced with anhydrous methanol or ethanol;
(3), again add trimethylchlorosilane and alkane with the Si-OH alkylation of gel skeleton surface, carry out constant pressure and dry then and make SiO
2Aerogel.
In the time of drying, gel shrinks accordingly, since the Si-OH on gel skeleton surface alkyl turn to stable Si-R; When gel drying its volume after the stagnation point slowly is returned to again near its original size, this phenomenon is called " rebound effect ".The present invention can be so that the reversible contraction that the gel after modifying can bear original volume 28%.
The invention has the advantages that: be starting material one,, greatly reduce the raw materials cost in the production process with a large amount of silicon tetrachloride as by-product of organosilicon industry production.Two, the used constant pressure and dry of the present invention and traditional supercritical drying contrast have also reduced the required condition of reaction greatly.Three, the present invention can not destroy SiO
2The aerogel nano-pore structure can stably improve speed of response simultaneously.
Embodiment
EXAMPLE l
To have and add silicon tetrachloride 50ml in the 500ml there-necked flask of agitator, water 100ml is adjusted to 3 with dilute hydrochloric acid with pH value, stirs, and reacts 1h; Add ammoniacal liquor then the pH value is adjusted to 8, add 150ml water and 50ml ethanol, stir and form gel, moisture/pure mixed solution is removed in extraction then, gets its coagulant liquid, add dehydrated alcohol 100ml, add trimethylchlorosilane 100ml, heptane 100ml, soaked 3 hours.Put into test tube, the foil sealing with the band pin hole is good then, puts into baking oven and carries out constant pressure and dry and make SiO
2Aerogel.
Embodiment 2
To have and add silicon tetrachloride 50ml in the 500ml there-necked flask of agitator, water 100ml is adjusted to 4 with dilute hydrochloric acid with pH value, stirs, and reacts 1h; Add ammoniacal liquor then the pH value is adjusted to 9, add 150ml water and 50ml ethanol, stir and form gel, moisture/pure mixed solution is removed in extraction then, gets its coagulant liquid, add anhydrous methanol 100ml, add trimethylchlorosilane 80ml, normal hexane 100ml, soaked 3 hours.Put into test tube, the foil sealing with the band pin hole is good then, puts into baking oven and carries out constant pressure and dry and make SiO
2Aerogel.
Embodiment 3
To have and add silicon tetrachloride 50ml in the 500ml there-necked flask of agitator, water 100ml is adjusted to 5 with dilute hydrochloric acid with pH value, stirs, and reacts 1h; Add ammoniacal liquor then the pH value is adjusted to 10, add 150ml water and 50ml ethanol, stir and form gel, moisture/pure mixed solution is removed in extraction then, gets its coagulant liquid, add dehydrated alcohol 100ml, add trimethylchlorosilane 50ml, heptane 80ml, soaked 3 hours.Put into test tube, the foil sealing with the band pin hole is good then, puts into baking oven and carries out constant pressure and dry and make SiO
2Aerogel.
Claims (5)
1. the preparation method of an aerosil, it may further comprise the steps:
(1), under the acidic conditions of pH=3-5, add silicon tetrachloride and water stirring reaction, regulate pH=8-10 with ammoniacal liquor then, add entry and ethanol again, the polycondensation that is hydrolyzed forms alcogel;
(2), then the extraction, remove moisture/pure mixed solution in the alcogel; Get its coagulant liquid, add anhydrous methanol or ethanol, the water in the gel pore/pure mixed solution is replaced with anhydrous methanol or ethanol;
(3), again add trimethylchlorosilane and alkane with the Si-OH alkylation of gel skeleton surface, carry out constant pressure and dry then and make SiO
2Aerogel.
2. the preparation method of a kind of aerosil according to claim 1, wherein: described alkane is heptane or normal hexane.
3. the preparation method of a kind of aerosil according to claim 1, wherein: the mol ratio that adds silicon tetrachloride and water under acidic conditions is 1: 2.
4. the preparation method of a kind of aerosil according to claim 1, wherein: when adding entry and ethanol under the alkaline condition, water: ethanol: the mol ratio of silicon tetrachloride is 3: 1: 1.
5. the preparation method of a kind of aerosil according to claim 1, wherein: the solvent for use consumption is anhydrous methanol or ethanol: trimethylchlorosilane: the volume ratio of alkane is 1--1.5: 1--1.5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2010102176876A CN101863480B (en) | 2010-06-25 | 2010-06-25 | Preparation method for silicon dioxide aerogel |
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| CN2010102176876A CN101863480B (en) | 2010-06-25 | 2010-06-25 | Preparation method for silicon dioxide aerogel |
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| CN101863480A true CN101863480A (en) | 2010-10-20 |
| CN101863480B CN101863480B (en) | 2012-02-29 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102897775A (en) * | 2011-07-25 | 2013-01-30 | 中国石油天然气股份有限公司 | Preparation method for high purity macroporous silica gel |
| CN103387417A (en) * | 2013-07-30 | 2013-11-13 | 湖北三江航天江北机械工程有限公司 | Dampproof method for porous ceramic material containing silicon hydroxyl |
| CN104760964A (en) * | 2015-04-29 | 2015-07-08 | 江西安德力高新科技有限公司 | Silicon dioxide aerogel preparation method |
| CN105051118A (en) * | 2013-02-05 | 2015-11-11 | 巴斯夫欧洲公司 | Method for producing porous or fine-particle solid inorganic materials |
| CN105031960A (en) * | 2015-08-19 | 2015-11-11 | 江西安德力高新科技有限公司 | Device and process for utilization of waste heat in aerogel production by adopting alcohol supercritical method |
| CN105236414A (en) * | 2015-09-21 | 2016-01-13 | 太仓市金锚新材料科技有限公司 | Silicon tetrachloride recycling method |
| CN106477589A (en) * | 2016-11-30 | 2017-03-08 | 四川微松新材料有限公司 | A kind of preparation method of the aerosil nothing discharging of waste liquid and system |
| CN107804852A (en) * | 2016-09-08 | 2018-03-16 | 新特能源股份有限公司 | Prepare the method and system of aerosil |
| CN115010140A (en) * | 2022-07-20 | 2022-09-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of super-hydrophobic silica aerogel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6017505A (en) * | 1995-10-14 | 2000-01-25 | Basf Aktiengesellschaft | Method of producing inorganic aerogels under subcritical conditions |
| CN1280550A (en) * | 1997-11-26 | 2001-01-17 | 卡伯特公司 | Method for producing silicon tetrachloride-based and organically modified aerogels |
| CN101137586A (en) * | 2005-03-09 | 2008-03-05 | 德古萨诺瓦拉科技股份公司 | Process for the production of monoliths by means of the sol-gel process |
-
2010
- 2010-06-25 CN CN2010102176876A patent/CN101863480B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6017505A (en) * | 1995-10-14 | 2000-01-25 | Basf Aktiengesellschaft | Method of producing inorganic aerogels under subcritical conditions |
| CN1280550A (en) * | 1997-11-26 | 2001-01-17 | 卡伯特公司 | Method for producing silicon tetrachloride-based and organically modified aerogels |
| CN101137586A (en) * | 2005-03-09 | 2008-03-05 | 德古萨诺瓦拉科技股份公司 | Process for the production of monoliths by means of the sol-gel process |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102897775A (en) * | 2011-07-25 | 2013-01-30 | 中国石油天然气股份有限公司 | Preparation method for high purity macroporous silica gel |
| CN102897775B (en) * | 2011-07-25 | 2014-08-06 | 中国石油天然气股份有限公司 | Preparation method for high purity macroporous silica gel |
| CN105051118A (en) * | 2013-02-05 | 2015-11-11 | 巴斯夫欧洲公司 | Method for producing porous or fine-particle solid inorganic materials |
| CN103387417A (en) * | 2013-07-30 | 2013-11-13 | 湖北三江航天江北机械工程有限公司 | Dampproof method for porous ceramic material containing silicon hydroxyl |
| CN103387417B (en) * | 2013-07-30 | 2015-02-18 | 湖北三江航天江北机械工程有限公司 | Dampproof method for porous ceramic material containing silicon hydroxyl |
| CN104760964A (en) * | 2015-04-29 | 2015-07-08 | 江西安德力高新科技有限公司 | Silicon dioxide aerogel preparation method |
| CN105031960A (en) * | 2015-08-19 | 2015-11-11 | 江西安德力高新科技有限公司 | Device and process for utilization of waste heat in aerogel production by adopting alcohol supercritical method |
| CN105236414A (en) * | 2015-09-21 | 2016-01-13 | 太仓市金锚新材料科技有限公司 | Silicon tetrachloride recycling method |
| CN107804852A (en) * | 2016-09-08 | 2018-03-16 | 新特能源股份有限公司 | Prepare the method and system of aerosil |
| CN107804852B (en) * | 2016-09-08 | 2019-12-06 | 新特能源股份有限公司 | Method and system for preparing silicon dioxide aerogel |
| CN106477589A (en) * | 2016-11-30 | 2017-03-08 | 四川微松新材料有限公司 | A kind of preparation method of the aerosil nothing discharging of waste liquid and system |
| CN106477589B (en) * | 2016-11-30 | 2019-04-26 | 四川微松新材料有限公司 | A kind of preparation method and system of the aerosil of no discharging of waste liquid |
| CN115010140A (en) * | 2022-07-20 | 2022-09-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of super-hydrophobic silica aerogel |
| CN115010140B (en) * | 2022-07-20 | 2024-01-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of super-hydrophobic silica aerogel |
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